CN103342466B - Strontium barium niobate based glass-ceramic dielectric material and preparation method thereof - Google Patents

Strontium barium niobate based glass-ceramic dielectric material and preparation method thereof Download PDF

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CN103342466B
CN103342466B CN201310262140.1A CN201310262140A CN103342466B CN 103342466 B CN103342466 B CN 103342466B CN 201310262140 A CN201310262140 A CN 201310262140A CN 103342466 B CN103342466 B CN 103342466B
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strontium barium
barium niobate
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CN103342466A (en
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陈国华
宋俊
刘涛涌
袁昌来
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Guilin University of Electronic Technology
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Abstract

The invention relates to a strontium barium niobate based glass-ceramic dielectric material and a preparation method thereof. The preparation method comprises the following steps of: with SrCO3, BaCO3, Nb2O5 and H3BO3 as starting raw materials, proportioning according to the mole ratio of aSrO.bBaO.cNb2O5.dB2O3; carrying out ball milling, mixing the raw materials for 8h, and drying; melting at the temperature of 1300 DEG C, and preserving the heat for 30min; then, rapidly cooling and annealing to obtain astomatous uniform glass; carrying out controllable crystallization at a certain temperature to obtain the glass-ceramic dielectric material. The glass-ceramic dielectric material obtained by using the method has the adjustable relative dielectric constant within the range of 21-143, the highest direct current breakdown field strength of 1300kV/cm and the highest energy density of 5.71J/cm<3>.

Description

A kind of strontium barium niobate base microcrystal glass dielectric substance and preparation method thereof
Technical field
The present invention relates to a kind of dielectric material of glass-ceramics and preparation method thereof.Specifically, a kind of SrO-BaO-Nb is related to 2o 5-B 2o 3system dielectric material of glass-ceramics and preparation method thereof, belongs to ceramic material field.
Background technology
Along with energy dilemma consciousness and the raising gradually of environmental consciousness, people start the development and utilization attempting novel energy.As the important support means of new energy technology, energy storage technology obtains various countries and pays much attention to.Wherein electrical condenser has that specific power is high, charge velocities is fast, resistance to circulation is aging because of it, is applicable to the advantages such as High Temperature High Pressure occasion and environmentally safe and receives much concern.Current electrical condenser is applied on some visual plants, as hybrid vehicle invertor, pulse-power apparatus etc.
But existing traditional impulse capacitor to there is unfavorable factor as low in energy storage density and easily to blast or discharging current is little, discharge life is short, is difficult to meet the demand that new technology further develops.Ceramic dielectric material has some superiority preparing in high density capacitors, but its maximum shortcoming is that anti-breaking down field strength is difficult to rise again.The size of current capacitor element is more and more less, and the anti-breaking down field strength of needs is also more and more higher.Therefore, the dielectric substance with high energy storage density is developed extremely urgent.
Devitrified glass has the high-k of pottery and the advantage of high breakdown strength two aspect of glass concurrently, thus becomes and prepare the dielectric ideal material of high energy storage density.At present, research mainly concentrates on titanate devitrified glass and leaded niobate microcrystalline glass system, and is mostly system based on silicate or silicon borate glass.But, because the disruptive strength of titanate devitrified glass is on the low side, finally cause energy storage density not high, and energy storage density worsen when applying high electric field; Leaded niobate microcrystalline glass receives a definite limitation owing to making it apply containing more toxic substance plumbous oxide in composition, separates out a large amount of NaNbO during thermal treatment simultaneously 3be disadvantageous to improving the disruptive strength of material, and energy storage density is also not very high.In addition, the temperature of fusion of two system glass is higher (more than 1500 DEG C), is unfavorable for reducing costs and energy-saving and emission-reduction.
Summary of the invention
The object of this invention is to provide a kind of low-temperature growth strontium barium niobate base microcrystal glass dielectric substance and preparation method thereof.Dielectric substance prepared by the method has the advantage of high-k and high breakdown field strength concurrently, thus overcomes the deficiency existed in the preparation of existing dielectric material of glass-ceramics.
