CN116217223B - SnO (tin oxide) 2 Base ceramic material and preparation method and application thereof - Google Patents

SnO (tin oxide) 2 Base ceramic material and preparation method and application thereof Download PDF

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CN116217223B
CN116217223B CN202310495628.2A CN202310495628A CN116217223B CN 116217223 B CN116217223 B CN 116217223B CN 202310495628 A CN202310495628 A CN 202310495628A CN 116217223 B CN116217223 B CN 116217223B
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powder
ceramic material
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base ceramic
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CN116217223A (en
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郇正利
常宁
韩利伟
曹光利
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Shandong Lians Intelligent Technology Co ltd
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Abstract

The invention provides SnO 2 A base ceramic material, a preparation method and application thereof. The SnO 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 85-98 parts of powder, bi 2 O 3 1 to 7.5 parts of powder, nb 2 O 5 1 to 7.5 parts of powder. The invention adopts a solid phase synthesis method to prepare (Bi+Nb) co-doped SnO 2 The ceramic material with giant dielectric property and low loss is successfully prepared by improving the preparation process and sintering mode. The giant dielectric ceramic material has high dielectric constant, low dielectric loss, stable frequency characteristic and temperature characteristic, can adapt to low-high temperature working environment, is very suitable for miniature capacitors, has great practical value in integrated circuits, solves the problem that the giant dielectric material has high dielectric constant and low dielectric loss, and has good frequency and temperature stability.

Description

SnO (tin oxide) 2 Base ceramic material and preparation method and application thereof
Technical Field
The invention relates to SnO 2 Base ceramic material and preparation method and application thereof, in particular to giant dielectric and low-loss SnO 2 A base ceramic material and a preparation method and application thereof, belonging to the technical field of ceramic preparation.
Background
The rapid progress of electronic science and technology, electronic devices and electronic systems are moving toward miniature lightweight, modular, highly integrated, highly reliable, and fast computing. Giant dielectric constant materials (CP, epsilon > 1000) are key materials for realizing the miniaturization, integration and high performance of electronic devices such as solid-state capacitors, dynamic storage, logic devices, energy storage and the like, and have great potential in various types of miniaturized electronic equipment and high-energy-density storage. In recent years, researchStudy of CaCu by the Subjects 3 Ti 4 O 12 (CCTO) materials, although having a large dielectric constant, are disadvantageous in that dielectric loss is too high and temperature stability is poor; baTiO 3 (BTO) dielectric materials, which have high dielectric constants due to ferroelectricity, but exhibit very high dielectric constants only near the Curie temperature point (120 ℃ C.), a steep decrease in giant dielectric constant beyond the phase transition temperature, and a relaxor ferroelectric Pb-based perovskite (e.g., pb (Zr, ti) O 3 ) The dielectric constant in the phase transition temperature region (ferroelectric-paraelectric) is very high, but the dielectric constant has a too large variation range along with the temperature rise, and the environment is seriously polluted. It remains a difficult challenge and important task to obtain an environmentally friendly bulk dielectric material that has a high dielectric constant, low dielectric loss, good single phase frequency and temperature stability at the same time.
The earliest researchers were studying SnO 2 In the case of materials, the analysis is mainly to remove the pressure-sensitive effect, and later researchers begin to try to study the doped SnO by a co-doping method 2 Dielectric behavior of ceramic materials. Hu et al by reacting with SnO 2 Mg doped in the matrix shows giant dielectric behavior, but dielectric loss is too high and the amplitude of change with frequency is too large; subsequently Khan et al prepared SnO by Co-doping (Zn, co) 2 Ceramics, although having a very high dielectric constant, have a high dielectric constant only in a very low frequency range; zaman and Wang also found a giant dielectric constant phenomenon by doping with other elements, and their losses were also very low. Chinese patent document CN112521144A provides a low-temperature giant dielectric inverse magnet ceramic material, and preparation and application thereof, wherein the ceramic material is prepared from SnO 2 Sintering the base ceramic powder material to obtain the SnO 2 The base ceramic powder material comprises SnO as a main component 2 The powder also comprises a modifier, wherein the modifier is transition metal oxide CoO and/or Ta 2 O 5 The molar ratio of the modifier in the ceramic powder composition is lower than 10%. However, the low-temperature giant dielectric inverse magnet ceramic material is excessively doped by measuring whether the material performance is excellent or not only by looking at the frequency stability but also by looking at the temperature stabilityThe metal element, although improving the performance of the ceramic material, has good frequency stability, but the dielectric constant and dielectric loss of the metal element have too large variation range with temperature, the dielectric performance has no good temperature stability, and the dielectric loss has a trend of sharply increasing in low temperature and high temperature areas.
