CN115974544A - In and Ta co-doped zinc oxide composite functional ceramic, preparation method and application thereof - Google Patents
In and Ta co-doped zinc oxide composite functional ceramic, preparation method and application thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000000919 ceramic Substances 0.000 title claims abstract description 91
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 23
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- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 16
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Abstract
The invention relates to the technical field of ceramic preparation, in particular to In and Ta co-doped zinc oxide composite functional ceramic, a preparation method and application thereof, and ZnO and Bi are prepared by 2 O 3 、Sb 2 O 3 、Ni 2 O 3 、Co 3 O 4 、MnO 2 、Al(NO 3 ) 3 、TiO 2 、In 2 O 3 、Ta 2 O 5 Mixing the powder in deionized water with ZrO 2 Ball milling the medium at the speed of 200r/min for 12 hours, and drying at 80 ℃ for 24 hours; mixing the obtained dry powder with a binder, and pressing into a green body; heating the obtained green body at a heating rate of 2 ℃/minHeating to 600 deg.C for 2h to remove binder; the obtained green body without the binder is sintered to 1200-1300 ℃ at the heating rate of 5 ℃/min, is kept warm for 90min, and is cooled to room temperature to obtain the zinc oxide low-pressure voltage-sensitive ceramic.
Description
Technical Field
The invention relates to the technical field of ceramic preparation, in particular to In and Ta co-doped zinc oxide composite functional ceramic, and a preparation method and application thereof.
Background
ZnO voltage sensitive ceramics are commonly used in electronic and industrial equipment to absorb transient surges and protect power systems. The nonlinear characteristic is the most important characteristic of the varistor and is represented by the formula I = KV α, where I is a current, K is a constant, V is a voltage, and α is a nonlinear coefficient. The higher the non-linear coefficient alpha is, the better the pressure sensitive performance is, the non-linear current-voltage characteristic of the ZnO pressure sensitive ceramic is related to the grain boundary barrier and the resistance, and the excellent non-linear characteristic can be achieved by adding some special additives, such as Bi 2 O 3 And V 2 O 5 And the like. ZnO pressure sensitive ceramics can be mainly classified into three categories: znO-Bi 2 O 3 Is of ZnO-V 2 O 5 Series and ZnO-Pr 6 O 11 Is described. Wherein, V 2 O 5 The pressure-sensitive porcelain can be sintered at the sintering temperature of less than 900 ℃ and simultaneously can make the sample compact, but V in the raw material 2 O 5 The system is toxic, and a large amount of air holes can be formed in the sintering process of the system, so that the performance of the pressure sensitive ceramic is influenced. ZnO-Pr 6 O 11 Is added with rare earth oxide Pr 6 O 11 But at a higher cost. ZnO-Bi 2 O 3 In the series of Bi 2 O 3 The generated Bi-rich liquid phase can enable the additive to be uniformly distributed. Some other additives, e.g. MnO 2 、Co 2 O 3 、Cr 2 O 3 、Sb 2 O 3 The isosegregation is in the crystal boundary, so that the nonlinear coefficient is improved. The addition of the crystal promoter can obviously enlarge crystal grains and reduce potential gradient by accelerating the solid-phase mass transfer process, thereby meeting the requirements of low-voltage pressure-sensitive ceramics. At present, much ZnO pressure sensitive ceramics for high pressure are researched, and few reports are reported about ZnO pressure sensitive ceramics suitable for low pressure occasions. In recent years, electronic equipment is miniaturized, the withstand voltage value of electronic components in a circuit is reduced, the circuit is easy to damage due to overvoltage operation, and low-voltage-sensitive ceramics can absorb internal and external surges to protect a power electronic circuit. However, in order to obtain a better nonlinear coefficient, the zinc oxide varistor is usually prepared, and the threshold voltage is also rapidly increased, so that the preparation of the low-voltage varistor ceramic is not facilitated.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
The invention aims to solve the problems that the existing preparation method for preparing low-pressure voltage-sensitive ceramic is difficult and the obtained low-pressure voltage-sensitive ceramic has poor performance, and provides In and Ta co-doped zinc oxide composite functional ceramic, and a preparation method and application thereof.
