Luminous multifunctional ZnO-Bi2O3-based voltage-sensitive ceramic as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of functional ceramic materials, and particularly relates to luminous multifunctional ZnO-Bi2O3-based voltage-sensitive ceramic as well as a preparation method and application thereof. The luminous multifunctional ZnO-Bi2O3-based voltage-sensitive ceramic provided by the invention has up-conversion luminescence performance, can detect red emitted light under the excitation of 980nm laser, has a high nonlinear coefficient, is adjustable between 34 and 40.3, has excellent comprehensive performance, and can be used for ensuring the nonlinear coefficient alphagt; when the voltage is 30, the voltage-sensitive voltage is as low as 424.2 V / mm, the leakage current IL is as low as 1.8 [mu] A / cm < 2 >, the energy consumption is low, the cost is low, and the method is green and environment-friendly.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional ceramic materials, and in particular relates to a luminous multifunctional ZnO-Bi2O3 based varistor ceramic and a preparation method and application thereof. Background Art

[0002] ZnO-Bi2O3-based varistor ceramics are polycrystalline ceramics made using traditional solid-phase synthesis methods, using ZnO as the primary raw material and small amounts of Bi2O3, Co2O3, MnO2, Cr2O3, Sb2O3, and SiO2 oxides. They exhibit excellent non-ohmic properties and high surge absorption capacity, and are widely used in electronics, subway and electrified railway locomotive power supply systems, and power distribution systems in the electric power industry.

[0003] In recent years, researchers have explored the effects of rare earth oxides (such as Ho2O3, Sc2O3, Dy2O3, Sm2O3, Lu2O3 or Er2O3) doping on the microstructure and electrical properties of ZnO-Bi2O3 based varistor ceramics. 2+ The replacement of ions by rare earths can increase the Schottky barrier height, thereby improving the nonlinear coefficient; on the other hand, the second phase distributed at the grain boundary or the Bi-rich phase containing rare earth ions can inhibit the growth of grains, thereby obtaining varistor ceramics with small grain size and high high voltage sensitive electric field.

[0004] However, as rare earth elements act as activators for upconversion photoluminescent materials, direct addition of rare earth oxides to ZnO-Bi2O3-based varistor ceramics, based on the conditions for achieving upconversion luminescence, fails to achieve upconversion luminescence performance. This is because during the sintering process, most of the rare earth ions are absorbed by Bi2O3, forming a Bi-rich phase that segregates at the grain boundaries, causing fluorescence quenching. Furthermore, due to the complex composition of ZnO-Bi2O3-based varistor ceramics, the luminescence of rare earth ions is easily absorbed by other dopant ions, such as Bi, Mn, Sb, Si, Co, Cr, or Ti. Therefore, no research has yet reported on ZnO-Bi2O3-based varistor ceramics with luminescence performance. Summary of the Invention

[0005] The purpose of the present invention is to provide a luminescent multifunctional ZnO-Bi2O3-based varistor ceramic and its preparation method and application. The luminescent multifunctional ZnO-Bi2O3-based varistor ceramic provided by the present invention has luminescent properties.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a luminescent multifunctional ZnO-Bi2O3-based varistor ceramic, which comprises the following raw materials, calculated by mole fraction: 1000 parts of ZE phosphor, 4.75-5.25 parts of manganese dioxide (MnO2), 1.9-2.1 parts of antimony trioxide (Sb2O3), 1.9-2.1 parts of silicon dioxide (SiO2) and 1.9-6.3 parts of bismuth trioxide (Bi2O3); the raw materials of the ZE phosphor include zinc oxide (ZnO) and erbium oxide (Er2O3).

[0008] Preferably, the molar ratio of ZnO to Er2O3 is 99.475-94.525:0.475-0.525.

[0009] Preferably, the preparation method of the ZE phosphor comprises the following steps: mixing ZnO and Er2O3 and performing a first sintering to obtain the ZE phosphor.

[0010] Preferably, the temperature of the first sintering is 1021-1129° C., and the holding time is 3.8-4.2 hours.

[0011] The present invention also provides a method for preparing the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic described in the above scheme, comprising the following steps:

[0012] After mixing ZE phosphor, MnO2, Sb2O3, SiO2 and Bi2O3, they are pressed into sheets, discharged and subjected to a second sintering in sequence. The temperature of the second sintering is 990-1010°C and the holding time is 2-5 hours to obtain the luminous multifunctional ZnO-Bi2O3-based varistor ceramic.

