CN1258783C - High-dielectric constant and reduction resistant dielectric material for capacitor with basic-metal electrode - Google Patents

Abstract

The present invention discloses a high-dielectric constant and reduction resistant dielectric material for a capacitor with a base metal electrode, which belongs to the preparing technical field of a capacitor material. Main components of the material comprise a solid solution Bax (ZrySnzTi1-y-z) O3 of BaTiO3, BaZrO3 and BaSnO3, and a ceramic material composed of a secondary additive and more than one rare earth oxide, the main components can be sintered in two steps in a temperature range of 1000 DEG C to 1350 DEG C and under reducing atmosphere, and the Y5V high-dielectric constant and reduction resistant dielectric material for a capacitor with a base metal electrode is formed, which has good dielectric property and microstructure. The material has a room temperature dielectric constant of 8000 to 15000, a capacitance temperature variance ratio of-82 % to +22%, room temperature dielectric loss not more than 2.5%, alternating current breakdown field strength higher than 4.5 kv/mm, and a ceramic grain size of 500 to 2500mm. The ceramic material and a base metal together can be fired into a monolith capacitor. The present invention is suitable for manufacturing an MLCC material which has the advantages of the large capacity of a base metal electrode and extensive use foreground.

Description

High-dielectric, reduction-resistant capacitive dielectric materials for base metal electrodes

technical field

The invention belongs to the technical field of capacitor materials, in particular to a high-dielectric and anti-reduction capacitor dielectric material used for base metal electrodes.

Background technique

With the rapid development of the electronics industry, miniaturization and light weight have become the development trend of various electronic products such as digital cameras, mobile phones, notebook computers, handheld computers, etc., which requires that the components that make up these electronic devices must be reduced in size and weight , and can adapt to the needs of surface mount technology (SMD). The components required by surface mount technology are chip components. Multilayer ceramic capacitors, multilayer ceramic inductors and chip resistors are the three most widely used passive components in chip components. Multilayer Ceramic Capacitors (Multilayer Ceramic Capacitors) is referred to as MLCC, which alternately stacks multilayer inner electrode materials and ceramic bodies, co-fires a monolithic body, and coats the outer electrodes on both ends of the monolithic body, respectively. Alternately exposed inner electrodes are electrically connected. According to the EIA (Electronic Industries Association) standard, the Y5V type MLCC refers to the capacitance value at 25°C as the reference, and within the temperature range from -30°C to +85°C, the capacity temperature change rate is between +22 %～-82%, dielectric loss (DF)≤2.5%. Y5V type MLCC is divided into two categories according to the composition: one is composed of lead-containing ferroelectrics, and the other is composed of non-lead ferroelectrics based on BaTiO ₃ solid solution. Among them, because the latter has less environmental pollution, and its mechanical strength, anti-aging performance, platability and reliability are superior to the former, the non-lead Y5V type MLCC has broad application prospects.