The technical scheme realizing the object of the invention is:
A kind of strontium barium niobate base microcrystal glass dielectric substance, its chemical formula is aSrObBaOcNb 2o 5dB 2o 3, wherein the molar percentage of each material is: 0.33≤a/b≤3.0, c=0.32, d=0.36, a+b+c+d=1.
A kind of preparation method of strontium barium niobate base microcrystal glass dielectric substance, it is the ratio by regulating SrO and BaO in devitrified glass composition, utilize high-temperature fusion and the controlled Crystallization method of subsequent heat treatment, prepare strontium barium niobate base microcrystal glass dielectric substance, specifically comprise the steps:
(1) SrCO of 99% is greater than with purity 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, in strict accordance with aSrObBaOcNb 2o 5dB 2o 3ratio batching, then these raw materials are added in horizontal ball mill ball-milling medium grinding 8h, after oven dry 1300 DEG C insulation 30min be melting into uniform glass liquid;
(2) be poured into rapidly in metal die shaping by the high temp glass liquid that step (1) obtains, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1 ~ 2cm 2rectangular glass sheet;
(3) sheet glass prepared by step (2) is carried out Controlled Crystallization, this Crystallization Process is divided into two steps: first make nucleation at 610 DEG C of insulation 2h, then make nuclei growth at 750-850 DEG C of insulation 3h, the strontium barium niobate obtaining having tungsten bronze structure is the dielectric material of glass-ceramics of principal crystalline phase;
(4) dielectric material of glass-ceramics that step (3) obtains is carried out processing treatment, rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
(5) glass-ceramic dielectric thin slice step (4) obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste, at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
Described abrading-ball is agate ball, and ball-milling medium is dehydrated alcohol or deionized water.
Described forming metal mold material is cast iron or copper, and shape is rectangle or circle.
The source of described middle temperature silver paste is commercially available.
Advantage of the present invention is, by control SrO-BaO-Nb 2o 5-B 2o 3the content of Sr and Ba in composition, obtains the dielectric material of glass-ceramics of a kind of high-k, high breakdown strength and high energy storage density; The specific inductivity of gained glass-ceramic dielectric is up to 143, and disruptive strength 850-1300kV/cm is adjustable; Can be used for the preparation of various high energy storage density and extra-high voltage capacitors; Reduce the temperature of fusion cast glass simultaneously, reach the object of energy-conserving and environment-protective.
Accompanying drawing explanation
Fig. 1 is SrO-BaO-Nb in embodiment 1,2,3,4,5 and 6 2o 5-B 2o 3the XRD figure spectrum of system glass-ceramic dielectric sample.
Embodiment
The description that the method that the present invention prepares strontium barium niobate base microcrystal glass dielectric substance can obtain clearly by following nonlimiting examples.
embodiment 1
A kind of strontium barium niobate base microcrystal glass dielectric substance and preparation method thereof, it forms Sr/Ba=0.33.
1. be greater than 99%SrCO with purity 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, according to SrO:BaO:Nb 2o 5: B 2o 3=a:b:c:d=0.08:0.24:0.32:0.36 molar ratio ingredient, the total consumption of all raw materials is 150 grams.Then these raw materials are added in horizontal ball mill ball-milling medium (agate ball and dehydrated alcohol) and grind 8h, after oven dry, be fused into glass metal at 1300 DEG C of insulation 30min;
2. be poured into rapidly in metal die shaping by the high temp glass liquid of step 1 gained, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1cm 2the rectangular glass sheet of left and right;
3. sheet glass step 2 prepared carries out Controlled Crystallization, and this Crystallization Process is divided into two steps: first 610 DEG C of insulation 2h nucleation, then make nuclei growth at 800 DEG C of insulation 3 h, obtain glass-ceramic dielectric dielectric medium, sample XRD figure spectrum as shown in Figure 1;
4. dielectric material of glass-ceramics step 3 obtained carries out processing treatment, and rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
5. glass-ceramic dielectric thin slice step 4 obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste (purchase of Gui Yanbo industry company), at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
Gained dielectric material of glass-ceramics specific inductivity be 132, dielectric loss is 0.015, and breaking down field strength is 951 kV/cm, and energy storage density is 5.29 J/cm 3.Test condition: test frequency 1kHz, room temperature; Disruptive strength is taking silicone oil as medium, and probe temperature is room temperature.
embodiment 2
A kind of strontium barium niobate base microcrystal glass dielectric energy storage material and preparation method thereof, it forms Sr/Ba=0.54.
