CN113603476A - Preparation method and electrochemical test of multi-point electrode zinc oxide pressure-sensitive ceramic - Google Patents

Preparation method and electrochemical test of multi-point electrode zinc oxide pressure-sensitive ceramic Download PDF

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CN113603476A
CN113603476A CN202110920052.0A CN202110920052A CN113603476A CN 113603476 A CN113603476 A CN 113603476A CN 202110920052 A CN202110920052 A CN 202110920052A CN 113603476 A CN113603476 A CN 113603476A
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zinc oxide
voltage
sensitive ceramic
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刘建科
李智智
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Shaanxi University of Science and Technology
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Abstract

The invention provides a preparation method and an electrochemical test of multi-point electrode zinc oxide voltage-sensitive ceramic. According to the multi-point electrode zinc oxide voltage-sensitive ceramic obtained in the invention, one zinc oxide voltage-sensitive ceramic can have high response characteristics under a plurality of voltage-sensitive voltages at the same time, so that effective protection on a plurality of circuits is achieved at the same time; the multi-point electrode zinc oxide pressure-sensitive ceramic greatly saves the manufacturing cost of the pressure-sensitive ceramic and has good economic benefit; the invention has simple principle and high safety, and is convenient for production, popularization and large-scale use.

Description

Preparation method and electrochemical test of multi-point electrode zinc oxide pressure-sensitive ceramic
Technical Field
The invention relates to the technical field of zinc oxide pressure-sensitive ceramics, in particular to a preparation method and an electrochemical test of multi-point electrode zinc oxide pressure-sensitive ceramics.
Background
Zinc oxide voltage sensitive ceramics are widely used in electronic and electrical systems for detecting and limiting transient voltage surges due to their excellent current-voltage characteristics and greater energy absorption capability. The nonlinear characteristics of zinc oxide pressure sensitive ceramics are attributed to the double schottky barrier present in the zinc oxide grain boundary layer. High non-linearity factors, i.e. faster time response and more efficient protection means, are considered to be the most important indicators. In addition, parameters such as voltage-dependent voltage, leakage current and residual voltage ratio of the zinc oxide voltage-sensitive ceramic also have great influence on practical application of the zinc oxide voltage-sensitive ceramic. In different circuit applications, the voltage-sensitive ceramic with proper voltage-sensitive voltage is needed, and even in the same circuit system, the voltage-sensitive ceramic with two or more voltage ranges is needed, so that the effective protection of the circuit is realized. The voltage-sensitive ceramic prepared by the traditional surface electrode process has specific voltage-sensitive voltage, and can not realize the protection of one voltage-sensitive ceramic on a plurality of elements with different voltage requirements.
Disclosure of Invention
The invention provides a preparation method and an electrochemical test of a multi-point electrode zinc oxide voltage-sensitive ceramic, aiming at the problem that the voltage-sensitive ceramic prepared by the traditional surface electrode process in the prior art has specific voltage-sensitive voltage and can not realize the protection of one voltage-sensitive ceramic on elements with different voltage requirements.
The invention is realized by the following technical scheme:
a preparation method of multi-point electrode zinc oxide pressure-sensitive ceramic comprises the following steps:
preparing materials: obtaining ingredients required for preparing the zinc oxide pressure-sensitive ceramic, and weighing;
ball milling: putting the weighed ingredients required by the zinc oxide pressure-sensitive ceramic, ultrapure water and zirconium balls into a ball-milling tank in proportion, and carrying out ball milling in a planetary ball mill;
drying, grinding and granulating: putting the ball-milled mixed slurry into an electrothermal blowing drying box, after drying the water, putting the mixed material into a mortar to be ground into powder, adding a PVA solution with the powder mass of 4%, putting the mixed material into a planetary ball mill to be ball-milled, then putting the mixed material into the electrothermal blowing drying box to be dried, and then granulating the dried powder;
dry pressing and forming and removing glue: dry-pressing the powder into a round green body under the action of hydraulic pressure by using a hydraulic press and a grinding tool, and putting the round green body into a box-type furnace for removing glue to obtain a sample;
and (3) sintering: sintering the sample in a box furnace to obtain a ceramic wafer, polishing the ceramic wafer, and performing thermal corrosion to obtain zinc oxide pressure-sensitive ceramic;
a multipoint electrode: and a plurality of point electrodes are respectively arranged on the upper polar plate and the lower polar plate of the zinc oxide pressure-sensitive ceramic, and the point electrodes of the upper polar plate and the lower polar plate are respectively connected.