At present for doping SnO 2 There are few reports on the related researches on the giant dielectric properties of ceramics, and the novel ceramic material is in the sprouting stage, so that SnO 2 The ceramic material has huge research space and wide application prospect, and can be a new member of the research field of giant dielectric materials in the future. Therefore, the study of doping SnO is continued 2 The giant dielectric property of the ceramic is of great significance. For the above reasons, the present inventors have made long-term studies and practices to finally obtain the present invention.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a SnO 2 A base ceramic material, a preparation method and application thereof. The invention develops the dielectric material with high dielectric constant, low dielectric loss and stable frequency and temperature by improving the new formula and the production process, and solves the problems that the current giant dielectric material can not have both the giant dielectric constant and the low dielectric loss and the temperature stability.
The technical scheme of the invention is as follows:
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 85-98 parts of powder, bi 2 O 3 1 to 7.5 parts of powder, nb 2 O 5 1 to 7.5 parts of powder, wherein Bi 2 O 3 And Nb (Nb) 2 O 5 The molar ratio of (2) is 1:1.
According to a preferred embodiment of the present invention, the SnO 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 90-95 parts of powder and Bi 2 O 3 2.5 to 5 parts of powder, nb 2 O 5 2.5-5 parts of powder, wherein Bi 2 O 3 And Nb (Nb) 2 O 5 The molar ratio of (2) is 1:1.
Above-mentionedSnO 2 The preparation method of the base ceramic material comprises the following steps:
(1) SnO is prepared 2 、Bi 2 O 3 And Nb (Nb) 2 O 5 The raw materials are mixed according to the proportion, ball milling is carried out, and mixed powder is obtained after filtration and drying;
(2) Adding an adhesive into the mixed powder obtained in the step (1) for granulating; vacuum packaging the material obtained by granulation, and performing temperature isostatic pressing to obtain a compressed material;
(3) Grinding, granulating and tabletting the compressed material obtained in the step (2) to obtain a green sheet, performing cold isostatic pressing and glue discharging treatment on the obtained green sheet, and sintering to obtain SnO 2 A base ceramic material.
According to the present invention, preferably, the ball milling step in the step (1) is: snO is prepared 2 、Bi 2 O 3 And Nb (Nb) 2 O 5 Mixing the raw materials according to the proportion, and then adding the mixture into a ball milling tank containing zirconia and deionized water for ball milling; the ball-material ratio in the ball milling process is 3-5:1; the mass of the deionized water and SnO 2 、Bi 2 O 3 And Nb (Nb) 2 O 5 The ratio of the total mass of the raw materials is 0.5-1:1; the ball milling rotating speed is 300-500 r/min, the ball milling process is provided with forward and reverse direction alternate rotation, the interval time is 5min, and the ball milling time is 10-15 h.
According to the invention, preferably, the drying in the step (1) is performed at 70-80 ℃ for 10-15 hours; the D90 particle size of the obtained mixed powder is 2.0-2.2 mu m.
Preferably, according to the present invention, the binder in step (2) is deionized water; the mass ratio of the adhesive to the mixed powder is 1-3:1.
According to the invention, preferably, the vacuum packaging in the step (2) is tabletting packaging under the pressure of 2-4 MPa by using a dry-pressing tablet press; the pressure of the temperature isostatic pressing is 300-350 MPa, the boosting rate of the temperature isostatic pressing is 2MPa/s, and the pressure maintaining time is 10s.
According to a preferred embodiment of the present invention, the granulating step in step (3) is: and adding deionized water into the powder obtained by grinding for granulation, wherein the mass ratio of the deionized water to the powder is 2-5:1.
According to the present invention, preferably, the tabletting step in the step (3) is as follows: and pressing the granulated material into green sheets with the diameter of 10mm and the thickness of 2mm under the pressure of 2-4 MPa.
According to a preferred embodiment of the invention, the conditions of the cold isostatic pressing in step (3) are: the pressure of the cold isostatic pressing is 300-350 MPa, the pressure rising rate of the cold isostatic pressing is 2MPa/s, and the pressure maintaining time is 10s.
According to the invention, preferably, the temperature of the glue discharging in the step (3) is 550-650 ℃, the time of the glue discharging is 0.5-2 h, and the heating rate is 3-5 ℃/min; the invention discharges the adhesive under specific conditions, and can make the ceramic have certain hardness.