In order to realize the purpose, the invention discloses a preparation method of In and Ta co-doped zinc oxide composite functional ceramic, which comprises the following steps:
s1: znO and Bi are mixed 2 O 3 、Sb 2 O 3 、Ni 2 O 3 、Co 3 O 4 、MnO 2 、Al(NO 3 ) 3 、TiO 2 、In 2 O 3 、Ta 2 O 5 Mixing the powder in deionized water with ZrO 2 Ball-milling the medium at the speed of 200r/min for 12 hours, and drying at the temperature of 80 ℃ for 24 hours;
s2: mixing the dry powder obtained in the step S1 with an adhesive, and pressing into a green body;
s3: heating the green body obtained in the step S2 to 600 ℃ at the heating rate of 2 ℃/min for 2h, and removing the binder;
s4: and (4) sintering the green body without the binder obtained in the step (S3) to 1200-1300 ℃ at the heating rate of 5 ℃/min, preserving the heat for 90min, and then cooling to room temperature.
ZnO and Bi in the step S1 2 O 3 、Sb 2 O 3 、Ni 2 O 3 、Co 3 O 4 、MnO 2 、Al(NO 3 ) 3 、TiO 2 、In 2 O 3 、Ta 2 O 5 The powder comprises 90-95 parts of ZnO by mole; bi 2 O 3 0.5-2 parts; sb 2 O 3 0.3-1 part; ni 2 O 3 0.2 to 1.5 portions; co 3 O 4 0.3 to 1.5 portions; mnO 2 0.3 to 1.5 portions; al (NO) 3 ) 3 0 to 0.2 portion; tiO 2 2 0-2 parts of; in 2 O 3 0.001 to 0.1 portion; ta 2 O 5 0.001 to 0.2 portion.
The binder in step S2 is 5wt.% polyvinyl alcohol PVA.
The diameter of the green body in the step S2 is 13mm.
And in the step S4, the temperature is reduced to 900 ℃ at the speed of 1 ℃/min, then is reduced to 600 ℃ at the speed of 3 ℃/min, and finally is reduced to the room temperature at the speed of 1 ℃/min.
The invention also discloses In prepared by the preparation method 2 O 3 And Ta 2 O 5 Codoped zinc oxide composite functional ceramic and application of the zinc oxide composite functional ceramic in absorbing overvoltage and storing energy in electronic components.
In this application 2 O 3 And Ta 2 O 5 The co-doping generates defect reaction, increases the nonlinear coefficient and simultaneously reduces the threshold voltage, thereby achieving the purpose of preparing the high-performance low-pressure zinc oxide composite functional ceramic.
Compared with the prior art, the invention has the beneficial effects that: the present invention utilizes In 2 O 3 And Ta 2 O 5 Codoping to prepare ZnO-Bi 2 O 3 Based on the zinc oxide composite functional ceramic,all samples prepared were homogeneous in microstructure. Samples of all compositions were pressure sensitive, with Ta 2 O 5 When the amount of (A) is 0.15mol%, the performance is best, the voltage gradient is 184V/mm, the nonlinear coefficient is 32.3, and the leakage current is 0.04. Mu.A. As shown by research, in 2 O 3 And Ta 2 O 5 After co-doping, a defect reaction occurs, so that the nonlinear coefficient increases and the threshold voltage slightly decreases. Moreover, the research of the invention also shows that the prepared ZnO voltage-sensitive ceramic has certain energy storage density and energy storage efficiency, the energy storage can reach 28.11 percent, and the ZnO voltage-sensitive ceramic is a potential energy storage material.
Drawings
FIG. 1 shows examples 5, 6, 7, 8, 9 and 10In 2 O 3 And Ta 2 O 5 XRD of the co-doped ZnO composite functional ceramic;
FIG. 2 shows example 5In 2 O 3 And Ta 2 O 5 SEM of co-doped ZnO composite functional ceramic;
FIG. 3 shows example 6In 2 O 3 And Ta 2 O 5 SEM of co-doped ZnO composite functional ceramic;
FIG. 4 shows example 7In 2 O 3 And Ta 2 O 5 SEM of co-doped ZnO composite functional ceramic;
FIG. 5 shows example 8In 2 O 3 And Ta 2 O 5 SEM of codoped ZnO composite functional ceramic;
FIG. 6 shows example 9In 2 O 3 And Ta 2 O 5 SEM of co-doped ZnO composite functional ceramic;
FIG. 7 shows example 10In 2 O 3 And Ta 2 O 5 SEM of co-doped ZnO composite functional ceramic;
FIG. 8 shows all examples In 2 O 3 And Ta 2 O 5 Relative density of the co-doped ZnO composite functional ceramic;
FIG. 9 shows examples 5, 6, 7, 8, 9 and 10In 2 O 3 And Ta 2 O 5 E-J curve of the co-doped ZnO composite functional ceramic;
FIG. 10 shows examples 5, 6, 7, 8, 9 and 10In 2 O 3 And Ta 2 O 5 The impedance spectrum of the co-doped ZnO composite functional ceramic;
FIG. 11 shows examples 5, 6, 7, 8, 9 and 10In 2 O 3 And Ta 2 O 5 Co-doping the dielectric of the ZnO composite functional ceramic;
FIG. 12 shows examples 5, 6, 7, 8, 9 and 10In 2 O 3 And Ta 2 O 5 And co-doping the ZnO composite functional ceramic to form an electric hysteresis loop.