Preferably, the weighed ingredients, ultrapure water and zirconium balls required by the zinc oxide pressure sensitive ceramic are subjected to ball milling in a planetary ball mill according to the ratio of 1:2: 2.
Furthermore, the ball milling time is 3-5 hours, and the rotation period is 30-60 min.
Preferably, the mixed slurry after ball milling is placed in an electrothermal blowing drying oven, and the temperature is kept for more than 5 hours at 100 ℃ for drying operation.
Preferably, the dried powder is granulated by a screen, wherein the screen mesh number range is as follows: 40 to 120 mesh.
Preferably, the distance between one point electrode in the lower polar plate of the zinc oxide voltage-sensitive ceramic and a plurality of point electrodes in the upper polar plate respectively represents different voltage-sensitive voltages, wherein the larger the distance is, the larger the voltage-sensitive voltage is.
The multi-point electrode zinc oxide pressure-sensitive ceramic is prepared by the preparation method of the multi-point electrode zinc oxide pressure-sensitive ceramic.
An electrochemical test, comprising the following steps:
and (3) respectively assembling one point electrode in the lower polar plate of the multi-point electrode zinc oxide voltage-sensitive ceramic with a plurality of point electrodes in the upper polar plate by adopting a digital source meter electrode, and detecting the voltage-current data of the multi-point electrode zinc oxide voltage-sensitive ceramic at room temperature to obtain the test result of the voltage-sensitive voltage change of the multi-point electrode zinc oxide voltage-sensitive ceramic.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention provides a preparation method of multi-point electrode zinc oxide voltage-sensitive ceramic, which is used for obtaining the multi-point electrode zinc oxide voltage-sensitive ceramic. According to the multi-point electrode zinc oxide voltage-sensitive ceramic obtained in the invention, one zinc oxide voltage-sensitive ceramic can have high response characteristics under a plurality of voltage-sensitive voltages at the same time, so that effective protection on a plurality of circuits is achieved at the same time; the multi-point electrode zinc oxide pressure-sensitive ceramic greatly saves the manufacturing cost of the pressure-sensitive ceramic and has good economic benefit; the invention has simple principle and high safety, and is convenient for production, popularization and large-scale use.
Drawings
FIG. 1 is a schematic diagram of a multi-point electrode of a zinc oxide pressure sensitive ceramic of the present invention;
FIG. 2 is a schematic diagram of the upper plate point electrode and wiring of the multi-point electrode zinc oxide voltage-sensitive ceramic of the present invention;
FIG. 3 is a schematic diagram of the lower plate point electrode and wiring of the multi-point electrode zinc oxide voltage-sensitive ceramic of the present invention;
FIG. 4 is an SEM image of a multi-point electrode zinc oxide pressure sensitive ceramic in the invention;
FIG. 5 is a schematic view showing the inter-electrode distance of the multi-point electrode zinc oxide pressure sensitive ceramic of the present invention;
FIG. 6 is a schematic diagram of the lower plate point electrode and wiring of the 2-point electrode zinc oxide voltage-sensitive ceramic in example 1 of the present invention;
FIG. 7 is a schematic diagram of the upper plate point electrode and wiring of the 2-point electrode zinc oxide voltage-sensitive ceramic in example 1 of the present invention;
FIG. 8 is a view of different electrode groups U-I according to example 1 of the present invention;
FIG. 9 is a schematic view of the lower plate point electrode and wiring of the 3-point electrode zinc oxide voltage-sensitive ceramic in example 2 of the present invention;
FIG. 10 is a schematic diagram of the upper plate point electrode and wiring of the 3-point electrode zinc oxide voltage-sensitive ceramic in example 2 of the present invention;
FIG. 11 is a view of different electrode groups U-I according to embodiment 2 of the present invention;
FIG. 12 is a schematic view of the bottom plate point electrode and wiring of the 5-point electrode zinc oxide voltage-sensitive ceramic in example 3 of the present invention;
FIG. 13 is a schematic diagram of the upper plate point electrode and wiring of the 5-point electrode zinc oxide pressure sensitive ceramic in example 3 of the present invention;
FIG. 14 is a diagram of different electrode groups U-I according to embodiment 3 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
the invention adopts the traditional solid heat sintering method to prepare the zinc oxide pressure-sensitive ceramic, and the preparation process and the test flow mainly comprise the steps of material preparation → ball milling → drying → grinding → granulation → dry pressure molding → adhesive removal → sintering → multipoint electrode silver → electrical performance test. The sample preparation and electrode design steps are described as necessary:
the invention provides a preparation method of multi-point electrode zinc oxide voltage-sensitive ceramic, which is used for obtaining the multi-point electrode zinc oxide voltage-sensitive ceramic, and can realize the voltage-sensitive ceramic with a certain range of voltage-sensitive voltage according to different point electrodes on the surface of the ceramic, and the application range is wide.