1. be greater than 99%SrCO with purity 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, according to SrO:BaO:Nb 2o 5: B 2o 3=a:b:c:d=0.112:0.208:0.32:0.36 molar ratio ingredient, the total consumption of all raw materials is 150 grams.Then these raw materials are added in horizontal ball mill ball-milling medium (agate ball and dehydrated alcohol) and grind 8h, after oven dry, be fused into glass metal at 1300 DEG C of insulation 30min;
2. be poured into rapidly in metal die shaping by the high temp glass liquid of step 1 gained, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1cm 2the rectangular glass sheet of left and right;
3. sheet glass step 2 prepared carries out Controlled Crystallization, and this Crystallization Process is divided into two steps: first 610 DEG C of insulation 2h nucleation, then make nuclei growth at 800 DEG C of insulation 3 h, obtain glass-ceramic dielectric dielectric medium, sample XRD figure spectrum as shown in Figure 1;
4. dielectric material of glass-ceramics step 3 obtained carries out processing treatment, and rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
5. glass-ceramic dielectric thin slice step 4 obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste (purchase of Gui Yanbo industry company), at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
The specific inductivity of gained dielectric material of glass-ceramics is 120, and dielectric loss is 0.0135, and breaking down field strength is 996 kV/cm, and energy storage density is 5.27J/cm 3.Test condition: test frequency 1kHz, room temperature; Disruptive strength is taking silicone oil as medium, and probe temperature is room temperature.
embodiment 3
A kind of strontium barium niobate base microcrystal glass dielectric energy storage material and preparation method thereof, it forms Sr/Ba=0.82.
1. be greater than 99%SrCO with purity 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, according to SrO:BaO:Nb 2o 5: B 2o 3=a:b:c:d=0.112:0.208:0.32:0.36 molar ratio ingredient, the total consumption of all raw materials is 150 grams.Then these raw materials are added in horizontal ball mill ball-milling medium (agate ball and dehydrated alcohol) and grind 8h, after oven dry, be fused into glass metal at 1300 DEG C of insulation 30min;
2. be poured into rapidly in metal die shaping by the high temp glass liquid of step 1 gained, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1cm 2the rectangular glass sheet of left and right;
3. sheet glass step 2 prepared carries out Controlled Crystallization, and this Crystallization Process is divided into two steps: first 610 DEG C of insulation 2h nucleation, then make nuclei growth at 800 DEG C of insulation 3 h, obtain glass-ceramic dielectric dielectric medium, sample XRD figure spectrum as shown in Figure 1;
4. dielectric material of glass-ceramics step 3 obtained carries out processing treatment, and rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
5. glass-ceramic dielectric thin slice step 4 obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste (purchase of Gui Yanbo industry company), at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
The specific inductivity of gained dielectric material of glass-ceramics is 117, and dielectric loss is 0.0128, and breaking down field strength is 1050 kV/cm, and energy storage density is 5.27J/cm 3.Test condition: test frequency 1kHz, room temperature; Disruptive strength is taking silicone oil as medium, and probe temperature is room temperature.
embodiment 4
A kind of strontium barium niobate base microcrystal glass dielectric energy storage material and preparation method thereof, it forms Sr/Ba=1.22.