According to the invention, the sintering temperature in the step (3) is 1200-1500 ℃, the sintering time is 3-5 h, and the heating rate is 3-5 ℃/min.
According to the present invention, the above SnO 2 The use of ceramic-based materials in miniature capacitors, high density stored energy devices, and integrated electronic devices. Giant dielectric and low-loss SnO prepared by the invention 2 The ceramic-based material plays a key role in realizing efficient energy storage in the future and super-strong power storage, and has a huge application prospect in the fields of multifunctional electronic equipment, energy storage devices and sensors.
The invention has the technical characteristics and beneficial effects that:
1. after theoretical research and a large number of experiments, the inventor selects element Bi with good performance to SnO 2 The base ceramic material is doped, so that the giant dielectric constant is maintained, and meanwhile, the dielectric loss is lower; while selecting a specific pentavalent donor element Nb doping with good compatibility to improve the giant dielectric properties thereof, because of Nb 5+ Is very close to Sn 4+ (r=0.69 a), nb element can be better doped into tin dioxide, thereby improving its dielectric properties. Experiments prove that the Bi+Nb co-doped SnO prepared by the invention 2 The ceramic generates a second phase when doped in low concentration in the ceramic sample, and the disappearance of the second phase appears as the continuous increase of the doping concentrationSingle SnO 2 A rutile phase; single doped Nb element obviously improves SnO 2 The dielectric constant of the base ceramic is 3.2×10 4 But its dielectric constant is also very high tan delta=0.08; single doping of Bi element to make SnO 2 The dielectric constant of the base ceramic is reduced by an order of magnitude of 3.48×10 3 But can reduce SnO 2 Dielectric loss of the base ceramic, tan δ=0.01; co-doping SnO with Bi+Nb 2 The dielectric performance of the ceramic is within the test frequency range (100 Hz-1 MHz), and the dielectric constant reaches 10 4 The dielectric loss is lower than 0.065, and the frequency stability is good; the dielectric constant reaches 10 within the test temperature range (-50-250 ℃) 3 In order, the dielectric loss is lower than 0.1, the temperature stability coefficient is lower than 15%, and the temperature stability is excellent. When the doping amount is 5%, the dielectric properties (ε' =2.88×10) of the obtained ceramic are as follows 4 Tan delta=0.047), the overall dielectric properties are most excellent.
2. The preparation method of the invention is simple and has low cost. The invention adopts the improvement on the traditional solid phase method: 1) The ball milling medium replaces alcohol with deionized water, so that the production cost is greatly reduced; 2) The granularity of the mixed powder after ball milling is analyzed, so that the doping success can be better ensured; 3) The adhesive replaces PVA solution with deionized water, so that the fluidity of the deionized water is better, and the granulation uniformity is ensured; 4) By adopting the warm isostatic pressing and the cold isostatic pressing, the non-uniform distribution of the traditional solid phase synthesis tabletting adhesives is greatly improved, meanwhile, the pre-sintering procedure after powder stirring in the traditional solid phase method is omitted, the production cost and the time cost are reduced, the sintering density of the ceramic is improved, and the dielectric property of the ceramic is greatly improved. The giant dielectric and low-loss SnO with more excellent performance is successfully prepared by the improvement 2 And (3) a base ceramic sample.
Drawings
FIG. 1 shows SnO prepared in examples 1 to 4 2 XRD pattern of the base ceramic material.
FIG. 2 is SnO prepared in comparative examples 1-2 2 XRD pattern of the base ceramic material.
FIG. 3 is SnO prepared in example 1 2 SEM of the base ceramic material.
FIG. 4 is SnO prepared in example 2 2 SEM of the base ceramic material.
FIG. 5 is SnO prepared in example 3 2 SEM of the base ceramic material.
FIG. 6 is SnO prepared in example 4 2 SEM of the base ceramic material.
FIG. 7 is SnO prepared in comparative example 1 2 SEM of the base ceramic material.
FIG. 8 is SnO prepared in comparative example 2 2 SEM of the base ceramic material.
FIG. 9 shows SnO prepared in examples 1 to 4 2 Dielectric spectrogram of the base ceramic material (frequency range: 100 Hz-1 MHz).
FIG. 10 shows SnO prepared in comparative examples 1 to 2 2 Dielectric spectrogram of the base ceramic material (frequency range: 100 Hz-1 MHz).