Detailed Description
The above and further features and advantages of the present invention will be described in more detail below with reference to the accompanying drawings, in which the materials are commercially available.
TABLE 1 formulation of ceramic powders for each of the examples and comparative examples
| Raw materials | ZnO | Bi 2 O 3 | Sb 2 O 3 | Ni 2 O 3 | Co 3 O 4 | MnO 2 | Al(NO 3 ) 3 | TiO 2 | In 2 O 3 | Ta 2 O 5 |
| Example 1 | 90 | 2 | 1 | 1.5 | 1.5 | 1.5 | 0.2 | 2 | 0.1 | 0.2 |
| Example 2 | 95 | 0.5 | 0.3 | 0.2 | 0.9 | 1 | 0.1 | 2 | 0.001 | 0.001 |
| Example 3 | 97.17 | 0.7 | 0.5 | 0.43 | 0.3 | 0.3 | 0.1 | 0.5 | 0 | 0 |
| Example 4 | 96.806 | 0.7 | 0.5 | 0.43 | 0.49 | 0.49 | 0.01 | 0.5 | 0 | 0.05 |
| Example 5 | 96.868 | 0.7 | 0.5 | 0.43 | 0.49 | 0.49 | 0.01 | 0.5 | 0.012 | 0 |
| Example 6 | 96.818 | 0.7 | 0.5 | 0.43 | 0.49 | 0.49 | 0.01 | 0.5 | 0.012 | 0.05 |
| Example 7 | 96.788 | 0.7 | 0.5 | 0.43 | 0.49 | 0.49 | 0.01 | 0.5 | 0.012 | 0.08 |
| Example 8 | 96.748 | 0.7 | 0.5 | 0.43 | 0.49 | 0.49 | 0.01 | 0.5 | 0.012 | 0.12 |
| Example 9 | 96.718 | 0.7 | 0.5 | 0.43 | 0.49 | 0.49 | 0.01 | 0.5 | 0.012 | 0.15 |
| Example 10 | 96.668 | 0.7 | 0.5 | 0.43 | 0.49 | 0.49 | 0.01 | 0.5 | 0.012 | 0.20 |
Example 1
A preparation method of In and Ta co-doped zinc oxide composite functional ceramic comprises the following steps:
the method comprises the following steps: according to the formulation of the ceramic powder of this example shown in Table 1, the ceramic powder material comprises 90 parts of ZnO and 2 parts of Bi by mole ratio 2 O 3 1 part of Sb 2 O 3 1.5 parts of Ni 2 O 3 1.5 parts of Co 3 O 4 1.5 parts of MnO 2 0.2 part of Al (NO) 3 ) 3 2 parts of TiO 2 0.1 part of In 2 O 3 0.2 part of Ta 2 O 5 ；
Step two: ball-milling at a speed of 200r/min for 12 hours, drying in an oven at 80 ℃ for 24 hours, mixing the powder with 5wt.% of polyvinyl alcohol (PVA), compressing into a green body with a diameter of 13mm, heating to 600 ℃ at a heating rate of 2 ℃/min, heating for 2 hours, and removing the binder;
step three: sintering to 1200 ℃ at a heating rate of 5 ℃/min, preserving heat for 90 minutes, cooling to 900 ℃ at 1 ℃/min, cooling to 600 ℃ at 3 ℃/min, and finally cooling to room temperature at 1 ℃/min; the zinc oxide composite functional ceramic of the present example was obtained.