Specifically, the preparation method comprises the following steps:
preparing materials: obtaining ingredients required for preparing the zinc oxide pressure-sensitive ceramic, and weighing;
ball milling: putting the weighed ingredients required by the zinc oxide pressure-sensitive ceramic, ultrapure water and zirconium balls into a ball-milling tank in proportion, and carrying out ball milling in a planetary ball mill;
drying, grinding and granulating: putting the ball-milled mixed slurry into an electrothermal blowing drying box, after drying the water, putting the mixed material into a mortar to be ground into powder, adding a PVA solution with the powder mass of 4%, putting the mixed material into a planetary ball mill to be ball-milled, then putting the mixed material into the electrothermal blowing drying box to be dried, and then granulating the dried powder;
dry pressing and forming and removing glue: dry-pressing the powder into a round green body under the action of hydraulic pressure by using a hydraulic press and a grinding tool, and putting the round green body into a box-type furnace for removing glue to obtain a sample;
and (3) sintering: sintering the sample in a box furnace to obtain a ceramic wafer, polishing the ceramic wafer, and performing thermal corrosion to obtain zinc oxide pressure-sensitive ceramic;
a multipoint electrode: arranging a plurality of point electrodes and a plurality of point electrodes of a lower polar plate on an upper polar plate of the zinc oxide pressure-sensitive ceramic, respectively connecting the plurality of point electrodes of the upper polar plate and the plurality of point electrodes of the lower polar plate, coating silver paste into silver point electrodes with proper sizes by using a silver coating grinding tool with a certain diameter to be used as welding points, and then welding a lead with each welding point by using an electric iron to ensure good and safe contact, as shown in fig. 1, 2 and 3.
Specifically, the weighed ingredients needed by the zinc oxide pressure-sensitive ceramic, ultrapure water and zirconium balls are subjected to ball milling in a planetary ball mill according to the proportion of 1:2:2, the ball milling time is 3-5 hours, and the rotation period is 30-60min
Specifically, the mixed slurry after ball milling is placed in an electrothermal blowing drying oven, and the temperature is kept for more than 5 hours at 100 ℃ for drying operation.
Specifically, the dried powder is granulated through a screen, wherein the screen mesh range is as follows: 40 to 120 mesh.
Specifically, the distance between one point electrode in the lower polar plate of the zinc oxide voltage-sensitive ceramic and a plurality of point electrodes in the upper polar plate represents different voltage-sensitive voltages, wherein the larger the distance is, the larger the voltage-sensitive voltage is.
Referring to fig. 2 and 3, the multi-point electrode zinc oxide pressure sensitive ceramic of the present invention is obtained by the above-mentioned preparation method of the multi-point electrode zinc oxide pressure sensitive ceramic.
The invention provides an electrochemical test, which specifically comprises the following steps:
and (3) respectively assembling one point electrode in the lower polar plate of the multi-point electrode zinc oxide voltage-sensitive ceramic with a plurality of point electrodes in the upper polar plate by adopting a digital source meter electrode, and detecting the voltage-current data of the multi-point electrode zinc oxide voltage-sensitive ceramic at room temperature to obtain the test result of the voltage-sensitive voltage change of the multi-point electrode zinc oxide voltage-sensitive ceramic.