Compared with lead-based ferroelectric ceramics, barium titanate and its solid solution materials need to be sintered at a higher temperature (1100 ° C ~ 1350 ° C), so multilayer ceramic capacitors composed of such materials need to use precious metals (Pt , Au, Pd, Ag and other metals and their alloys, etc.) as internal electrodes. The high price of these precious metals has greatly increased the production cost of MLCC, and the use of cheap metal materials to replace noble metals as internal electrode materials has become an important way to reduce the cost of MLCC. Commonly used base metal internal electrode materials include Ni, Fe, Co, Cu and their alloys. When sintered in air, the internal electrode base metal in MLCC will be oxidized by oxygen in the air to form oxides that are not easily conductive and lose As an internal electrode, the sintering of the base metal internal electrode MLCC must use a neutral or reducing atmosphere. At the same time, in order to ensure that barium titanate-based dielectric ceramics are not reduced to semiconductors when sintered in a neutral or reducing atmosphere, and have sufficient insulation performance and high breakdown resistance, the sintering of the base metal inner electrode MLCC generally adopts two stages. Type sintering, that is, sintering at a relatively high temperature range of 1100°C to 1350°C to obtain a dense monolithic body, the oxygen partial pressure of the sintering atmosphere is between 10 ^-6 and 10 ^-12 Pa, and then at 1000°C to 1100 Annealing is carried out in an atmosphere with an oxygen partial pressure of 10 ^-3 ~ 10 ^-8 Pa at a temperature of ℃, so as to improve the insulation resistance and breakdown resistance of ceramics and ensure the reliability of MLCC. The atmosphere in the sintering process is generally composed of nitrogen, hydrogen and water vapor, or nitrogen, carbon monoxide and carbon dioxide, and the sintering atmosphere and annealing atmosphere with a specific oxygen partial pressure can be obtained by adjusting the composition of the mixed gas. At present, in the US patent US 5361187, the Y5V dielectric ceramic uses (Ba _1-x Ca _x )(Ti _1-yz Sn _y Zr _z )O ₃ based solid solution as the main material, and obtains a relatively high room temperature dielectric constant (8000 ~19000), but can only be sintered in air, which limits the application of this type of material in base metal inner electrode MLCC. U.S. Patent US 6078494 uses modified (Ba _x Ca _y )(T _z Zr _w )O ₃ perovskite ferroelectric ceramics to obtain anti-reduction Y5V type high-dielectric (≥20000) ceramics, but its composition is very complicated and the process The conditions are harsh, and the grain size of ceramics is large (3-5 μm), and the dielectric loss at room temperature is large, so it is not suitable for manufacturing high-performance multilayer ceramic capacitors with a single-layer dielectric thickness less than 10 μm.

Contents of the invention

The purpose of the present invention is to provide a high dielectric and anti-reduction capacitor dielectric material for base metal electrodes with simple preparation process, simple and adjustable formula, easy control of sintering conditions, and excellent dielectric properties. The material is composed of main material solid solution and The secondary additive composition is characterized in that: the main material solid solution Ba _x ( _{Zry Snz} Ti _1-yz ) O ₃ is composed of barium titanate BaTiO ₃ , barium zirconate BaZrO ₃ and barium stannate BaSnO ₃ , wherein 0.995≤x≤1.01, 0.10≤y≤0.20, 0≤z≤0.10, the number of moles in the formula is 96-98mol%; the amount of the secondary additives accounts for 2-4mol% of the total amount of materials, Precursors including CaO, TiO ₂ , SiO ₂ , Li ₂ O, MnO ₂ , ZnO and one or more rare earth oxides M ₂ O ₃ , or secondary additives; The ratio of the meter is: CaO: 0.3～1.0mol%; TiO ₂ : 0.1～0.5mol%; SiO ₂ : 0～0.5mol%; Li ₂ O: 0.2～1.5mol%; MnO ₂ : 0.4～1.4mol% ; ZnO: 0.8-2.5 mol%; Re ₂ O ₃ : 0.2-1.2 mol%.

The particle size of the constituent materials of the main material solid solution is required to be less than 1000nm; the powder particle size of the secondary additive is required to be less than 600nm; The deposit is calcined at 800°C to 900°C and ball milled.

The precursors of the secondary additives include carbonates, hydroxides, oxalates, acetates, nitrates, citrates and alkoxides: titanium tetrabutoxide, or calcium ethoxide, or zinc ethoxide.

M in the rare earth oxide M ₂ O ₃ represents: La-lanthanum, Ce-cerium, Pr-praseodymium, Nd-neodymium, Sm-samarium, Eu-europium, Gd-gadolinium, Tb-terbium, Dy-dysprosium, Ho - Holmium, Er-erbium, Tm-thulium, Yb-ytterbium, Lu-lutetium, and Y-yttrium.