1. be greater than 99%SrCO with purity 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, according to SrO:BaO:Nb 2o 5: B 2o 3=a:b:c:d=0.112:0.208:0.32:0.36 molar ratio ingredient, the total consumption of all raw materials is 150 grams.Then these raw materials are added in horizontal ball mill ball-milling medium (agate ball and dehydrated alcohol) and grind 8h, after oven dry, be fused into glass metal at 1300 DEG C of insulation 30min;
2. be poured into rapidly in metal die shaping by the high temp glass liquid of step 1 gained, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1cm 2the rectangular glass sheet of left and right;
3. sheet glass step 2 prepared carries out Controlled Crystallization, and this Crystallization Process is divided into two steps: first 610 DEG C of insulation 2h nucleation, then make nuclei growth at 800 DEG C of insulation 3 h, obtain glass-ceramic dielectric dielectric medium, sample XRD figure spectrum as shown in Figure 1;
4. dielectric material of glass-ceramics step 3 obtained carries out processing treatment, and rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
5. glass-ceramic dielectric thin slice step 4 obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste (purchase of Gui Yanbo industry company), at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
The specific inductivity of gained dielectric material of glass-ceramics is 36, and dielectric loss is 0.0079, and breaking down field strength is 1158 kV/cm, and energy storage density is 2.14J/cm 3.Test condition: test frequency 1kHz, room temperature; Disruptive strength is taking silicone oil as medium, and probe temperature is room temperature.
embodiment 5
A kind of strontium barium niobate base microcrystal glass dielectric energy storage material and preparation method thereof, it forms Sr/Ba=1.86.
1. be greater than 99%SrCO with purity 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, according to SrO:BaO:Nb 2o 5: B 2o 3=a:b:c:d=0.112:0.208:0.32:0.36 molar ratio ingredient, the total consumption of all raw materials is 150 grams.Then these raw materials are added in horizontal ball mill ball-milling medium (agate ball and dehydrated alcohol) and grind 8h, after oven dry, be fused into glass metal at 1300 DEG C of insulation 30min;
2. be poured into rapidly in metal die shaping by the high temp glass liquid of step 1 gained, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1cm 2the rectangular glass sheet of left and right;
3. sheet glass step 2 prepared carries out Controlled Crystallization, and this Crystallization Process is divided into two steps: first 610 DEG C of insulation 2h nucleation, then make nuclei growth at 800 DEG C of insulation 3 h, obtain glass-ceramic dielectric dielectric medium, sample XRD figure spectrum as shown in Figure 1;
4. dielectric material of glass-ceramics step 3 obtained carries out processing treatment, and rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
5. glass-ceramic dielectric thin slice step 4 obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste (purchase of Gui Yanbo industry company), at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
The specific inductivity of gained dielectric material of glass-ceramics is 31, and dielectric loss is 0.0063, and breaking down field strength is 1177 kV/cm, and energy storage density is 1.90J/cm 3.Test condition: test frequency 1kHz, room temperature; Disruptive strength is taking silicone oil as medium, and probe temperature is room temperature.
embodiment 6
A kind of strontium barium niobate base microcrystal glass dielectric energy storage material and preparation method thereof, it forms Sr/Ba=3.0.
1. be greater than 99%SrCO with purity 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, according to SrO:BaO:Nb 2o 5: B 2o 3=a:b:c:d=0.112:0.208:0.32:0.36 molar ratio ingredient, the total consumption of all raw materials is 150 grams.Then these raw materials are added in horizontal ball mill ball-milling medium (agate ball and dehydrated alcohol) and grind 8h, after oven dry, be fused into glass metal at 1300 DEG C of insulation 30min;
2. be poured into rapidly in metal die shaping by the high temp glass liquid of step 1 gained, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1cm 2the rectangular glass sheet of left and right;
3. sheet glass step 2 prepared carries out Controlled Crystallization, and this Crystallization Process is divided into two steps: first 610 DEG C of insulation 2h nucleation, then make nuclei growth at 800 DEG C of insulation 3 h, obtain glass-ceramic dielectric dielectric medium, sample XRD figure spectrum as shown in Figure 1;
4. dielectric material of glass-ceramics step 3 obtained carries out processing treatment, and rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
5. glass-ceramic dielectric thin slice step 4 obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste (purchase of Gui Yanbo industry company), at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
The specific inductivity of gained dielectric material of glass-ceramics is 26.0, and dielectric loss is 0.0042, and breaking down field strength is 1248 kV/cm, and energy storage density is 1.79J/cm 3.Test condition: test frequency 1kHz, room temperature; Disruptive strength is taking silicone oil as medium, and probe temperature is room temperature.
embodiment 7
A kind of strontium barium niobate base microcrystal glass dielectric substance and preparation method thereof, it forms Sr/Ba=0.33.