Referring to fig. 4, a SEM image of a general zinc oxide varistor ceramic with excellent nonlinearity and relatively uniform grain distribution shows that the varistor field strength of the zinc oxide varistor ceramic is mainly affected by grain boundary resistance, double schottky barrier height and grain size, so that the varistor ceramic with uniform microstructure and excellent and stable nonlinearity can be approximated as E having a small variation in varistor field strength in all directions0Therefore, the following are:
Figure BDA0003207047320000061
wherein d isminA distance of up and down facing the two point electrodes, U0A voltage-dependent voltage applied to two point electrodes facing each other from above and below, E0The pressure-sensitive field strength.
Referring to fig. 5, the upper and lower plates of the multi-point electrode zinc oxide voltage-sensitive ceramic are different point electrodes, and the direction of the voltage-sensitive field intensity, i.e. the connection direction of the upper and lower point electrodes, also changes accordingly. Because the microstructure of the selected sample is uniform, the nonlinearity of the zinc oxide pressure-sensitive ceramic has certain stability. Thus, the same zinc oxide voltage-sensitive ceramic can have a certain voltage-sensitive voltage Ux(E0dmin≤Ux≤E0dmax) Has high response characteristic, and has good economic benefit and application prospect.
Example 1
Preparation of a sample:
preparing materials: 15g of the ingredients for preparing the zinc oxide pressure-sensitive ceramic are weighed by an electronic balance, and the ingredients comprise 95.4 mol percent of ZnO and 1.8mol percent of Bi2O3、1mol％MnO2、1mol％TiO2And 0.8 mol% Sb2O3。
Ball milling: putting the weighed raw materials, ultrapure water and zirconium balls into a ball milling tank according to the proportion of 1:2:2, and carrying out ball milling in a planetary ball mill for 3 hours with the rotation period of 30 min.
Drying, grinding and granulating: and (3) putting the ball-milled mixed slurry into an electric heating air blast drying box, and preserving the heat for more than 5 hours at the temperature of 100 ℃ to ensure that the water is completely dried. And (3) putting the dried mixed material into a mortar to be ground into powder, adding two drops of PVA solution with the powder mass of 4%, putting the powder into a planetary ball mill to be ball-milled for 30min, putting the mixed slurry into an electric heating blast drying box, preserving the heat for more than 5h at 100 ℃, and sieving the dried powder with a sieve of more than 40 and less than 120 meshes to granulate.
Dry pressing and forming and removing glue: the powder was dry pressed into a round green compact with a diameter of 12mm and a thickness of 1.24mm using a hydraulic press and a 12mm diameter grinding tool at a hydraulic pressure of 7 MPa. And then putting the pressed round green body into a box-type furnace, heating to 600 ℃ at the speed of 3 ℃/min, and preserving heat for 5h to remove the glue.
And (3) sintering: the temperature program of the box furnace was set according to the appropriate sintering schedule for the samples. After sintering, the ceramic wafer can be polished to enable the surface of the ceramic wafer to have a mirror reflection effect by the appearance and the uniformity of crystal grains observed under a scanning electron microscope, and then hot corrosion is carried out at the temperature of not lower than the sintering temperature and within 100 ℃.
Multi-point electrode design: fig. 7 shows the point electrodes and the wiring of the upper electrode plate, and 2 point electrodes, namely the point electrode 1 and the point electrode 2, are distributed in total. The distance between the point electrode 1 and the point electrode 2 is 2mm, and according to the geometrical relationship, the connecting line distances of the electrodes 0-1 and 0-2 are respectively 1.240mm and 2.353mm, as shown in table 1. Fig. 6 shows the point electrodes and the wiring of the lower plate, and 1 point electrode, namely the point electrode 0, is distributed in total. The position of the dot electrode 0 on the lower plate is the same as the position of the dot electrode 1 on the upper plate. Firstly, silver paste is coated into silver point electrodes with proper sizes by a silver coating grinding tool with a certain diameter to be used as welding points, and then a lead is welded with each welding point by an electric iron, so that good contact and safety are ensured.