[0013] Preferably, the tableting process comprises the following steps: mixing the mixture and the binder, followed by screening, granulating and pressing.

[0014] Preferably, the pressing pressure is 80-120 MPa, and the holding time is 1-2 minutes.

[0015] Preferably, the temperature of the plastic discharge is 580-620° C., and the heat preservation time is 5-6 hours.

[0016] Preferably, the target particle size of the granulation is 250 to 300 microns.

[0017] The present invention also provides the use of the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic described in the above scheme or the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic obtained by the preparation method described in the above scheme in a photovoltaic integrated system.

[0018] The present invention provides a luminescent multifunctional ZnO-Bi2O3-based varistor. The present invention uses ZE phosphor as a fluorescence source to impart upconversion luminescence performance to the luminescent multifunctional ZnO-Bi2O3-based varistor, and uses Bi2O3 as a nonlinear inducer. The ZE phosphor and Bi2O3 inducer both enhance the nonlinearity and reduce the varistor voltage. The luminescent multifunctional ZnO-Bi2O3-based varistor provided by the present invention has upconversion luminescence performance, can detect red emission light under 980nm laser excitation, has a high nonlinear coefficient, and the nonlinear coefficient is adjustable between 34 and 40.3. It has excellent comprehensive performance. When the nonlinear coefficient α is guaranteed to be greater than 30, the varistor voltage is as low as 424.2V / mm, and the leakage current I L As low as 1.8μA / cm 2 , low energy consumption, low cost, and green and environmentally friendly.

[0019] The present invention also provides a method for preparing the luminescent, multifunctional ZnO-Bi2O3-based varistor ceramic described in the above-mentioned scheme. The preparation method provided by the present invention is simple in steps and can produce the luminescent, multifunctional ZnO-Bi2O3-based varistor ceramic by low-temperature sintering. This method is suitable for industrial-scale production and provides a reference for the production of optoelectronic integrated varistor devices.

[0020] The present invention also provides for the use of the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic described in the above scheme, or the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic obtained by the preparation method described in the above scheme, in an optoelectronic integrated system. The luminescent multifunctional ZnO-Bi2O3-based varistor ceramic provided by the present invention provides unlimited possibilities for the preparation of low-cost, highly nonlinear, and low-potential-gradient optoelectronic integrated varistor ceramics, and has great application prospects in optoelectronic integrated systems. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0022] Figure 1 The XRD diffraction patterns of the ZE-MSS-xB varistor ceramic prepared in Example 1 and the control group; wherein a is ZnO ceramic, Bi2O3 ceramic containing Bi-rich phase, BiSb2O7 ceramic and ZE-MSS-xB varistor ceramic (Mn9Zn6Sb2Si4O 28 ) full X-ray diffraction spectrum, b is the enlarged view near 36.4° in a;

[0023] Figure 2 This is a microscopic scanning electron microscope image of the ZE-MSS-xB varistor ceramic prepared in Example 2; wherein a is a component with x=0, b is a component with x=0.2, c is a component with x=0.4, and d is a component with x=0.6;

[0024] Figure 3 CV performance analysis diagram of the ZE-MSS-xB varistor ceramic prepared in Example 2; wherein, a is the CV curve fitting diagram of the ZE-MSS-xB varistor ceramic with x=0.2, 0.4 and 0.6 components, and b is the trend diagram of the nonlinear coefficient and barrier height with Bi2O3 doping amount;

[0025] Figure 4 The up-conversion luminescence spectra and CIE chromaticity diagram of the ZE-MSS-xB varistor and ZE phosphor prepared in Example 1; wherein a is the up-conversion luminescence spectrum of the ZE-MSS-xB varistor with x=0, 0.2, 0.4 and 0.6 components, and b is the CIE chromaticity diagram. DETAILED DESCRIPTION

[0026] The present invention provides a luminescent multifunctional ZnO-Bi2O3-based varistor ceramic, which comprises the following raw materials by molar fraction:

[0027] 1000 parts of ZE phosphor, 4.75-5.25 parts of MnO2, 1.9-2.1 parts of Sb2O3, 1.9-2.1 parts of SiO2 and 1.9-6.3 parts of Bi2O3; the raw materials of the ZE phosphor include ZnO and Er2O3.