FIG. 11 shows SnO prepared in comparative examples 3 to 6 2 Dielectric spectrogram of the base ceramic material (frequency range: 100 Hz-1 MHz).
FIG. 12 shows SnO prepared in comparative examples 7 to 10 2 Dielectric spectrogram of the base ceramic material (frequency range: 100 Hz-1 MHz).
FIG. 13 is a schematic diagram of the preparation of SnO according to example 2 2 The temperature spectrum of the base ceramic material (frequency range: 1 kHz-1 MHz; temperature range: 100 ℃ below zero-350 ℃).
Detailed Description
The invention is further illustrated by, but not limited to, the following specific examples.
The raw materials used in the examples are all conventional raw materials and are commercially available; the methods are prior art unless specified otherwise.
Example 1
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 97 parts of powder, bi 2 O 3 1.5 parts of powder, nb 2 O 5 1.5 parts of powder.
The above SnO 2 The preparation method of the base ceramic material comprises the following steps:
step 1: and (3) mixing the raw materials according to the molar parts, and uniformly mixing.
Step 2: placing the raw materials which are uniformly mixed in the step 1 into a ball milling tank in which zirconia and deionized water are placed, ball milling for 12 hours at the rotating speed of 400/min, wherein the ball material ratio in the ball milling process is 4:1, and SnO is adopted 2 、Bi 2 O 3 And Nb (Nb) 2 O 5 The ratio of the total mass of the powder to the mass of the deionized water is 4:3, and the ball milling process is provided with alternate rotation in the forward and reverse directions, and the interval time is 5min; filtering, and drying the obtained feed liquid at 80 ℃ for 10 hours to obtain mixed powder; the D90 particle size of the obtained mixed powder is 2.0-2.2 mu m.
Step 3: adding deionized water into the mixed powder obtained in the step 2 for granulating (the mass ratio of the deionized water to the mixed powder is 2:1), tabletting and packaging by using a dry-pressing tabletting machine under the pressure of 2MPa, and then placing the mixed powder into a warm isostatic pressing machine for maintaining the pressure for 10s under the pressure of 350MPa, wherein the boosting rate of the warm isostatic pressing is 2MPa/s.
Step 4: grinding and sieving the powder subjected to medium-temperature isostatic pressing in the step 3 (20 meshes), adding deionized water for granulating (the mass ratio of the deionized water to the powder is 4:1), pressing into green sheets with the diameter of 10mm and the thickness of 2mm under the pressure of 4MPa, and cold isostatic pressing for 10s under the pressure of 300MPa in a cold isostatic pressing machine at the boosting rate of 2MPa/s;
step 5: heating the green sheet subjected to the cold isostatic pressing in the step 4 to 650 ℃ at a heating rate of 3 ℃/min, continuously heating for 2 hours, and discharging the adhesive; continuously heating to 1200 ℃ at the heating rate of 3 ℃/min and preserving heat for 4 hours to obtain giant dielectric and low-loss SnO 2 The base ceramic material is SnO 2 A base ceramic material.
Example 2
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 95 parts of powder, bi 2 O 3 2.5 parts of powder, nb 2 O 5 2.5 parts of powder.
The above SnO 2 The preparation of the base ceramic material is as described in example 1.
Example 3
SnO (tin oxide) 2 A base ceramic material comprising the following components in parts by moleThe preparation method comprises the following steps: snO (SnO) 2 90 parts of powder, bi 2 O 3 5 parts of powder, nb 2 O 5 5 parts of powder.
The above SnO 2 The preparation of the base ceramic material is as described in example 1.
Example 4
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 85 parts of powder, bi 2 O 3 7.5 parts of powder, nb 2 O 5 7.5 parts of powder.
The above SnO 2 The preparation of the base ceramic material is as described in example 1.
Comparative example 1
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 95 parts of powder, nb 2 O 5 5 parts of powder.
The above SnO 2 The preparation of the base ceramic material is as described in example 1.
Comparative example 2
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 95 parts of powder, bi 2 O 3 5 parts of powder.
The above SnO 2 The preparation of the base ceramic material is as described in example 1.
Comparative example 3
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 97 parts of powder, al 2 O 3 1.5 parts of powder, nb 2 O 5 1.5 parts of powder.
The above SnO 2 The preparation of the base ceramic material is as described in example 1.
Comparative example 4
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 95 parts of powder, al 2 O 3 2.5 parts of powder, nb 2 O 5 2.5 parts of powder.