Test and test results
The electrodes of the KEITHLEY2410 type digital source meter are respectively connected with 0-1 point electrodes and 0-2 point electrodes. The results of the voltage-current data of the test samples at room temperature are shown in table 1, and the voltage-current (U-I) characteristic curves are shown in fig. 8.
Table 1 shows the distance d between the upper and lower point electrodes and the theoretical value U of the voltage-dependent voltage1mAAnd actual value of U'1mAAnd a non-linear coefficient. In which the non-linear coefficient
Figure BDA0003207047320000081
(wherein U is1mAAnd U0.1mAThe voltage values are respectively corresponding to the current of 1mA and 0.1 mA. )
Figure BDA0003207047320000082
TABLE 1 Point electrode connectionCorresponding upper and lower point electrode connecting line distance d and voltage-dependent voltage theoretical value U1mAAnd actual value of U'1mAAnd nonlinear coefficient
As shown in FIG. 8, the voltage-sensitive voltage of the ZnO varistor increases with the distance between the electrode connecting lines of the upper and lower plate points, and the 3-group-connected ZnO varistor exhibits good nonlinearity, as can be seen from Table 1, within the allowable error range, the test and theoretical analysis are consistent, i.e., the same ZnO varistor can have a certain voltage-sensitive voltage Ux＝E0dx(E0dmin≤Ux≤E0dmax) Wherein d isxThe distance between the point electrodes of the upper and lower polar plates is the connecting line distance.
Example 2
Preparation of a sample:
preparing materials: 15g of the ingredients for preparing the zinc oxide pressure-sensitive ceramic are weighed by an electronic balance, and the ingredients comprise 95.4 mol percent of ZnO and 1.8mol percent of Bi2O3、1mol％MnO2、1mol％SiO2And 0.8 mol% Sb2O3。
Ball milling: putting the weighed raw materials, ultrapure water and zirconium balls into a ball milling tank according to the proportion of 1:2:2, and carrying out ball milling in a planetary ball mill for 3 hours with the rotation period of 30 min.
Drying, grinding and granulating: and (3) putting the ball-milled mixed slurry into an electric heating air blast drying box, and preserving the heat for more than 5 hours at the temperature of 100 ℃ to ensure that the water is completely dried. And (3) putting the dried mixed material into a mortar to be ground into powder, adding two drops of PVA solution with the powder mass of 4%, putting the powder into a planetary ball mill to be ball-milled for 30min, putting the mixed slurry into an electric heating blast drying box, preserving the heat for more than 5h at 100 ℃, and sieving the dried powder with a sieve of more than 40 and less than 120 meshes to granulate.
Dry pressing and forming and removing glue: the powder was dry pressed into a round green compact with a diameter of 12mm and a thickness of 1.24mm using a hydraulic press and a 12mm diameter grinding tool at a hydraulic pressure of 7 MPa. And then putting the pressed round green body into a box-type furnace, heating to 600 ℃ at the speed of 3 ℃/min, and preserving heat for 5h to remove the glue.
And (3) sintering: the temperature program of the box furnace was set according to the appropriate sintering schedule for the samples. After sintering, the ceramic wafer can be polished to enable the surface of the ceramic wafer to have a mirror reflection effect by the appearance and the uniformity of crystal grains observed under a scanning electron microscope, and then hot corrosion is carried out at the temperature of not lower than the sintering temperature and within 100 ℃.
Multi-point electrode design: fig. 10 shows the point electrodes and the wiring of the upper plate, and 3 point electrodes, namely, the point electrode 1, the point electrode 2 and the point electrode 3 are distributed in total. The distances between the point electrode 1 and the point electrodes 2 and 3 are 1.22mm and 1.85mm, respectively, and according to the geometrical relationship, the connection distances of the electrodes 0-1, 0-2 and 0-3 are 1.24mm, 1.74mm and 2.23mm, respectively, as shown in table 2. Fig. 9 shows the lower plate point electrode and the wiring, and 1 point electrode, namely point electrode 0, is distributed. The position of the dot electrode 0 on the lower plate is the same as the position of the dot electrode 1 on the upper plate. Firstly, silver paste is coated into silver point electrodes with proper sizes by a silver coating grinding tool with a certain diameter to be used as welding points, and then a lead is welded with each welding point by an electric iron, so that good contact and safety are ensured.