[0028] Calculated by mole fraction, the raw materials of the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic provided by the present invention include 1000 parts of ZE phosphor; the raw materials of the ZE phosphor include ZnO and Er2O3; the molar ratio of ZnO to Er2O3 can be 99.475~94.525:0.475~0.525, specifically 99.5:0.5.

[0029] In the present invention, the preparation method of the ZE phosphor comprises the following steps: mixing ZnO and Er2O3 (referred to as the first mixing) and sintering them (referred to as the first sintering) to obtain the ZE phosphor.

[0030] In the present invention, the first mixing can be the first ball milling; the ball-to-material ratio of the first ball milling can be 8 to 10:1, the ball milling time can be 10 to 12 hours, the ball milling speed can be 240 to 300 rpm, and the ball milling solvent can be anhydrous ethanol or deionized water; the mass ratio of the solvent of the first ball milling to the dry material (ZE phosphor, MnO2, Sb2O3, SiO2 and Bi2O3) can be 4 to 5:1, specifically 4.5:1.

[0031] In the present invention, the equipment for the first ball milling can be a planetary ball mill, a sand mill or an industrial ceramic powder mixing device; in a specific embodiment of the present invention, the equipment for the first ball milling can be a QM-3SP2 planetary ball mill produced by Nanjing Nanda Instrument Co., Ltd., an RT001 horizontal sand mill produced by Shanghai Ruite Mechanical and Electrical Equipment Co., Ltd. or a ZSH mixer produced by Shanghai Kairi Machinery Manufacturing Co., Ltd.

[0032] In the present invention, the ball-milled product may be dried after the first ball milling; the drying may be oven drying; the oven drying temperature may be 100-120° C., specifically 110° C., until dry.

[0033] In the present invention, the temperature of the first sintering can be 1021-1129° C., specifically 1075° C., and the holding time can be 3.8-4.2 hours, specifically 4 hours; the atmosphere of the first sintering can be air; and the equipment for the first sintering can be a muffle furnace.

[0034] Based on the molar fraction of the ZE phosphor, the raw materials of the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic provided by the present invention include 4.75 to 5.25 parts of MnO2, specifically 4.9 parts, 5 parts or 5.1 parts.

[0035] Based on the molar fraction of the ZE phosphor, the raw materials of the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic provided by the present invention include 1.9 to 2.1 parts of Sb2O3, specifically 2 parts.

[0036] Based on the molar fraction of the ZE phosphor, the raw materials of the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic provided by the present invention include 1.9 to 2.1 parts of SiO2, specifically 2 parts.

[0037] Based on the molar fraction of the ZE phosphor, the raw materials of the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic provided by the present invention include 1.9 to 6.3 parts of Bi2O3, specifically 2 parts, 3 parts, 4 parts, 5 parts or 6 parts.

[0038] The present invention also provides a method for preparing the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic described in the above scheme, comprising the following steps:

[0039] After mixing ZE phosphor, MnO2, Sb2O3, SiO2 and Bi2O3, they are pressed into sheets, discharged and sintered in sequence. The sintering temperature is 990-1010°C and the holding time is 2-5 hours to obtain the luminous multifunctional ZnO-Bi2O3-based varistor ceramic.

[0040] The present invention mixes ZE phosphor, MnO2, Sb2O3, SiO2, and Bi2O3 (referred to as a second mixing process) to obtain a mixture. In the present invention, the second mixing process can be a second ball milling process. The ball-to-material ratio of the second ball milling process can be 8 to 10:1, the ball milling time can be 10 to 12 hours, the ball milling speed can be 240 to 300 rpm, and the ball milling solvent can be anhydrous ethanol or deionized water. The mass ratio of the solvent to the dry materials (ZE phosphor, MnO2, Sb2O3, SiO2, and Bi2O3) in the second ball milling process can be 4 to 5:1, specifically 4.5:1.

[0041] In the present invention, the equipment for the second ball milling can be a planetary ball mill, a sand mill or an industrial ceramic powder mixing device; in a specific embodiment of the present invention, the equipment for the second ball milling can be a QM-3SP2 planetary ball mill produced by Nanjing Nanda Instrument Co., Ltd., an RT001 horizontal sand mill produced by Shanghai Ruite Mechanical and Electrical Equipment Co., Ltd. or a ZSH mixer produced by Shanghai Kairi Machinery Manufacturing Co., Ltd.