Example 2
A preparation method of In and Ta co-doped zinc oxide composite functional ceramic comprises the following steps:
the method comprises the following steps: according to the formulation of the ceramic powder of this example shown in Table 1, the ceramic powder material comprises 95 parts ZnO and 0.5 part Bi by mol 2 O 3 0.3 part of Sb 2 O 3 0.2 part of Ni 2 O 3 0.9 part of Co 3 O 4 1 part of MnO 2 0.1 part of Al (NO) 3 ) 3 2 parts of TiO 2 0.001 part of In 2 O 3 0.001 part of Ta 2 O 5 ；
Step two: ball-milling at 200r/min for 12 hr, drying in 80 deg.C oven for 24 hr, mixing the powder with 5wt.% polyvinyl alcohol (PVA), compressing into green body with diameter of 13mm, heating to 600 deg.C at a heating rate of 2 deg.C/min for 2 hr, and removing binder;
step three: sintering at a heating rate of 5 ℃/min to 1250 ℃, preserving heat for 90 minutes, cooling to 900 ℃ at a speed of 1 ℃/min, cooling to 600 ℃ at a speed of 3 ℃/min, and finally cooling to room temperature at a speed of 1 ℃/min; the zinc oxide composite functional ceramic of the present example was obtained.
Example 3
A preparation method of In and Ta co-doped zinc oxide composite functional ceramic comprises the following steps:
the method comprises the following steps: according to the formulation of the ceramic powder of this example shown in Table 1, the ceramic powder material was composed of, by mole, 97.17 parts of ZnO and 0.7 part of Bi 2 O 3 0.5 part of Sb 2 O 3 0.43 part of Ni 2 O 3 0.3 part of Co 3 O 4 0.3 part of MnO 2 0.1 part of Al (NO) 3 ) 3 0.5 part of TiO 2 ；
Step two: ball-milling at 200r/min for 12 hr, drying in 80 deg.C oven for 24 hr, mixing the powder with 5wt.% polyvinyl alcohol (PVA), compressing into green body with diameter of 13mm, heating to 600 deg.C at a heating rate of 2 deg.C/min for 2 hr, and removing binder;
step three: sintering to 1300 ℃ at the heating rate of 5 ℃/min, preserving heat for 90 minutes, cooling to 900 ℃ at 1 ℃/min, cooling to 600 ℃ at 3 ℃/min, and finally cooling to room temperature at 1 ℃/min; the zinc oxide composite functional ceramic of the present example was obtained.
Example 4
A preparation method of In and Ta co-doped zinc oxide composite functional ceramic comprises the following steps:
the method comprises the following steps: according to the formulation of the ceramic powder of this example shown in Table 1, the ceramic powder material comprises 96.876 parts of ZnO and 0.7 part of Bi by mole ratio 2 O 3 0.5 part of Sb 2 O 3 0.43 part of Ni 2 O 3 0.49 parts of Co 3 O 4 0.49 parts of MnO 2 0.01 part of Al (NO) 3 ) 3 0.5 part of TiO 2 0.05 part of In 2 O 3 ；
Step two: ball-milling at a speed of 200r/min for 12 hours, drying in an oven at 80 ℃ for 24 hours, mixing the powder with 5wt.% of polyvinyl alcohol (PVA), compressing into a green body with a diameter of 13mm, heating to 600 ℃ at a heating rate of 2 ℃/min, heating for 2 hours, and removing the binder;
step three: sintering to 1250 ℃ at the heating rate of 5 ℃/min, preserving heat for 90 minutes, cooling to 900 ℃ at 1 ℃/min, cooling to 600 ℃ at 3 ℃/min, and finally cooling to room temperature at 1 ℃/min; the zinc oxide composite functional ceramic of the present example was obtained.