The electrodes of the KEITHLEY2410 type digital source meter are respectively connected with 0-1 point electrodes, 0-2 point electrodes and 0-3 point electrodes. The results of the voltage-current data of the test samples at room temperature are shown in Table 2, and the voltage-current (U-I) characteristic curves are shown in FIG. 11.
Table 2 shows the distance d between the upper and lower point electrodes and the theoretical value U of the voltage-dependent voltage1mAAnd actual value of U'1mAAnd a non-linear coefficient. In which the non-linear coefficient
Figure BDA0003207047320000101
(wherein U is1mAAnd U0.1mAThe voltage values are respectively corresponding to the current of 1mA and 0.1 mA. )
Figure BDA0003207047320000102
Table 2 shows the distance d between the upper and lower point electrodes and the theoretical value U of the voltage-dependent voltage1mAAnd actual value of U'1mAAnd nonlinear coefficient
As shown in FIG. 10, the voltage-sensitive voltage of the ZnO varistor increases with the distance between the electrode connecting lines of the upper and lower plate points, and the 3-group-connected ZnO varistor exhibits good nonlinearity, as can be seen from Table 2, within the allowable error range, the test and theoretical analysis are consistent, i.e., the same ZnO varistor can have a certain voltage-sensitive voltage Ux＝E0dx(E0dmin≤Ux≤E0dmax) Wherein d isxThe distance between the point electrodes of the upper and lower polar plates is the connecting line distance.
Example 3
Preparation of a sample:
preparing materials: 15g of the ingredients for preparing the zinc oxide pressure-sensitive ceramic are weighed by an electronic balance, and the ingredients comprise 95.4 mol percent of ZnO and 1.8mol percent of Bi2O3、1mol％MnO2、1mol％SiO2And 0.8 mol% Sb2O3。
Ball milling: putting the weighed raw materials, ultrapure water and zirconium balls into a ball milling tank according to the proportion of 1:2:2, and carrying out ball milling in a planetary ball mill for 3 hours with the rotation period of 30 min.
Drying, grinding and granulating: and (3) putting the ball-milled mixed slurry into an electric heating air blast drying box, and preserving the heat for more than 5 hours at the temperature of 100 ℃ to ensure that the water is completely dried. And (3) putting the dried mixed material into a mortar to be ground into powder, adding two drops of PVA solution with the powder mass of 4%, putting the powder into a planetary ball mill to be ball-milled for 30min, putting the mixed slurry into an electric heating blast drying box, preserving the heat for more than 5h at 100 ℃, and sieving the dried powder with a sieve of more than 40 and less than 120 meshes to granulate.
Dry pressing and forming and removing glue: the powder was dry pressed into a round green compact with a diameter of 12mm and a thickness of 1.24mm using a hydraulic press and a 12mm diameter grinding tool at a hydraulic pressure of 7 MPa. And then putting the pressed round green body into a box-type furnace, heating to 600 ℃ at the speed of 3 ℃/min, and preserving heat for 5h to remove the glue.
And (3) sintering: the temperature program of the box furnace was set according to the appropriate sintering schedule for the samples. After sintering, the ceramic wafer can be polished to enable the surface of the ceramic wafer to have a mirror reflection effect by the appearance and the uniformity of crystal grains observed under a scanning electron microscope, and then hot corrosion is carried out at the temperature of not lower than the sintering temperature and within 100 ℃.