The above SnO 2 Base ceramicThe materials were prepared as described in example 1.
Comparative example 5
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 90 parts of powder, al 2 O 3 5 parts of powder, nb 2 O 5 5 parts of powder.
The above SnO 2 The preparation of the base ceramic material is as described in example 1.
Comparative example 6
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 85 parts of powder, al 2 O 3 7.5 parts of powder, nb 2 O 5 7.5 parts of powder.
The above SnO 2 The preparation of the base ceramic material is as described in example 1.
Comparative example 7
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 97 parts of powder, in 2 O 3 1.5 parts of powder, ta 2 O 5 1.5 parts of powder.
The above SnO 2 The preparation of the base ceramic material is as described in example 1.
Comparative example 8
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 95 parts of powder, in 2 O 3 2.5 parts of powder, ta 2 O 5 2.5 parts of powder.
The above SnO 2 The preparation of the base ceramic material is as described in example 1.
Comparative example 9
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 90 parts of powder, in 2 O 3 5 parts of powder, ta 2 O 5 5 parts of powder.
The above SnO 2 The preparation of the base ceramic material is as described in example 1.
Comparative example 10
SnO (tin oxide) 2 The base ceramic material is prepared from the following raw materials in parts by mole: snO (SnO) 2 85 parts of powder, in 2 O 3 7.5 parts of powder, ta 2 O 5 7.5 parts of powder.
The above SnO 2 The preparation of the base ceramic material is as described in example 1.
The comprehensive analysis is as follows:
SnO obtained in examples and comparative examples 2 The following performance tests are respectively carried out on the base ceramic material:
the performance test of the silver electrode comprises dielectric constant (epsilon') and dielectric loss (tan delta). The dielectric property spectrum test adopts an impedance analyzer to test the dielectric property spectrum of a sample, adopts a bridge method to test, and adopts the principle that: when the bridge is balanced, the products of the two side pairs of impedance are equal, and the capacitance value (C) and the loss value (tan delta) of the capacitor can be obtained through conversion. The dielectric temperature spectrum test adopts an impedance analyzer and a comprehensive Physical Property Measuring System (PPMS) and a whole set of test software. The temperature change can be precisely controlled by a computer program, and the change curve of dielectric properties with temperature at different frequencies can be tested, and the results are shown in tables 1-3.
TABLE 1 results of Performance test of ceramic samples of examples 1-4 and comparative examples 1-2 (at 1 kHz)
Figure SMS_1
Table 2 results of the ceramic sample Performance test (at 1 kHz) in comparative examples 3-6
Figure SMS_2
Table 3 results of the ceramic sample Performance test (at 1 kHz) in comparative examples 6-10
Figure SMS_3
(1) XRD analysis
The XRD patterns of examples 1, 2, 3, and 4 are shown in fig. 1. As can be seen from FIG. 1 (a), all of the samples used exhibited SnO as seen in the XRD diffraction pattern 2 The rutile phase, however, had a second phase formed in example 1 and example 2, and it was found by analysis that the second phase was Bi, an oxide of Bi 1.7 Sn 2 O 6.62 The method comprises the steps of carrying out a first treatment on the surface of the According to the Hume-rother rule, the ratio of the difference between the ionic radius of the doping element and the ionic radius of the matrix element to the ionic radius of the matrix element, when the ratio is higher than 15%, the doping element easily forms an interstitial solid solution in the matrix; whereas below 15%, alternative solid solutions are readily formed. Calculation shows that, | (R) Sn -R Bi )/R Sn I= | (69-117)/69|=69.6% is much higher than 15%, | (R) Sn -R Nb )/ R Sn I= | (69-78)/69|=13.4% below 15%, so Bi tends to form interstitial solid solutions and Nb tends to form substitutional solid solutions. From the XRD patterns it can be seen that a second phase is produced in examples 1 and 2, which indicates that a certain amount of Bi also forms an alternative solid solution. Then with further increase of doping amount, the second phase in example 3 and example 4 starts to disappear, and the single SnO is presented 2 Rutile phase. The main peak of FIG. 1 (b) (110) is significantly shifted gradually toward lower scattering angles and glancing angle increases with doping amountθIn a gradual decrease, it is shown that co-doped SnO 2 The sample lattice of the ceramic expands and the unit cell volume increases and the dopant ions enter the host lattice. (110) The reason for the shift of the main peak to the low scattering angle is the coordination number crystal Sn 4+ Radius of 0.69A, bi 3+ Radius of 1.17 a and Nb 5+ Radius of 0.78 a, doping element Bi 3+ And Nb (Nb) 5+ Radius of (a) is greater than Ti 4+ Ion radius, nb 5+ And Bi (Bi) 3+ Substituted Ti 4+ After the position of (a), the lattice parameter becomes larger, so that the main peak of (110) is significantly shifted to a small angle, which indicates that Bi and Nb elements are successfully doped into SnO 2 In the crystal lattice.