The specific process steps for manufacturing multilayer ceramic capacitors-MLCC are as follows:

(1) Mix powdered barium carbonate, zirconium dioxide, tin dioxide and titanium dioxide, use water as the medium, and zirconia balls as the grinding medium, and ball mill in a nylon tank for 24 hours;

(2) calcining the dried above-mentioned mixture at 1100°C<T≤1200°C under a low partial oxygen pressure of 10 ^-7 to 1.2×10 ^-12 to synthesize a solid solution main material with a perovskite structure;

(3) The precursor of the secondary additive is required to be uniformly mixed in the form of a solution, then dried and deposited, and then the deposit is calcined at 800° C. to 900° C. and ball milled.

(4) Grinding of the main material of the solid solution: using water as the medium and zirconia balls as the grinding medium, ball milling in a nylon tank for 48 hours to obtain the main material powder with a particle size of less than 1000nm;

(5) Mix the above solid solution powder with secondary additives, add appropriate organic solvent n-propyl acetate, binder polyvinyl butyral, plasticizer dioctyl phthalate, dispersant polyacrylic acid Ammonium, using zirconia balls as a grinding medium in a nylon tank for ball milling for 48 hours to obtain cast slurry;

(6) Casting the dielectric layer with the above-mentioned casting slurry: the thickness of the dielectric layer is 10 μm or less;

(7) printing a base metal internal electrode layer on the above-mentioned dielectric layer, and then stacking the tape-cast dielectric layers printed with internal electrodes, cutting after hot pressing to form a MLCC green body;

(8) Debinding: In the temperature range of 300°C to 340°C, keep warm in the air for 20 hours to remove organic substances in the MLCC green body, and the heating rate of the debinding process is not higher than 10°C/h;

(9) Sintering in a reducing atmosphere: a mixed gas of N ₂ /H ₂ /H ₂ O is introduced during the sintering process, the oxygen partial pressure is controlled within the range of 10 ^-6 ~ 10 ^-12 Pa, and the furnace temperature is controlled at 1100 ℃＜T＜1350℃;

(10) Annealing under weak oxidation conditions: the furnace temperature is 1000°C<T<1100°C, heat preservation for 2 to 4 hours, and the oxygen partial pressure is controlled within the range of 10 ^-3 to 10 ^-8 Pa;

(11) Coating terminal electrodes: the terminal electrodes are Cu or Ag, the furnace temperature is 700°C-850°C, heat preservation for 1 hour, nitrogen protection, and after natural cooling, a Y5V base metal inner electrode multilayer ceramic capacitor is obtained.

The beneficial effect of the invention is that according to the material formula of the invention, a Y5V type high dielectric and anti-reduction capacitor dielectric material with excellent performance can be sintered at a temperature of 1200°C or lower than 1350°C. Its room temperature dielectric constant can be controlled between 8,000 and 15,000, and the temperature change rate in the range of -30°C to +85°C is +22% to -82%, which meets the requirements of EIA-Y5V, and the dielectric loss at room temperature is ≤2.5%. The AC breakdown field strength is higher than 4.5kV/mm, and the ceramic grain size is between 500nm and 2,500nm. It is suitable for the manufacture of multilayer ceramic capacitors with thin layers (≤10μm), number of layers, and large capacity using base metal as the internal electrode material.

Description of drawings

Fig. 1 is the variation curve of the dielectric constant and temperature of embodiment 1 sample;

Fig. 2 is the photomicrostructure of the natural surface of embodiment 1 sample;

Fig. 3 is the variation curve of the dielectric constant and temperature of embodiment 2 sample;

Fig. 4 is the photomicrostructure of the natural surface of embodiment 2 sample;

Fig. 5 is the variation curve of the dielectric constant and temperature of embodiment 3 samples;

Fig. 6 is a photo of the microstructure of the natural surface of the sample of Example 3.