[0042] In the present invention, the second ball milling may further include drying the ball milled product; the drying may be oven drying; the oven drying temperature may be 100-120° C., specifically 110° C., until dry.

[0043] After mixing, the present invention sequentially subjects the mixture to tableting, plasticizing, and sintering (referred to as the second sintering) to obtain the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic. In the present invention, the tableting may include the following steps: mixing the mixture with a binder, followed by screening, granulation, and pressing.

[0044] In the present invention, the binder may be polyol; the polyol may be polyvinyl alcohol (PVA); the mass ratio of the binder to the mixture is 5 to 8:100, specifically 6:100 or 7:100.

[0045] In the present invention, the aperture of the sieve can be 0.25 to 0.3 mm; the target particle size of the granulation can be 250 to 300 μm, specifically 280 μm.

[0046] In the present invention, the pressing pressure may be 80-120 MPa, specifically 100 MPa, and the holding time may be 1-2 minutes, specifically 1.5 minutes.

[0047] In the present invention, the temperature of the plastic discharge can be 580-620° C., specifically 600° C., and the holding time can be 5-6 hours, specifically 5.5 hours; the plastic discharge can be carried out in a muffle furnace.

[0048] In the present invention, the temperature of the second sintering can be 990-1010°C, specifically 1000°C, and the holding time can be 2-5 hours, specifically 3 hours or 4 hours; the atmosphere of the second sintering can be air; and the equipment for the second sintering can be a muffle furnace.

[0049] The present invention also provides the use of the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic described in the above scheme or the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic obtained by the preparation method described in the above scheme in a photovoltaic integrated system.

[0050] The luminescent multifunctional ZnO-Bi2O3-based varistor provided by the present invention provides unlimited possibilities for the preparation of low-cost, highly nonlinear, low potential gradient optoelectronic integrated varistor ceramics, and has great application prospects in optoelectronic integrated systems.

[0051] In order to further illustrate the present invention, the scheme of the present invention is described in detail below with reference to the accompanying drawings and embodiments, but they should not be understood as limiting the scope of protection of the present invention.

[0052] Example 1

[0053] ZE-MSS-xB varistor ceramics with x=0, 0.2, 0.4 or 0.6 were prepared by solid-phase synthesis method. The specific steps are as follows:

[0054] (1) Weigh ZnO and Er2O3 raw materials according to the chemical composition molar ratio of 99.5:0.5;

[0055] (2) Using deionized water as the solvent, the raw materials weighed in step (1) were placed in a ball mill and ball milled at a ball-to-material ratio of 9:1 and a mass ratio of solvent to dry material of 4.5:1. The ball milling was performed at 270 rpm for 11 hours.

[0056] (3) drying the milled slurry in an oven at 100°C;

[0057] (4) placing the powder obtained in step (3) into a muffle furnace and sintering at 1075° C. for 4 hours to obtain ZE phosphor;

[0058] (5) Weigh ZE phosphor, MnO2, Sb2O3 and SiO2 raw materials according to the chemical composition molar ratio of 100:0.5:0.2:0.2;

[0059] (6) adding Bi2O3 according to the molar ratio in the overall formulation, i.e., ZE-MSS-xB, x = 0, 0.2, 0.4, or 0.6;

[0060] (7) Using deionized water as solvent, the raw materials weighed in step (6) were placed in a ball mill with a ball-to-material ratio of 9:1 and a mass ratio of solvent to dry material of 4.5:1, and ball milling was performed at 270 rpm for 11 hours;

[0061] (8) After ball milling, the slurry is placed in an oven and dried at 100°C;

[0062] (9) The dried raw material is directly added to a polyvinyl alcohol (PVA) binder at a mass ratio of the binder to the mixture of 6:100, sieved with a 60-mesh (0.25 mm) sieve, and granulated. After pressing and molding, the mixture is heated at 600°C in a muffle furnace for 6 h to obtain a molded ceramic body;

[0063] (10) The molded ceramic body obtained in step (9) is placed in a muffle furnace and sintered at 1000° C. for 2 hours to obtain ZE-MSS-xB varistor ceramics.