Example 5
A preparation method of In and Ta co-doped zinc oxide composite functional ceramic comprises the following steps:
the method comprises the following steps: according to the formulation of the ceramic powder of this example shown in Table 1, the ceramic powder material comprises, in terms of mole ratio, 96.88 parts of ZnO and 0.7 part of Bi 2 O 3 0.5 parts of Sb 2 O 3 0.43 parts of Ni 2 O 3 0.49 parts of Co 3 O 4 0.49 parts of MnO 2 0.01 part of Al (NO) 3 ) 3 0.5 part of TiO 2 0.012 parts of Ta 2 O 5 ；
Step two: ball-milling at 200r/min for 12 hr, drying in 80 deg.C oven for 24 hr, mixing the powder with 5wt.% polyvinyl alcohol (PVA), compressing into green body with diameter of 13mm, heating to 600 deg.C at a heating rate of 2 deg.C/min for 2 hr, and removing binder;
step three: sintering to 1250 ℃ at the heating rate of 5 ℃/min, preserving heat for 90 minutes, cooling to 900 ℃ at 1 ℃/min, cooling to 600 ℃ at 3 ℃/min, and finally cooling to room temperature at 1 ℃/min; the zinc oxide composite functional ceramic of the present example was obtained.
Example 6
A preparation method of In and Ta co-doped zinc oxide composite functional ceramic comprises the following steps:
the method comprises the following steps: according to the formulation of the ceramic powder of this example shown in Table 1, the ceramic powder material comprises 96.876 parts of ZnO and 0.7 part of Bi by mole ratio 2 O 3 0.5 parts of Sb 2 O 3 0.43 parts of Ni 2 O 3 0.49 parts of Co 3 O 4 0.49 parts of MnO 2 0.01 part of Al (NO) 3 ) 3 0.5 part of TiO 2 0.012 parts of In 2 O 3 0.05 part of Ta 2 O 5 ；
Step two: ball-milling at 200r/min for 12 hr, drying in 80 deg.C oven for 24 hr, mixing the powder with 5wt.% polyvinyl alcohol (PVA), compressing into green body with diameter of 13mm, heating to 600 deg.C at a heating rate of 2 deg.C/min for 2 hr, and removing binder;
step three: sintering at a heating rate of 5 ℃/min to 1250 ℃, preserving heat for 90 minutes, cooling to 900 ℃ at a speed of 1 ℃/min, cooling to 600 ℃ at a speed of 3 ℃/min, and finally cooling to room temperature at a speed of 1 ℃/min; the zinc oxide composite functional ceramic of the present example was obtained.
Example 7
A preparation method of In and Ta co-doped zinc oxide composite functional ceramic comprises the following steps:
the method comprises the following steps: the basic results are shown in Table 1The formula of the ceramic powder comprises 96.872 parts of ZnO and 0.7 part of Bi according to molar ratio 2 O 3 0.5 parts of Sb 2 O 3 0.43 parts of Ni 2 O 3 0.49 parts of Co 3 O 4 0.49 parts of MnO 2 0.01 part of Al (NO) 3 ) 3 0.5 part of TiO 2 0.012 parts of In 2 O 3 0.08 part of Ta 2 O 5 ；
Step two: ball-milling at 200r/min for 12 hr, drying in 80 deg.C oven for 24 hr, mixing the powder with 5wt.% polyvinyl alcohol (PVA), compressing into green body with diameter of 13mm, heating to 600 deg.C at a heating rate of 2 deg.C/min for 2 hr, and removing binder;
step three: sintering to 1250 ℃ at the heating rate of 5 ℃/min, preserving heat for 90 minutes, cooling to 900 ℃ at 1 ℃/min, cooling to 600 ℃ at 3 ℃/min, and finally cooling to room temperature at 1 ℃/min; the zinc oxide composite functional ceramic of the present example was obtained.
Example 8
A preparation method of In and Ta co-doped zinc oxide composite functional ceramic comprises the following steps:
the method comprises the following steps: according to the formulation of the ceramic powder of this example shown in Table 1, the ceramic powder material was composed of 96.868 parts by mole of ZnO and 0.7 part by mole of Bi 2 O 3 0.5 parts of Sb 2 O 3 0.43 parts of Ni 2 O 3 0.49 parts of Co 3 O 4 0.49 parts of MnO 2 0.01 part of Al (NO) 3 ) 3 0.5 part of TiO 2 0.012 parts of In 2 O 3 0.12 part of Ta 2 O 5 ；
Step two: ball-milling at a speed of 200r/min for 12 hours, drying in an oven at 80 ℃ for 24 hours, mixing the powder with 5wt.% of polyvinyl alcohol (PVA), compressing into a green body with a diameter of 13mm, heating to 600 ℃ at a heating rate of 2 ℃/min, heating for 2 hours, and removing the binder;
step three: sintering to 1250 ℃ at the heating rate of 5 ℃/min, preserving heat for 90 minutes, cooling to 900 ℃ at 1 ℃/min, cooling to 600 ℃ at 3 ℃/min, and finally cooling to room temperature at 1 ℃/min; the zinc oxide composite functional ceramic of the present example was obtained.