Multi-point electrode design: fig. 13 shows the point electrodes and the wiring of the upper plate, and 5 point electrodes, namely, the point electrode 1, the point electrode 2, the point electrode 3, the point electrode 4 and the point electrode 5 are distributed in total. The distances between the point electrode 1 and the point electrodes 2, 3, 4 and 5 are 1.4mm, 2.8mm, 4.2mm and 5.6mm, respectively, and according to the geometrical relationship, the distances between the connecting lines of the electrodes 0-1, 0-2, 0-3, 0-4 and 0-5 are 1.24mm, 1.87mm, 3.06mm, 4.38 and 5.74mm, respectively, as shown in table 3, can be obtained. Fig. 12 shows the lower plate point electrodes and the wiring, and 1 point electrode, namely the point electrode 0, is distributed in total. The position of the dot electrode 0 on the lower plate is the same as the position of the dot electrode 1 on the upper plate. Firstly, silver paste is coated into silver point electrodes with proper sizes by a silver coating grinding tool with a certain diameter to be used as welding points, and then a lead is welded with each welding point by an electric iron, so that good contact and safety are ensured.
Test and test results
The electrodes of the KEITHLEY2410 type digital source meter are respectively a 0-1 point electrode assembly, a 0-2 point electrode assembly, a 0-3 point electrode assembly, a 0-4 point electrode assembly and a 0-5 point electrode assembly. The results of the voltage-current data of the test samples at room temperature are shown in Table 3, and the voltage-current (U-I) characteristic curves are shown in FIG. 14.
Table 3 shows the distance d between the upper and lower point electrodes and the theoretical value U of the voltage-dependent voltage1mAAnd actual value of U'1mAAnd a non-linear coefficient. In which the non-linear coefficient
Figure BDA0003207047320000121
(wherein U is1mAAnd I0.1mAThe voltage values are respectively corresponding to the current of 1mA and 0.1 mA. )
Figure BDA0003207047320000122
TABLE 3 Upper and lower point electrode connection lines corresponding to the point electrode connection modesDistance d, theoretical value of voltage-dependent voltage U1mAAnd actual value of U'1mAAnd the nonlinear coefficient is as shown in fig. 14, the voltage-sensitive voltage of the zinc oxide voltage-sensitive ceramic increases with the distance between the upper and lower plate point electrode connecting lines, and the 5-group method zinc oxide voltage-sensitive ceramic shows better nonlinearity, as can be obtained from table 3, within the error allowable range, the experiment is more consistent with the theoretical analysis, that is, the same zinc oxide voltage-sensitive ceramic can have a certain voltage-sensitive voltage Ux＝E0dx(E0dmin≤Ux≤E0dmax) Wherein d isxThe distance between the point electrodes of the upper and lower polar plates is the connecting line distance.
In summary, the invention provides a preparation method of a multi-point electrode zinc oxide voltage-sensitive ceramic, the multi-point electrode zinc oxide voltage-sensitive ceramic is obtained by the method, the designed multi-point electrode zinc oxide voltage-sensitive ceramic can realize voltage-sensitive ceramic with a certain range of voltage-sensitive voltage by connecting different point electrodes on the surfaces of a ceramic upper polar plate and a ceramic lower polar plate, and the application range is wide. According to the multi-point electrode zinc oxide voltage-sensitive ceramic obtained in the invention, one zinc oxide voltage-sensitive ceramic can have high response characteristics under a plurality of voltage-sensitive voltages at the same time, so that effective protection on a plurality of circuits is achieved at the same time; the multi-point electrode zinc oxide pressure-sensitive ceramic greatly saves the manufacturing cost of the pressure-sensitive ceramic and has good economic benefit; the invention has simple principle and high safety, and is convenient for production, popularization and large-scale use.
Meanwhile, the same zinc oxide voltage-sensitive ceramic obtained by electrochemical test of the multi-point electrode zinc oxide voltage-sensitive ceramic has a certain voltage-sensitive voltage Ux(E0dmin≤Ux≤E0dmax) The method has high response characteristic and good economic benefit and application prospect.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.