Comparative examples 1 and 2 XRD patterns of ceramic materials obtained by doping Nb and Bi elements, respectively, alone are shown in FIG. 2. As can be seen from FIG. 2 (a), all of the samples exhibited SnO 2 The rutile phase, but in comparative example 2, has a second phase formed, bi is an oxide of Bi as co-doped with Nb+Bi 1.7 Sn 2 O 6.62 Single Nb-doped SnO 2 A rutile phase; the main peak of FIG. 2 (b) (110) is significantly shifted gradually toward lower scattering angles and glancing angle increases with doping amountθIn a gradual decrease, it is shown that co-doped SnO 2 The sample lattice of the ceramic expands and the unit cell volume increases and the dopant ions enter the host lattice.
(2) SEM analysis;
SEM images of example 1, example 2, example 3 and example 4 are shown in fig. 3, 4, 5 and 6 respectively, and all ceramic surface microscopic morphologies with different doping contents can be observed from the images, and all samples are clearly visible in the sintering dense and seamless grain boundaries. When bi+nb co-doping is performed, the grain size of the ceramic sample increases and decreases as the doping amount increases, and the grain size becomes maximum when the doping amount is as in example 2, and starts to decrease again when the doping amount is further increased. The average grain size can be obtained by linear intercept calculation, and as the doping increases, the grain size of the BNSO ceramic shows a trend of increasing and decreasing, and as is obvious from the figure, the grain size of the sample of example 2 is maximum, white small particles are generated on large crystal particles, and the oxide of Bi is primarily judged, which is the same as the result in XRD analysis.
SEM images of comparative example 1 and comparative example 2 are shown in fig. 7 and 8, respectively, and the microscopic morphology of the surface of the ceramic sample doped with Nb and Bi alone can be observed from the images, and the grain boundaries of the compact and seamless grains are clearly visible for all samples. Doping Nb element alone to SnO 2 The crystal grain of the ceramic sample is reduced, and the size of the crystal grain is obviously increased when the Bi element is singly doped, which shows that the doping of the Bi element can promote the growth and development of the crystal grain of the sample.
(3) Analysis of dielectric Properties
FIG. 9 shows the production of example 1, example 2, example 3, example 4The dielectric properties (epsilon' and tan delta) of the prepared ceramic sample at room temperature are plotted against the frequency, and the frequency range is 100 Hz-1 MHz. As is clear from FIG. 9, the Bi+Nb co-doped ceramics, with increasing doping content, have dielectric constants of 10 for all ceramic samples throughout the frequency range of 100Hz to 1MHz 4 Magnitude, and as frequency increases, dielectric constant remains stable; the dielectric loss of all samples was kept below 0.1 in the test frequency range and had good frequency stability. As can be seen in FIG. 9, the sample of example 2 has a dielectric constant as high as 2.88X10 at a frequency of 1kHz 4 The dielectric loss was 0.047.
FIG. 10 shows the dielectric properties (. Epsilon.' and tan. Delta.) of the ceramic samples prepared in comparative example 1 and comparative example 2 at room temperature versus frequency, with the frequency range of 100 Hz-1 MHz. As is clear from FIG. 10, the dielectric constant of the ceramic sample is kept at 10 at 100 Hz-1 MHz in the frequency range of Nb element single-doped ceramic 4 Magnitude, this suggests that doping Nb element alone can improve the giant dielectric properties of the sample, but its dielectric loss is also very high; the dielectric constant of the ceramic sample is reduced to 10 in the frequency range of 100 Hz-1 MHz when the Bi element is singly doped 3 In order of magnitude, but correspondingly, its dielectric loss is also reduced, below that of the co-doped bi+nb element ceramic sample. Taken together, it is shown that the doping effect of Nb element is to improve SnO 2 The dielectric constant of the base ceramic sample, the doping of Bi element reduces SnO 2 Loss of the base ceramic sample. Co-doping Bi+Nb element, the ceramic sample has dielectric loss with practical application value while keeping giant dielectric.