Example 9
A preparation method of In and Ta co-doped zinc oxide composite functional ceramic comprises the following steps:
the method comprises the following steps: according to the formulation of the ceramic powder of this example shown in Table 1, the ceramic powder material was composed of 96.864 parts by mole of ZnO and 0.7 part by mole of Bi 2 O 3 0.5 parts of Sb 2 O 3 0.43 parts of Ni 2 O 3 0.49 parts of Co 3 O 4 0.49 parts of MnO 2 0.01 part of Al (NO) 3 ) 3 0.5 part of TiO 2 0.012 parts of In 2 O 3 0.15 part of Ta 2 O 5 ；
Step two: ball-milling at 200r/min for 12 hr, drying in 80 deg.C oven for 24 hr, mixing the powder with 5wt.% polyvinyl alcohol (PVA), compressing into green body with diameter of 13mm, heating to 600 deg.C at a heating rate of 2 deg.C/min for 2 hr, and removing binder;
step three: sintering to 1250 ℃ at the heating rate of 5 ℃/min, preserving heat for 90 minutes, cooling to 900 ℃ at 1 ℃/min, cooling to 600 ℃ at 3 ℃/min, and finally cooling to room temperature at 1 ℃/min; the zinc oxide composite functional ceramic of the present example was obtained.
Example 10
A preparation method of In and Ta co-doped zinc oxide composite functional ceramic comprises the following steps:
the method comprises the following steps: according to the formulation of the ceramic powder of this example shown in Table 1, the ceramic powder material was composed of 96.864 parts by mole of ZnO and 0.7 part by mole of Bi 2 O 3 0.5 parts of Sb 2 O 3 0.43 part of Ni 2 O 3 0.49 parts of Co 3 O 4 0.49 parts of MnO 2 0.01 part of Al (NO) 3 ) 3 0.5 part of TiO 2 0.012 parts of In 2 O 3 0.20 part of Ta 2 O 5 ；
Step two: ball-milling at 200r/min for 12 hr, drying in 80 deg.C oven for 24 hr, mixing the powder with 5wt.% polyvinyl alcohol (PVA), compressing into green body with diameter of 13mm, heating to 600 deg.C at a heating rate of 2 deg.C/min for 2 hr, and removing binder;
step three: sintering to 1250 ℃ at the heating rate of 5 ℃/min, preserving heat for 90 minutes, cooling to 900 ℃ at 1 ℃/min, cooling to 600 ℃ at 3 ℃/min, and finally cooling to room temperature at 1 ℃/min; the zinc oxide composite functional ceramic of the present example was obtained.
Performance testing
Aiming at the zinc oxide composite functional ceramic obtained in the embodiment, the following performance tests are respectively carried out:
(1) The electrode and the pressure-sensitive performance detection comprise a nonlinear coefficient alpha and a voltage gradient V T Leakage current I L ；
The examination results are shown in table 2:
TABLE 2 pressure sensitive Property test data for each example
| Non-linear coefficient alpha | Potential gradient V T (V/mm) | Leakage current I L (μA) | |
| Example 1 | 20.3 | 227 | 1.57 |
| Example 2 | 21.2 | 224 | 1.32 |
| Example 3 | 20.7 | 304 | 2.86 |
| Example 4 | 20.4 | 208 | 0.56 |
| Example 5 | 25.1 | 191 | 0.42 |
| Example 6 | 15.3 | 207 | 0.8 |
| Example 7 | 22.8 | 196 | 0.7 |
| Example 8 | 28.2 | 191 | 0.32 |
| Example 9 | 32.3 | 184 | 0.04 |
| Example 10 | 27.0 | 198 | 0.2 |
As is clear from Table 2, examples 4 to 10 have smaller potential gradients and higher nonlinear coefficients than examples 1 to 3, and are more advantageous for achieving low voltage. In examples 6 to 10, the threshold voltage was first lowered and then raised as the doping content was increased, which is mainly due to doped Ta 2 O 5 The free electron concentration is increased by introducing electrons, the resistivity of zinc oxide crystal grains is reduced, and the threshold voltage is reduced. In 3 + As acceptors, ta can be trapped 5+ The introduced electrons are doped to suppress leakage current.