Detailed ways

The invention is a high dielectric and anti-reduction capacitor dielectric material for base metal electrodes with simple preparation process, simple and adjustable formula, easy control of sintering conditions and excellent dielectric properties. The material is composed of barium titanate BaTiO ₃ and zirconium Barium oxide BaZrO ₃ and barium stannate BaSnO ₃ solid solution Ba _x ( _Zry Sn _z Ti _1-yz )O ₃ and secondary additive composition, the main material solid solution Ba _x (Zry _y Sn _z Ti _1-yz )O _3. The number of moles in the formula is 96-98 mol%; the amount of the secondary additive accounts for 2-4 mol% of the total amount of materials. Among them, 0.995≤x≤1.01, 0.10≤y≤0.20, 0≤z≤0.10, the particle size of the main material is required to be less than 1000nm. The secondary additives include CaO, TiO ₂ , SiO ₂ , Li ₂ O, MnO ₂ , ZnO and one or more rare earth oxides M ₂ O ₃ , or the precursors of the secondary additives: including carbon salt, hydroxide, oxalate, acetate, nitrate, citrate, and alkoxide (titanium tetrabutoxide, calcium ethoxide, zinc ethoxide, etc., not specific to a certain alkoxide). The ratio of each material described is (by mole): CaO: 0.3-1.0 mol%; TiO ₂ : 0.1-0.5 mol%; SiO ₂ : 0-0.5 mol%; Li ₂ O: 0.2-1.5 mol%; MnO ₂ : 0.4-1.4 mol %; ZnO: 0.8-2.5 mol %; Re ₂ O ₃ : 0.2-1.2 mol %.

M in rare earth oxide M ₂ O ₃ represents: La-lanthanum, Ce-cerium, Pr-praseodymium, Nd-neodymium, Sm-samarium, Eu-europium, Gd-gadolinium, Tb-terbium, Dy-dysprosium, Ho-holmium , Er-erbium, Tm-thulium, Yb-ytterbium, Lu-lutetium, and Y-yttrium.

In the above-mentioned secondary addition, the powder particle size requires less than 600nm, and the precursor of the secondary addition requires a solution (solvent is generally water, ethanol, acetic acid or their mixture, for carbonate, acetate, nitric acid Salt and other salts that are easily soluble in water, the solvent is water, ethanol can be used for alkoxide to prevent hydrolysis, acetate, oxalate, etc. can be mixed with acetic acid or an aqueous solution of acetic acid as a solvent) and then dried and deposited , and then the deposit is calcined at 800°C to 900°C and ball milled.

The specific process steps for manufacturing MLCC are as follows:

(1) Mix powdered barium carbonate, zirconium dioxide, tin dioxide and titanium dioxide, use water as the medium, and zirconia balls as the grinding medium, and ball mill in a nylon tank for 24 hours;

(2) calcining the dried above-mentioned mixture at 1100°C<T≤1200°C under a low partial oxygen pressure of 10 ^-7 to 1.2×10 ^-12 to synthesize a solid solution main material with a perovskite structure;

(3) Grinding of the main material of the solid solution: using water as the medium and zirconia balls as the grinding medium, ball milling in a nylon tank for 48 hours to obtain the main material powder with a particle size of less than 1000nm;

(4) Mix the above-mentioned solid solution powder with secondary additives, add appropriate organic solvents, binders, plasticizers, dispersants, etc., and use zirconia balls as grinding media in nylon tanks for 48 hours to obtain fluid extended slurry;

(5) Casting the dielectric layer with the above-mentioned casting slurry: the thickness of the dielectric layer is 10 μm or less;

(6) Print a base metal internal electrode layer on the above-mentioned dielectric layer, then superimpose the tape-cast dielectric layers printed with internal electrodes, and cut after hot pressing to form a MLCC green body;

(7) Debinding: In the temperature range of 300°C to 340°C, keep warm in the air for 20 hours to remove organic substances in the MLCC green body, and the heating rate of the debinding process is not higher than 10°C/h;

(8) Sintering in a reducing atmosphere: During the sintering process, a mixed gas of N ₂ /H ₂ /H ₂ O is introduced to control the partial pressure of oxygen in the range of 10 ^-6 ~ 10 ^-12 Pa. The furnace temperature is controlled by The temperature is raised to 1250°C at a rate of 200°C/hour, and the holding time is 2 hours;

(9) Annealing under weak oxidation conditions: the furnace temperature is 1000°C<T<1100°C, heat preservation for 2 to 4 hours, and the oxygen partial pressure is controlled within the range of 10 ^-3 to 10 ^-8 Pa;

(10) Coating terminal electrodes: the terminal electrodes are Cu or Ag, the furnace temperature is 700°C-850°C, heat preservation for 1 hour, nitrogen protection, and after natural cooling, a Y5V type base metal inner electrode multilayer ceramic capacitor is obtained.