[0064] Example 2

[0065] ZE-MSS-xB varistor ceramics with x=0, 0.2, 0.4 or 0.6 were prepared by solid-phase synthesis method. The specific steps are as follows:

[0066] (1) Weigh ZnO and Er2O3 raw materials according to the chemical composition molar ratio of 99.5:0.5;

[0067] (2) Using anhydrous ethanol as solvent, the raw materials weighed in step (1) were placed in a ball mill and ball milled at a ball-to-material ratio of 9:1 and a mass ratio of solvent to dry material of 4.5:1. The ball milling was performed at 270 rpm for 11 hours.

[0068] (3) drying the milled slurry in an oven at 100°C;

[0069] (4) placing the powder obtained in step (3) into a muffle furnace and sintering at 1075° C. for 4 hours to obtain ZE phosphor;

[0070] (5) Weigh ZE phosphor, MnO2, Sb2O3 and SiO2 raw materials according to the chemical composition molar ratio of 100:0.5:0.2:0.2;

[0071] (6) adding Bi2O3 according to the molar ratio in the overall formulation, i.e., ZE-MSS-xB, x = 0, 0.2, 0.4, or 0.6;

[0072] (7) Using anhydrous ethanol as solvent, the raw materials weighed in step (6) were placed in a ball mill with a ball-to-material ratio of 9:1 and a mass ratio of solvent to dry material of 4.5:1, and ball milling was performed at 270 rpm for 11 hours;

[0073] (8) After ball milling, the slurry is placed in an oven and dried at 100°C;

[0074] (9) The dried raw material is directly added to a polyvinyl alcohol (PVA) binder at a mass ratio of the binder to the mixture of 7:100, sieved with a 60-mesh (0.25 mm) sieve, granulated, pressed and molded, and then heated in a muffle furnace at 600° C. for 6 h to obtain a molded ceramic body;

[0075] (10) The molded ceramic body obtained in step (9) is placed in a muffle furnace and sintered at 1000° C. for 2 hours to obtain ZE-MSS-xB varistor ceramics.

[0076] Test Example 1

[0077] The ZE-MSS-xB piezoresistive ceramic prepared in Example 1 was ultrasonically cleaned and then subjected to XRD analysis. The results are as follows: Figure 1 shown.

[0078] according to Figure 1 It can be seen that the main crystalline phase of ZE-MSS-xB varistor ceramics is ZnO hexagonal wurtzite, and the secondary crystalline phases are a small amount of Bi2O3 phase and bismuth-rich phase. With the doping of Bi2O3, BiSb2O7 phase appears in the composition. With the increase of doping amount, a large amount of Bi-rich phase (including Bi 7.65 Zn 0.35 O 11.83 、Bi 7.89 Sb 0.11 O 12+x 、Bi 7.72 Mn 0.28 O 12.14 and Bi 54 SiO 83 four phases).

[0079] Test Example 2

[0080] The ZE-MSS-xB piezoresistive ceramic prepared in Example 2 was ultrasonically cleaned and then analyzed by scanning electron microscopy. The results are as follows: Figure 2 shown.

[0081] according to Figure 2It can be seen that the varistor ceramics tend to be denser after the doping amount increases. With the increase of Bi2O3 doping amount, the grain size of ZnO gradually increases and then stabilizes, which makes the varistor voltage decrease first and then increase. When x≥0.4, the varistor ceramics begin to have no pores, the average grain size d increases from 5.14μm to 5.56μm (c~d), and the density ρ increases from 5.02g / cm 3 Increased to 5.42g / cm 3 .

[0082] Test Example 3

[0083] The upper and lower surfaces of the ZE-MSS-xB varistor ceramic prepared in Example 2 were coated with silver paste and sintered at 500°C for 20 minutes to form silver electrodes. The CV performance test and analysis were performed. The results are as follows: Figure 3 As shown in Table 1, the average grain size d, density ρ, nonlinear coefficient α, and varistor voltage E of ZE-MSS-xB varistor ceramics are statistically analyzed. 1mA and leakage current J L And performance parameters such as bias capacitance CV.

[0084] Table 1 Electrical performance parameters of ZE-MSS-xB varistor ceramics prepared in Example 1

[0085]

[0086]

[0087] according to Figure 3 It can be seen that after the measured CV raw data are normalized, the barrier heights under different compositions are obtained by linear fitting calculation. It is found that the barrier height shows the same change trend as the nonlinear coefficient with the increase of Bi2O3 doping amount, and its value reaches the maximum when x=0.4wt%, which are 1.18eV and 40.3 respectively, indicating that the varistor performance of ZE-MSS-xB varistor ceramics is optimal under this composition.