(2) XRD analysis;
the XRD patterns of example 5, example 6, example 7, example 8, example 9 and example 10 are shown in fig. 1. The experimental result shows that the main crystal phase is ZnO phase, and a small amount of Bi exists 2 O 3 Phase and Bi 4 Ti 3 O 12 Explanation of codoping Ta 2 O 5 And In 2 O 3 Has no significant influence on the main crystal phase of the sample.
(3) SEM analysis;
SEM images of example 5, example 6, example 7, example 8, example 9 and example 10 are shown in FIGS. 2-7. The microstructure of all samples was relatively uniform and dense. The variation rule of the crystal grain size is consistent with that of the threshold voltage, and is respectively 10.95 μm,12.03 μm,11.68 μm,13.24 μm,14.69 μm,13.98 μm,15.02 μm,15.09 μm,15.49 μm and 14.54 μm.
(4) And (3) macroscopic performance detection: including density detection.
FIG. 8 is a graph showing the calculation of Ta at a sintering temperature of 1250 ℃ by Archimedes' method measurement in all examples 2 O 5 And In 2 O 3 Relative density of co-doped ZnO voltage-sensitive ceramicsAnd (4) degree. The relative density of the green compact was about 60%, the relative density after sintering was 96.1%,96.3%,96.2%,96.4%,96.6%,97.1%,96.5%,96.1%,97.0%,96.1%, and it can be seen that the density of all samples was higher than 96%. With example 6 having the highest relative density. Overall, doping with Ta 2 O 5 And In 2 O 3 The co-doping has little influence on the density of the sample, and the obtained density is higher.
(5) E-J Curve analysis
FIG. 9 is an E-J curve of examples 5, 6, 7, 8, 9 and 10. The inflection point appearing between the pre-breakdown region and the breakdown region of the E-J curve is a non-ohmic characteristic. The larger the curve inclination, the larger the nonlinear coefficient, and the better the pressure-sensitive performance. It can be seen from the figure that all samples have non-linear characteristics with increasing doping content, with the non-linear characteristic of example 9 being the best.
(6) Analyzing an impedance spectrum;
the impedance spectra of samples tested at room temperature for examples 5, 6, 7, 8, 9, and 10 are shown in fig. 10. R g And R gb Are two parameters that may reflect the effect on the grain boundaries, texture and defects of the sample. The ZnO composite functional ceramic has difficulty in obtaining complete semicircular impedance at room temperature, but the trend of grain boundary resistance can still be predicted from the graph, which shows that all samples have similar relaxation behavior. With Ta 2 O 5 And In 2 O 3 The grain boundary resistance of the doped sample is larger than that of the undoped sample, and the electrical performance tends to be stable. For analyzing Ta in samples of different compositions 2 O 5 And In 2 O 3 The effect of the grain resistance was observed as a partial enlarged view at high frequency. The increase in grain resistance followed by the decrease in grain resistance with increasing doping may be due to a defect reaction that occurs when doping to a certain amount, producing a large amount of charge, decreasing the grain resistance, but overall Ta 2 O 5 And In 2 O 3 The influence on the grain resistance is small.
(7) Dielectric analysis;
the dielectric properties of the samples tested at room temperature for examples 5, 6, 7, 8, 9, 10 are shown in fig. 11. Dielectric constant of all samples was 10 2 ～10 7 Hz is in a descending trend. According to the polarization mechanism, local charge accumulation occurs inside the high conductivity ZnO grains, resulting in space charge polarization. The dielectric constant decreases more gradually with the increase of frequency, which shows that the dielectric constant has certain dependence on frequency. In the plot of dielectric loss versus frequency of the sample at 10 5 ～10 7 The frequency of Hz gives rise to loss peaks due to relaxation caused by the hopping motion of trapped electrons or holes. During the relaxation of the medium, energy loss occurs during the polarization of the medium and may reach a peak of the energy loss, and this region is called a diffusion region. Since the dielectric polarization needs a period of time to stabilize, the frequency range of the dispersion region is wide.