Give examples again below to further illustrate as follows:

Example 1, first synthesize perovskite solid solution according to Ba _x ( _Zry Sn _z Ti _1-yz )O ₃ (where x=1.005, y=0.13, z=0.04), the synthesis temperature is 1150°C, and the solid solution after ball milling The particle size is 570nm. Then according to Ba _x ( _{Zry Snz} Ti _1-yz )O ₃ solid solution: 96mol%; CaO: 0.4mol%; TiO ₂ : 0.5mol%; SiO ₂ : 0.2mol%; Li ₂ O: 0.4mol%; MnO ₂ : 0.6mol%; ZnO: 1.4mol%; Sm ₂ O ₃ : 0.3mol%; Dy ₂ O ₃ : 0.2mol% Proportional weighing. Mix the above materials, add an appropriate organic additive n-propyl acetate and ball mill, then cast into a film, superimpose with the printed Ni electrode to make a MLCC green body, after debinding, sinter in a reducing atmosphere (during the sintering process Introduce N ₂ /H ₂ , humidify at the same time, control the oxygen partial pressure at ^10-11 Pa, raise the temperature to 1260°C at a rate of 200°C/hour, and keep it for 2 hours), and then anneal under weak oxidation conditions (furnace The temperature was kept at 1100°C for 2 hours, and the oxygen partial pressure was controlled at 10 ^-7 Pa). Then apply and burn the Cu terminal electrode (furnace temperature at 850°C, heat preservation for 1 hour, nitrogen protection). Performance tests were performed on the above-mentioned multilayer ceramic capacitors, and the electrical performance parameters are shown in Table 1. The curve in Fig. 1 shows the variation curve of the dielectric constant of the sample in this embodiment with temperature, and Fig. 2 shows the microstructure of the natural surface of the sample, and the grain size is between 1500-2000 nm.

Table 1 Electrical performance parameters of sample 1 Ingredients Sintering conditions TCC(%)(-30℃) Dielectric constant(25℃) TCC(%)(85℃) TCC(%)(T _C ＝15℃) tgδ(%)(25℃) ρ25℃(Ω·cm) E _B25℃ (ACkV/mm) Ba _1.005 (Zr _0.13 Sn _0.04 Ti _0.83 )O ₃ 1260℃×2 hours -62.8 12200 -70.4 +9.4 1.30 2.0×10 ¹¹ 4.9

Example 2, first synthesize perovskite solid solution according to Ba _x ( _Zry Sn _z Ti _1-yz )O ₃ (where x=1.002, y=0.17, z=O), the synthesis temperature is 1150°C, and the solid solution after ball milling The particle size is 410 nm. Then according to Ba _x ( _{Zry Snz} Ti _1-yz )O ₃ solid solution: 97mol%; CaO: 0.3mol%; TiO ₂ : 0.1mol%; SiO ₂ : 0.2mol%; Li ₂ O: 0.2mol%; MnO ₂ : 0.5mol%; ZnO: 1.2mol%; Nd ₂ O ₃ : 0.2mol%; La ₂ O ₃ : 0.3mol% Proportional weighing. Mix the above materials, add an appropriate organic additive n-propyl acetate and ball mill, then cast into a film, superimpose with the printed Ni electrode to make a MLCC green body, after debinding, sinter in a reducing atmosphere (during the sintering process Introduce N ₂ /H ₂ , humidify at the same time, control the oxygen partial pressure at ^10-11 Pa, raise the temperature to 1220°C at a rate of 200°C/hour, and keep it for 2 hours), and then anneal under weak oxidation conditions (furnace The temperature was kept at 1100°C for 3 hours, and the oxygen partial pressure was controlled at 10 ^-7 Pa). Then apply and burn Cu terminal electrodes (furnace temperature at 850°C, keep warm for 1 hour, nitrogen protection). Performance tests were performed on the above-mentioned multilayer ceramic capacitors, and the electrical performance parameters are shown in Table 2. The curve in Fig. 3 shows the variation curve of the dielectric constant of the sample in this embodiment with temperature, and Fig. 4 shows the microstructure of the fresh section of the sample, and the grain size is between 800-1000nm.