1. be greater than 99%SrCO with purity 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, according to SrO:BaO:Nb 2o 5: B 2o 3=a:b:c:d=0.08:0.24:0.32:0.36 molar ratio ingredient, the total consumption of all raw materials is 150 grams.Then these raw materials are added in horizontal ball mill ball-milling medium (agate ball and dehydrated alcohol) and grind 8h, after oven dry, be fused into glass metal at 1300 DEG C of insulation 30min;
2. be poured into rapidly in metal die shaping by the high temp glass liquid of step 1 gained, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1cm 2the rectangular glass sheet of left and right;
3. sheet glass step 2 prepared carries out Controlled Crystallization, and this Crystallization Process is divided into two steps: first 610 DEG C of insulation 2h nucleation, then make nuclei growth at 850 DEG C of insulation 3 h, obtain glass-ceramic dielectric dielectric medium, sample XRD figure spectrum as shown in Figure 1;
4. dielectric material of glass-ceramics step 3 obtained carries out processing treatment, and rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
5. glass-ceramic dielectric thin slice step 4 obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste (purchase of Gui Yanbo industry company), at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
Gained dielectric material of glass-ceramics specific inductivity be 143, dielectric loss is 0.0183, and breaking down field strength is 850 kV/cm, and energy storage density is 4.57 J/cm 3.Test condition: test frequency 1kHz, room temperature; Disruptive strength is taking silicone oil as medium, and probe temperature is room temperature.
embodiment 8
A kind of strontium barium niobate base microcrystal glass dielectric substance and preparation method thereof, it forms Sr/Ba=0.33.
1. be greater than 99%SrCO with purity 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, according to SrO:BaO:Nb 2o 5: B 2o 3=a:b:c:d=0.08:0.24:0.32:0.36 molar ratio ingredient, the total consumption of all raw materials is 150 grams.Then these raw materials are added in horizontal ball mill ball-milling medium (agate ball and dehydrated alcohol) and grind 8h, after oven dry, be fused into glass metal at 1300 DEG C of insulation 30min;
2. be poured into rapidly in metal die shaping by the high temp glass liquid of step 1 gained, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1cm 2the rectangular glass sheet of left and right;
3. sheet glass step 2 prepared carries out Controlled Crystallization, and this Crystallization Process is divided into two steps: first 610 DEG C of insulation 2h nucleation, then make nuclei growth at 750 DEG C of insulation 3 h, obtain glass-ceramic dielectric dielectric medium, sample XRD figure spectrum as shown in Figure 1;
4. dielectric material of glass-ceramics step 3 obtained carries out processing treatment, and rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
5. glass-ceramic dielectric thin slice step 4 obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste (purchase of Gui Yanbo industry company), at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
Gained dielectric material of glass-ceramics specific inductivity be 76, dielectric loss is 0.0095, and breaking down field strength is 980 kV/cm, and energy storage density is 3.23 J/cm 3.Test condition: test frequency 1kHz, room temperature; Disruptive strength is taking silicone oil as medium, and probe temperature is room temperature.
embodiment 9
A kind of strontium barium niobate base microcrystal glass dielectric energy storage material and preparation method thereof, it forms Sr/Ba=3.0.
1. be greater than 99%SrCO with purity 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, according to SrO:BaO:Nb 2o 5: B 2o 3=a:b:c:d=0.112:0.208:0.32:0.36 molar ratio ingredient, the total consumption of all raw materials is 150 grams.Then these raw materials are added in horizontal ball mill ball-milling medium (agate ball and dehydrated alcohol) and grind 8h, after oven dry, be fused into glass metal at 1300 DEG C of insulation 30min;
2. be poured into rapidly in metal die shaping by the high temp glass liquid of step 1 gained, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1cm 2the rectangular glass sheet of left and right;
3. sheet glass step 2 prepared carries out Controlled Crystallization, and this Crystallization Process is divided into two steps: first 610 DEG C of insulation 2h nucleation, then make nuclei growth at 850 DEG C of insulation 3 h, obtain glass-ceramic dielectric dielectric medium, sample XRD figure spectrum as shown in Figure 1;
4. dielectric material of glass-ceramics step 3 obtained carries out processing treatment, and rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
5. glass-ceramic dielectric thin slice step 4 obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste (purchase of Gui Yanbo industry company), at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
The specific inductivity of gained dielectric material of glass-ceramics is 21.0, and dielectric loss is 0.0036, and breaking down field strength is 1300 kV/cm, and energy storage density is 1.79J/cm 3.Test condition: test frequency 1kHz, room temperature; Disruptive strength is taking silicone oil as medium, and probe temperature is room temperature.