[0088] According to Table 1, when x = 0.4, the nonlinear coefficient is the highest at 40.3, which corresponds to the maximum barrier height Φ in Table 1. b =1.18; E of ZE-MSS-xB varistor ceramic 1mA It first increases from 161.8 V / mm at x=0wt% to 991.7 V / mm at x=0.2wt%, and then gradually decreases to 424.2 V / mm.

[0089] Test Example 4

[0090] The ZE-MSS-xB piezoresistive ceramic prepared in Example 1 was ultrasonically cleaned and the upconversion luminescence performance was analyzed. The results are as follows: Figure 4 shown.

[0091] according to Figure 4 As can be seen from a in Figure 1, with the introduction of a small amount of Bi2O3 (x = 0.2), an obvious green emission peak appears in the spectrum under 980nm laser irradiation. 2 H 11 / 2 / 4 S 3 / 2 → 4 I 15 / 2 (peak at ~525 and ~557nm) transition; with the gradual increase of Bi2O3 content (x≥0.4), the green luminescence peak gradually weakened; according to Figure 4 As can be seen in b, as the Bi2O3 content increases from 0 to 0.6 mol%, the color of the light changes from the original red light to Turns yellow-green Then it gradually turned red The above results show that the introduction of Bi2O3 not only forms Bi-rich phase at the grain boundary, but also partially 3+ The ions will enter the ZnO lattice, which will have a significant impact on the luminescence properties of ZE-MSS-xB varistor ceramics.

[0092] As can be seen from the above examples, the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic provided by the present invention has luminescent properties, can detect red emitted light under 980nm laser excitation, has a high nonlinear coefficient, and the nonlinear coefficient is adjustable between 34 and 40.3. It has excellent comprehensive performance. When the nonlinear coefficient α is guaranteed to be greater than 30, the varistor voltage is as low as 424.2V / mm, and the leakage current I L As low as 1.8μA / cm 2 .

[0093] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A luminescent multifunctional ZnO-Bi2O3 based varistor ceramic, characterized in that: The following raw materials are included in molar proportions: 1000 parts of ZE phosphor, 4.75-5.25 parts of manganese dioxide, 1.9-2.1 parts of antimony trioxide, 1.9-2.1 parts of silicon dioxide and 1.9-6.3 parts of bismuth trioxide; The raw materials of the ZE phosphor include zinc oxide and erbium oxide.

2. The luminescent multifunctional ZnO-Bi2O3-based varistor ceramic according to claim 1, characterized in that: The molar ratio of ZnO to Er2O3 is 99.475-94.525:0.475-0.

525.

3. The luminescent multifunctional ZnO-Bi2O3-based varistor according to claim 1 or 2, characterized in that: The preparation method of the ZE phosphor comprises the following steps: ZnO and Er2O3 are mixed and subjected to a first sintering to obtain the ZE phosphor.

4. The luminescent multifunctional ZnO-Bi2O3-based varistor ceramic according to claim 3, characterized in that: The temperature of the first sintering is 1021-1129° C., and the holding time is 3.8-4.2 hours.

5. The method for preparing the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic according to any one of claims 1 to 4, characterized in that: The following steps are involved: After mixing ZE phosphor, MnO2, Sb2O3, SiO2 and Bi2O3, they are pressed into sheets, discharged and subjected to a second sintering in sequence. The temperature of the second sintering is 990-1010°C and the holding time is 2-5 hours to obtain the luminous multifunctional ZnO-Bi2O3-based varistor ceramic.

6. The preparation method according to claim 5, characterized in that The tableting process comprises the following steps: mixing the mixture and the binder, followed by screening, granulating and pressing.

7. The preparation method according to claim 6, characterized in that The pressing pressure is 80-120 MPa, and the holding time is 1-2 minutes.

8. The preparation method according to claim 5 or 6, characterized in that: The temperature of the plastic discharge is 580-620° C., and the heat preservation time is 5-6 hours.

9. The preparation method according to claim 6, characterized in that The target particle size of the granulation is 250 to 300 microns.

10. Use of the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic according to any one of claims 1 to 4 or the luminescent multifunctional ZnO-Bi2O3-based varistor ceramic obtained by the preparation method according to any one of claims 5 to 9 in optoelectronic integrated systems.

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