Table 2 Electrical performance parameters of sample 2 Ingredients Sintering conditions TCC(%)(-30℃) Dielectric constant(25℃) TCC(%)(85℃) TCC(%)(T _C ＝10℃) tgδ(%)(25℃) ρ25℃(Ω·cm) E _B25℃ (ACkV/mm) Ba _1.002 (Zr _0.17 Ti _0.83 )O ₃ 1220℃×2 hours -49.4 8816 -65.3 +9.3 1.07 3.2×10 ¹¹ 5.1

Example 3, the perovskite solid solution was first synthesized according to Ba _x ( _{Zry Snz} Ti _1-yz )O ₃ (where x=0.998, y=0.14, z=0.08), the synthesis temperature was 1150°C, and the solid solution after ball milling The particle size is 650nm. Then according to Ba _x ( _{Zry Snz} Ti _1-yz )O ₃ solid solution: 97mol%; CaO: 0.8mol%; TiO ₂ : 0.2mol%; SiO ₂ : 0mol%; Li ₂ O: 0.2mol%; MnO ₂ : 0.4mol%; ZnO: 1.0mol%; Yb ₂ O ₃ : 0.2mol%; Ho ₂ O ₃ : 0.2mol%. Mix the above materials, add an appropriate organic additive n-propyl acetate and ball mill, then cast into a film, superimpose with the printed Ni electrode to make a MLCC green body, after debinding, sinter in a reducing atmosphere (during the sintering process Introduce N ₂ /H ₂ , humidify at the same time, control the oxygen partial pressure at ^10-11 Pa, raise the temperature to 1300°C at a rate of 200°C/hour, and keep it for 2 hours), and then anneal under weak oxidation conditions (furnace The temperature was kept at 1050°C for 4 hours, and the oxygen partial pressure was controlled at 10 ^-7 Pa). Then apply and burn the Cu terminal electrode (furnace temperature at 850°C, heat preservation for 1 hour, nitrogen protection). Performance tests were performed on the above-mentioned multilayer ceramic capacitors, and the electrical performance parameters are shown in Table 3. The curve in Fig. 5 shows the variation curve of the dielectric constant of the sample in this embodiment with temperature, and Fig. 6 shows the microstructure of the natural surface of the sample, and the grain size is between 1500-2500nm.

Table 3 Electrical performance parameters of sample 3 Ingredients Sintering conditions TCC(%)(-30℃) Dielectric constant(25℃) TCC(%)(85℃) TCC(%)(T _C ＝15℃) Tgδ(%)(25℃) ρ ₂₅ ℃ (Ω·cm) E _B25℃ (ACkV/mm) Ba _0.998 (Zr _0.14 Sn _0.08 Ti _0.78 )O ₃ 1220℃×2 hours -66.7 13610 -72.2 +8.9 1.58 2.8×10 ¹¹ 4.7