Claims (8)

1. The preparation method of the multi-point electrode zinc oxide pressure-sensitive ceramic is characterized by comprising the following steps:
preparing materials: obtaining ingredients required for preparing the zinc oxide pressure-sensitive ceramic, and weighing;
ball milling: putting the weighed ingredients required by the zinc oxide pressure-sensitive ceramic, ultrapure water and zirconium balls into a ball-milling tank in proportion, and carrying out ball milling in a planetary ball mill;
drying, grinding and granulating: putting the ball-milled mixed slurry into an electrothermal blowing drying box, after drying the water, putting the mixed material into a mortar to be ground into powder, adding a PVA solution with the powder mass of 4%, putting the mixed material into a planetary ball mill to be ball-milled, then putting the mixed material into the electrothermal blowing drying box to be dried, and then granulating the dried powder;
dry pressing and forming and removing glue: dry-pressing the powder into a round green body under the action of hydraulic pressure by using a hydraulic press and a grinding tool, and putting the round green body into a box-type furnace for removing glue to obtain a sample;
and (3) sintering: sintering the sample in a box furnace to obtain a ceramic wafer, polishing the ceramic wafer, and performing thermal corrosion to obtain zinc oxide pressure-sensitive ceramic;
a multipoint electrode: and a plurality of point electrodes are respectively arranged on the upper polar plate and the lower polar plate of the zinc oxide pressure-sensitive ceramic, and the point electrodes of the upper polar plate and the lower polar plate are respectively connected.
2. The preparation method of the multi-point electrode zinc oxide pressure-sensitive ceramic according to claim 1, wherein the weighed ingredients of the zinc oxide pressure-sensitive ceramic, ultrapure water and zirconium balls are subjected to ball milling in a planetary ball mill according to a ratio of 1:2: 2.
3. The preparation method of the multi-point electrode zinc oxide pressure-sensitive ceramic as claimed in claim 2, wherein the ball milling time is 3-5 hours, and the rotation period is 30-60 min.
4. The preparation method of the multipoint electrode zinc oxide pressure sensitive ceramic according to claim 1, wherein the ball-milled mixed slurry is placed in an electrothermal blowing drying oven and is subjected to heat preservation for more than 5 hours at 100 ℃ for drying operation.
5. The preparation method of the multi-point electrode zinc oxide pressure-sensitive ceramic according to claim 1, wherein the dried powder is granulated by a screen mesh, wherein the screen mesh range is as follows: 40 to 120 mesh.
6. The preparation method of the multi-point electrode zinc oxide voltage-sensitive ceramic according to claim 1, wherein the distance between one point electrode in the lower polar plate and a plurality of point electrodes in the upper polar plate of the zinc oxide voltage-sensitive ceramic represents different voltage-sensitive voltages, wherein the larger the distance is, the larger the voltage-sensitive voltage is.
7. A multi-point electrode zinc oxide pressure-sensitive ceramic obtained by the method for preparing the multi-point electrode zinc oxide pressure-sensitive ceramic according to any one of claims 1 to 6.
8. An electrochemical test, comprising the steps of:
and (3) respectively assembling one point electrode in the lower polar plate of the multi-point electrode zinc oxide voltage-sensitive ceramic of claim 7 with a plurality of point electrodes in the upper polar plate by using a digital source meter electrode, and detecting the voltage-current data of the multi-point electrode zinc oxide voltage-sensitive ceramic at room temperature to obtain the test result of the voltage-sensitive voltage change of the multi-point electrode zinc oxide voltage-sensitive ceramic.
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CN106373685A (en) * 2016-08-29 2017-02-01 广西新未来信息产业股份有限公司 Low-voltage voltage-sensitive resistor pack and fabrication method thereof
CN109950013A (en) * 2017-12-20 2019-06-28 成都铁达电子股份有限公司 A kind of ceramic chip and piezoresistor
CN111517778A (en) * 2020-05-20 2020-08-11 华南理工大学 Low-temperature sintered zinc oxide pressure-sensitive ceramic and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102142308A (en) * 2011-01-12 2011-08-03 深圳顺络电子股份有限公司 Laminated voltage-sensitive resistor array
CN103187668A (en) * 2011-12-31 2013-07-03 辽宁省轻工科学研究院 Zinc oxide base multilayer pressure-sensitive planar array for filtering connector
CN105510683A (en) * 2015-12-29 2016-04-20 清华大学 Method for testing current distribution uniformity inside single voltage-dependent resistor valve block within wide temperature range
CN106373685A (en) * 2016-08-29 2017-02-01 广西新未来信息产业股份有限公司 Low-voltage voltage-sensitive resistor pack and fabrication method thereof
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