(8) Analyzing a hysteresis loop;
fig. 12 is hysteresis curves of examples 5, 6, 7, 8, 9, and 10. Ceramic materials often have high dielectric constants, and the relative dielectric constants of different ceramic systems are between several digits and tens of thousands of digits, so that the ceramic materials have the advantages of high resistivity and breakdown strength, good thermal stability, high reliability and the like. The ceramic energy storage capacitor has the advantages of high power density, short charging and discharging time, long cycle life, wide temperature application range, mature process and the like. According to the graph, the energy storage densities of the embodiments 6, 7, 8, 9 and 10 are respectively 3.99J, 4.04J, 3.61J, 3.94J and 3.87J, and the energy storage efficiencies of the embodiments 6, 7, 8, 9 and 10 are respectively 21.30%, 22.97%, 17.49%, 24.67% and 28.11%. The ZnO composite functional ceramic has certain energy storage density and energy storage efficiency, and is a potential energy storage material.
(9) Aging analysis;
at a temperature of 120 ℃,85% U 1mA The samples of all examples were then aged for 12 hours and the resulting aged pressure sensitive properties and rate of change are shown in Table 3. It can be seen that it is oldThe voltage is reduced after the conversion, and the leakage current is increased. The change rate of the threshold voltage is respectively-8.0%, -6.6%, -10.3%, -5.2%, -4.5%, -1.9%, -2.0%, -5.2%, -2.2%, -1.0%, the potential gradient change rate of embodiment 3 is greater than 10%, and the other samples can not pass through the aging experiment, and are doped with Ta simultaneously through the aging experiment 2 O 5 And In 2 O 3 The ageing properties of (2) are significantly better.
TABLE 3 pressure sensitive Properties and Rate of Change after aging for the examples
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A preparation method of In and Ta zinc oxide composite functional ceramic is characterized by comprising the following steps:
s1: znO and Bi are mixed 2 O 3 、Sb 2 O 3 、Ni 2 O 3 、Co 3 O 4 、MnO 2 、Al(NO 3 ) 3 、TiO 2 、In 2 O 3 、Ta 2 O 5 Mixing the powder in deionized water with ZrO 2 Ball-milling the medium at the speed of 200r/min for 12 hours, and drying at the temperature of 80 ℃ for 24 hours;
s2: mixing the dry powder obtained in the step S1 with an adhesive, and pressing into a green body;
s3: heating the green body obtained in the step S2 to 600 ℃ at the heating rate of 2 ℃/min for 2h, and removing the binder;
s4: and (4) sintering the green body without the binder obtained in the step (S3) to 1200-1300 ℃ at the heating rate of 5 ℃/min, preserving the heat for 90min, and then cooling to room temperature to obtain the zinc oxide composite functional ceramic.
2. The method for preparing In and Ta co-doped zinc oxide composite functional ceramic according to claim 1, wherein ZnO and Bi In the step S1 2 O 3 、Sb 2 O 3 、Ni 2 O 3 、Co 3 O 4 、MnO 2 、Al(NO 3 ) 3 、TiO 2 、In 2 O 3 、Ta 2 O 5 The mol parts of the powder are as follows: 90-95 parts of ZnO; bi 2 O 3 0.5-2 parts; sb 2 O 3 0.3-1 part; ni 2 O 3 0.2 to 1.5 portions; co 3 O 4 0.3 to 1.5 portions; mnO 2 0.3 to 1.5 portions; al (NO) 3 ) 3 0 to 0.2 portion; tiO 2 2 0-2 parts of a solvent; in 2 O 3 0.001 to 0.1 portion; ta 2 O 5 0.001 to 0.2 portion.
3. The method for preparing In and Ta co-doped zinc oxide composite functional ceramic according to claim 1, wherein the binder In the step S2 is 5wt.% of polyvinyl alcohol (PVA).
4. The method for preparing the In and Ta co-doped zinc oxide pressure-sensitive composite functional ceramic according to claim 1, wherein the diameter of the green body In the step S2 is 13mm.
5. The method for preparing In and Ta co-doped zinc oxide pressure-sensitive composite functional ceramic according to claim 1, wherein the temperature is reduced In the step S4 at 1 ℃/min to 900 ℃, then at 3 ℃/min to 600 ℃, and finally at 1 ℃/min to room temperature.
6. An In and Ta co-doped zinc oxide composite functional ceramic prepared by the preparation method of any one of claims 1 to 5.
7. The use of the In and Ta co-doped zinc oxide composite functional ceramic of claim 6In the protection of power electronic devices and energy storage.
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