embodiment 10
A kind of strontium barium niobate base microcrystal glass dielectric energy storage material and preparation method thereof, it forms Sr/Ba=3.0.
1. be greater than 99%SrCO with purity 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, according to SrO:BaO:Nb 2o 5: B 2o 3=a:b:c:d=0.112:0.208:0.32:0.36 molar ratio ingredient, the total consumption of all raw materials is 150 grams.Then these raw materials are added in horizontal ball mill ball-milling medium (agate ball and dehydrated alcohol) and grind 8h, after oven dry, be fused into glass metal at 1300 DEG C of insulation 30min;
2. be poured into rapidly in metal die shaping by the high temp glass liquid of step 1 gained, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1cm 2the rectangular glass sheet of left and right;
3. sheet glass step 2 prepared carries out Controlled Crystallization, and this Crystallization Process is divided into two steps: first 610 DEG C of insulation 2h nucleation, then make nuclei growth at 750 DEG C of insulation 3 h, obtain glass-ceramic dielectric dielectric medium, sample XRD figure spectrum as shown in Figure 1;
4. dielectric material of glass-ceramics step 3 obtained carries out processing treatment, and rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
5. glass-ceramic dielectric thin slice step 4 obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste (purchase of Gui Yanbo industry company), at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
The specific inductivity of gained dielectric material of glass-ceramics is 28, and dielectric loss is 0.0048, and breaking down field strength is 1300 kV/cm, and energy storage density is 2.09J/cm 3.Test condition: test frequency 1kHz, room temperature; Disruptive strength is taking silicone oil as medium, and probe temperature is room temperature.
embodiment 11
A kind of strontium barium niobate base microcrystal glass dielectric energy storage material and preparation method thereof, it forms Sr/Ba=0.82.
1. be greater than 99%SrCO with purity 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, according to SrO:BaO:Nb 2o 5: B 2o 3=a:b:c:d=0.112:0.208:0.32:0.36 molar ratio ingredient, the total consumption of all raw materials is 150 grams.Then these raw materials are added in horizontal ball mill ball-milling medium (agate ball and dehydrated alcohol) and grind 8h, after oven dry, be fused into glass metal at 1300 DEG C of insulation 30min;
2. be poured into rapidly in metal die shaping by the high temp glass liquid of step 1 gained, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1cm 2the rectangular glass sheet of left and right;
3. sheet glass step 2 prepared carries out Controlled Crystallization, and this Crystallization Process is divided into two steps: first 610 DEG C of insulation 2h nucleation, then make nuclei growth at 850 DEG C of insulation 3 h, obtain glass-ceramic dielectric dielectric medium, sample XRD figure spectrum as shown in Figure 1;
4. dielectric material of glass-ceramics step 3 obtained carries out processing treatment, and rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
5. glass-ceramic dielectric thin slice step 4 obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste (purchase of Gui Yanbo industry company), at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
The specific inductivity of gained dielectric material of glass-ceramics is 120, and dielectric loss is 0.0136, and breaking down field strength is 900 kV/cm, and energy storage density is 4.30J/cm 3.Test condition: test frequency 1kHz, room temperature; Disruptive strength is taking silicone oil as medium, and probe temperature is room temperature.
embodiment 12
A kind of strontium barium niobate base microcrystal glass dielectric energy storage material and preparation method thereof, it forms Sr/Ba=0.82.