FIG. 11 shows the dielectric properties (. Epsilon.' and tan. Delta.) of the ceramic samples of comparative examples 3 to 6 at room temperature versus frequency in the range of 100Hz to 1MHz. In FIG. 11, it is shown that all ceramics are co-doped with SnO in the frequency range of 100 Hz-1 MHz with increasing doping content 2 The dielectric constant of the ceramic sample was kept at 10 at all times 3 Magnitude, and as frequency increases, dielectric constant remains stable; the dielectric loss of all samples was kept below 0.1 in the test frequency range and had good frequency stability.As can be seen, the sample of comparative example 4 has a dielectric constant as high as 7.37X10 at a frequency of 1kHz 3 The dielectric loss was 0.03.
The examples are compared with comparative examples 3-6, when the pentavalent doping elements are the same, the different trivalent doping elements Bi and Al can obviously improve the dielectric constant of the ceramic sample when doping Bi, compared with the doped Al, the dielectric constant of the ceramic sample is improved by one order of magnitude, and the difference between the reduction of the dielectric loss is not great, which indicates that the doping of Bi improves SnO 2 The dielectric properties of the ceramic are significantly improved.
FIG. 12 shows the dielectric properties (. Epsilon.' and tan. Delta.) of the ceramic samples obtained in comparative examples 7 to 10 at room temperature versus frequency in the range of 100Hz to 1MHz. In FIG. 12, it is shown that in+Ta co-doped SnO In the frequency range of 100 Hz-1 MHz with the increase of the doping content of all ceramics 2 The dielectric constant of the ceramic sample was kept at 10 at all times 3 Magnitude, and as frequency increases, dielectric constant remains stable; the dielectric loss of all samples was kept below 0.1 in the test frequency range and had good frequency stability. As can be seen, the sample of comparative example 2 has a dielectric constant as high as 9.6X10 at a frequency of 1kHz 3 The dielectric loss was 0.035.
The embodiment is compared with the comparative example, the dielectric constant of the ceramic sample can be obviously improved when the Bi+Nb is doped compared with the Al+Nb and in+Ta, the dielectric constant of the ceramic sample is improved by one order of magnitude, and the difference between the dielectric constants is not great for the reduction of the dielectric loss of the ceramic sample, so that the doping of the Bi+Nb has great practical application and research values.
FIG. 13 shows the dielectric constant and dielectric loss versus temperature for the ceramic of example 2 over different frequencies (1 kHz-1 MHz). As can be seen in FIG. 13, the ceramic of example 2 exhibits a large dielectric constant (> 10) in the range of-100 to 350 DEG C 3 ) The dielectric constants of all samples are within the range of-100-350 ℃, and the dielectric constants of the samples are slowly increased along with the temperature rise. The dielectric constants and dielectric losses of all co-doped samples appear as relaxation peaks at a temperature of about 0 DEG CThis is due to the change in valence state of Sn ions. In addition, all the ceramics have good temperature stability in dielectric loss values within the temperature range of-100 to 250 ℃ and the values are all below 0.2. When the temperature is higher than 250 c, the dielectric constant increases sharply, which can be well explained by the increase in conductivity. The temperature stability coefficient is an important parameter for measuring the temperature stability of ceramics, and can represent the degree of change of dielectric properties of dielectrics with temperature in a certain temperature range, and the smaller the value is, the more stable the value is. The temperature stability coefficient can be calculated by using the general expression (1):
Figure SMS_4
ΔC/C 25℃ representing the temperature stability coefficient of the ceramic, C T Is a capacitance value. In order to meet the practical application requirements of electronic devices, the temperature stability coefficient of the dielectric constant of the X-R type capacitor (calculated under the same doping amount) should be less than +/-15% relative to room temperature. According to the calculation of the formula (1), the temperature stability coefficients of the ceramic samples with different doping amounts at 25-250 ℃ are 22.5%, 12.5%, 22% and 11.3%, respectively. It can be seen that the ceramic of example 2 has a significant stability in the temperature range 25-250 c, with a temperature coefficient of less than 15%. When the temperature is greater than 250 ℃, the dielectric constant begins to increase substantially, which may be related to the increased thermal motion of the ions at high temperatures.