In the above-mentioned embodiments, in the temperature range of 1100°C<T≤1200°C, a barium titanate solid solution-based base metal internal electrode high dielectric and reduction-resistant capacitor dielectric material meeting the performance index requirements of EIA-Y5V was prepared. Its room temperature dielectric constant can be controlled between 8,000 and 1,5000, the capacity temperature change rate between -30°C and +85°C is between +22% and -82%, and the dielectric loss is less than 2.5%. The insulation resistivity is about 10 ¹¹ Ω·cm, and the AC breakdown voltage is greater than 4.5KV/mn. Utilizing the formula and process of the invention, the anti-reduction barium titanate solid solution-based Y5V type MLCC material can be obtained with wide sintering temperature range, adjustable performance, good stability and reproducibility. Moreover, the crystal grains of the material are uniform, and the ceramic grain size is between 500nm and 2,500nm. It can be applied to large-capacity, ultra-thin layer (dielectric layer thickness less than 10 μm) multilayer ceramic capacitors, and is a MLCC material with broad application prospects.

1 to 6 above are the temperature characteristic curves and surface micromorphology of the dielectric constants of the samples corresponding to Examples 1 to 3. The test temperature of the medium temperature characteristic is -55℃～+125℃.

The meanings of the parameters in Table 1 to Table 3 are as follows:

TCC(-30°C): rate of change of capacity temperature at -30°C; TCC(85°C): rate of change of capacity temperature at 85°C;

tgδ(25℃): dielectric loss at room temperature, test frequency is 1kHz, test voltage is 1.0V;

TCC(T)%＝100×(ε(T)-ε(25℃))/ε(25℃): capacity temperature change rate;

ρ(25°C): Room temperature resistivity, the test condition is DC voltage 100V, hold for 60s;

E _b (25°C): AC breakdown field strength at room temperature, the frequency of the AC electric field is 50Hz.

Claims (4)

1. a kind of high dielectric for base metal electrode, anti-reduction capacitance medium material, this material is made up of main material solid solution and secondary additive, it is characterized in that: described main material solid solution Ba _x ( _Zry Sn _z Ti _1-yz )O ₃ is composed of barium titanate BaTiO ₃ and barium zirconate BaZrO ₃ and barium stannate BaSnO ₃ , in which 0.995≤x≤1.01, 0.10≤y≤0.20, 0≤z≤0.10, accounted for in the formula The molar number is 96-98mol%; the amount of the secondary additive accounts for 2-4mol% of the total material, including CaO, TiO ₂ , SiO ₂ , Li ₂ O, MnO ₂ , ZnO and one or one The above rare earth oxide M ₂ O ₃ , or the precursor of the secondary additive; the molar ratio of each material of the secondary additive is: CaO: 0.3～1.0mol%; TiO ₂ : 0.1～0.5mol %; SiO ₂ : 0-0.5 mol %; Li ₂ O: 0.2-1.5 mol %; MnO ₂ : 0.4-1.4 mol %; ZnO: 0.8-2.5 mol %; M ₂ O ₃ : 0.2-1.2 mol %. 2. The high dielectric material for base metal electrodes according to claim 1, characterized in that: the particle size of the constituent materials of the main material solid solution requires less than 1000nm; the secondary additive powder The particle size is required to be less than 600nm; the precursor of the secondary additive is required to be mixed uniformly in the form of a solution and then dried and deposited, and then the deposit is calcined at 800°C to 900°C and ball milled. 3. The high dielectric, anti-reduction capacitor dielectric material for base metal electrodes according to claim 1, characterized in that: the precursor of the secondary additive comprises carbonate, hydroxide, oxalate, Acetates, nitrates, citrates and alkoxides: titanium tetrabutoxide, or calcium ethoxide, or zinc ethoxide. 4. The high-dielectric, anti-reduction capacitor dielectric material for base metal electrodes according to claim 1, characterized in that: M represents in the rare earth oxide M ₂ O ₃ : La-lanthanum, Ce-cerium, Pr - Praseodymium, Nd-Neodymium, Sm-Samarium, Eu-Eurium, Gd-Gadolinium, Tb-Terbium, Dy-Dysprosium, Ho-Holmium, Er-Erbium, Tm-Thulium, Yb-Ytterbium, Lu-Lutetium, and Y- yttrium.

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