1. be greater than 99%SrCO with purity 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, according to SrO:BaO:Nb 2o 5: B 2o 3=a:b:c:d=0.112:0.208:0.32:0.36 molar ratio ingredient, the total consumption of all raw materials is 150 grams.Then these raw materials are added in horizontal ball mill ball-milling medium (agate ball and dehydrated alcohol) and grind 8h, after oven dry, be fused into glass metal at 1300 DEG C of insulation 30min;
2. be poured into rapidly in metal die shaping by the high temp glass liquid of step 1 gained, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1cm 2the rectangular glass sheet of left and right;
3. sheet glass step 2 prepared carries out Controlled Crystallization, and this Crystallization Process is divided into two steps: first 610 DEG C of insulation 2h nucleation, then make nuclei growth at 750 DEG C of insulation 3 h, obtain glass-ceramic dielectric dielectric medium, sample XRD figure spectrum as shown in Figure 1;
4. dielectric material of glass-ceramics step 3 obtained carries out processing treatment, and rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
5. glass-ceramic dielectric thin slice step 4 obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste (purchase of Gui Yanbo industry company), at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
The specific inductivity of gained dielectric material of glass-ceramics is 51, and dielectric loss is 0.0063, and breaking down field strength is 1070 kV/cm, and energy storage density is 2.58 J/cm 3.Test condition: test frequency 1kHz, room temperature; Disruptive strength is taking silicone oil as medium, and probe temperature is room temperature.

Claims (6)

1. a strontium barium niobate base microcrystal glass dielectric substance, is characterized in that: the chemical formula of this material is aSrObBaOcNb 2o 5dB 2o 3, wherein by mole% counting: 0.33≤a/b≤3.0, c=0.32, d=0.36, a+b+c+d=1.
2. a preparation method for strontium barium niobate base microcrystal glass dielectric substance, is characterized in that: comprise the steps:
(1) with SrCO 3, BaCO 3, Nb 2o 5, H 3bO 3for starting raw material, according to aSrObBaOcNb 2o 5dB 2o 3ratio batching, then these raw materials are added in horizontal ball mill ball-milling medium grinding 8h, after oven dry 1300 DEG C insulation 30min be melting into uniform glass liquid; Described a, b, c, d are by mole% counting: 0.33≤a/b≤3.0, c=0.32, d=0.36, a+b+c+d=1;
(2) be poured into rapidly in metal die shaping by the high temp glass liquid that step (1) obtains, the 10h that then anneals in the annealing furnace of 550 DEG C eliminates stress, and finally cutting into area is 1 ~ 2cm 2rectangular glass sheet;
(3) sheet glass prepared by step (2) is carried out Controlled Crystallization, this Crystallization Process is divided into two steps: first make nucleation at 610 DEG C of insulation 2h, then make nuclei growth at 750-850 DEG C of insulation 3h, the strontium barium niobate obtaining having tungsten bronze structure is the glass-ceramic dielectric of principal crystalline phase;
(4) glass-ceramic dielectric that step (3) obtains is carried out processing treatment, rubbing down becomes thickness to be the thin slice of 0.05 ~ 1mm;
(5) glass-ceramic dielectric thin slice step (4) obtained through silk screen printing or manual application adhesive property and electroconductibility good in warm silver paste, at 600 DEG C, sintering curing forms argent electrode, i.e. obtained dielectric material of glass-ceramics.
3. the preparation method of strontium barium niobate base microcrystal glass dielectric substance according to claim 2, is characterized in that, in described step (1), and SrCO 3, BaCO 3, Nb 2o 5, H 3bO 3purity is all greater than 99 wt%.
4. the preparation method of strontium barium niobate base microcrystal glass dielectric substance according to claim 2, it is characterized in that: in described step (1), abrading-ball is agate ball.
5. the preparation method of strontium barium niobate base microcrystal glass dielectric substance according to claim 2, it is characterized in that: in described step (1), ball-milling medium is dehydrated alcohol or deionized water.
6. the preparation method of strontium barium niobate base microcrystal glass dielectric substance according to claim 2, it is characterized in that: in described step (2), forming metal mold material is cast iron or copper, and shape is rectangle or circle.
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