The foregoing description of the preferred embodiment of the invention is merely illustrative of the invention and is not intended to be limiting. It will be appreciated by persons skilled in the art that many variations, modifications, and even equivalents may be made thereto without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. SnO (tin oxide) 2 The base ceramic material is characterized by being prepared from the following raw materials in parts by mole: snO (SnO) 2 85-98 parts of powder, bi 2 O 3 1 to 7.5 parts of powder, nb 2 O 5 1 to 7.5 parts of powder, wherein Bi 2 O 3 And Nb (Nb) 2 O 5 The molar ratio of (2) is 1:1;
the SnO 2 The dielectric property of the base ceramic material is within the test frequency range of 100 Hz-1 MHz, and the dielectric constant is 10 4 Magnitude, dielectric loss is lower than 0.065; in the test temperature range of-50 to 250 ℃, the dielectric constant is 10 3 In order of magnitude, the dielectric loss is lower than 0.1.
2. The SnO of claim 1 2 The base ceramic material is characterized by being prepared from the following raw materials in parts by mole: snO (SnO) 2 90-95 parts of powder and Bi 2 O 3 2.5 to 5 parts of powder, nb 2 O 5 2.5-5 parts of powder, wherein Bi 2 O 3 And Nb (Nb) 2 O 5 The molar ratio of (2) is 1:1.
3. SnO according to claim 1 or 2 2 The preparation method of the base ceramic material comprises the following steps:
(1) SnO is prepared 2 、Bi 2 O 3 And Nb (Nb) 2 O 5 The raw materials are mixed according to the proportion, ball milling is carried out, and mixed powder is obtained after filtration and drying;
(2) Adding an adhesive into the mixed powder obtained in the step (1) for granulating; vacuum packaging the material obtained by granulation, and performing temperature isostatic pressing to obtain a compressed material;
(3) Grinding, granulating, tabletting and forming the compressed material obtained in the step (2) to obtain a green sheet, performing cold isostatic pressing and glue discharging treatment on the obtained green sheet, and sintering to obtain SnO 2 A base ceramic material.
4. The SnO of claim 3 2 The preparation method of the base ceramic material is characterized in that the ball milling step in the step (1) is as follows: snO is prepared 2 、Bi 2 O 3 And Nb (Nb) 2 O 5 Mixing the raw materials according to the proportion, and then adding the mixture into a ball milling tank containing zirconia and deionized water for ball milling; the ball-material ratio in the ball milling process is 3-5:1; the mass of the deionized water and SnO 2 、Bi 2 O 3 And Nb (Nb) 2 O 5 The ratio of the total mass of the raw materials is 0.5-1:1; the ball milling rotating speed is 300-500 r/min, the ball milling process is provided with forward and reverse direction alternate rotation, the interval time is 5min, and the ball milling time is 10-15 h; the drying is carried out for 10-15 hours at the temperature of 70-80 ℃; the D90 particle size of the obtained mixed powder is 2.0-2.2 mu m.
5. The SnO of claim 3 2 The preparation method of the base ceramic material is characterized in that the adhesive in the step (2) is deionized water; the mass ratio of the adhesive to the mixed powder is 1-3:1;
the vacuum packaging is tabletting packaging under the pressure of 2-4 MPa by using a dry pressing tablet press; the pressure of the temperature isostatic pressing is 300-350 MPa, the boosting rate of the temperature isostatic pressing is 2MPa/s, and the pressure maintaining time is 10s.
6. The SnO of claim 3 2 The preparation method of the base ceramic material is characterized in that the granulating step in the step (3) is as follows: adding deionized water into the powder obtained by grinding for granulation, wherein the mass ratio of the deionized water to the powder is 2-5:1;
the tabletting and forming steps are as follows: and pressing the powder obtained by granulation into a green sheet with the diameter of 10mm and the thickness of 2mm under the pressure of 2-4 MPa.
7. The SnO of claim 3 2 A method for preparing a base ceramic material, characterized in that the conditions for cold isostatic pressing in step (3) are: the pressure of the cold isostatic pressing is 300-350 MPa, the pressure rising rate of the cold isostatic pressing is 2MPa/s, and the pressure maintaining time is 10s.
8. The SnO of claim 3 2 The preparation method of the base ceramic material is characterized in that the temperature of the glue discharging in the step (3) is 600-700 ℃, the time of glue discharging is 0.5-2 h, and the heating rate is 3-5 ℃/min.
9. The SnO of claim 3 2 A method for producing a base ceramic material, characterized by the steps of(3) The sintering temperature is 1200-1500 ℃, the sintering time is 3-5 h, and the heating rate is 3-5 ℃/min.
10. SnO according to claim 1 or 2 2 The use of a ceramic-based material in miniature capacitors, high density stored energy devices or integrated electronic devices.
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