CN105418068A - Novel niobate-base glass ceramic energy-storing material and preparation method and application thereof - Google Patents
Novel niobate-base glass ceramic energy-storing material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a novel niobate-base glass ceramic energy-storing material and a preparation method and application thereof. The chemical composition of the material is [(Ba<1-x>Sr<x>) <2>NaNb<5>O<15>] <0.6>-[SiO<2>] <0.4>, wherein 0<=x<=1. With BaCO3, SrCO3, NaCO3, Nb2O5 and SiO2 powder being raw materials, the mass of each component is weighed according to the designed chemical composition, the components are subjected to ball milling and even mixing and then added into a crucible to be molten at high temperature, and high-temperature melt is rapidly poured into a preheated copper mold for stress removal and then cut into slices with the thickness of 1.0 mm; the glass slices are placed into an annealing furnace to be subjected to controlled crystallization, and through controlling ingredients of the glass raw materials and optimizing a crystallization technology, the prepared niobate glass ceramic has high energy-storing density and reliability. Compared with the prior art, the method is simple, and through testing of experiments, the prepared glass ceramic material has high energy-storing density and charging and discharging efficiency and is expected to be used as a novel energy-storing capacitor material.
Description
Technical field
The invention belongs to field of dielectric energy storage material, especially relate to a kind of novel niobate glass-ceramic energy storage material and its preparation method and application.
Background technology
In order to meet the miniaturization of pulse power system and light-weighted requirement, development as the dielectric materials of core component faces more challenges, the energy storage density how improving dielectric substance further becomes the focus of research, and various countries material supplier author is just trying to explore to study has high-k, the low dielectric material connecing electrical loss and high dielectric strength.Ferroelectric niobates glass-ceramic is paid close attention to widely because the dielectric properties of its excellence cause in this field in recent years.What be widely studied at present mainly contains strontium barium niobate (SrxBa1-xNb2O6, x=0.25-0.75), lead meta-columbute (PbNb
2o
6), barium sodium niobate (BNN) (Ba
2naNb
5o
15), the system such as potassium niobate (KNbO3), sodium columbate (NaNbO3).
In niobate glass-ceramic system, what the energy storage density of report was higher at present is mainly lead meta-columbute (PbNb
2o
6) base glass-ceramic system, the people such as Du Jun adopt the method for controlled crystallization to prepare NaNbO
3-PbNb
2o
6-SiO
2, (Pb, Sr) Nb
2o
6-NaNbO
3-SiO
2etc. system glass-ceramic, by optimal preparation technology, obtain higher energy-storage property ([Preparationandcharacterizationofdielectricglass-ceramics inNa
2o – PbO – Nb
2o
5– SiO
2system, MaterialsLetters59 (2005) 2821-2826]).But these systems are all containing plumbous, and at high temperature facial pallor is volatile, to environment evil again.There is bibliographical information, the AF45 glass that Schott AG produces has high breakdown voltage resistant, record it in laboratory and breakdown voltage resistantly reach 12MV/cm, the maximum energy storage density of AF45 glass reaches 35J/cm3 ([Alkali-freeglassasahighenergydensitydielectricmaterial after tested, MaterialsLetters63 (2009) 1245-1248]), but the composition of AF45 glass is too complicated, and the viscosity of this glass is too large, be difficult to prepare under normal conditions.The people such as Zeng effectively improve BaO-SrO-Nb by doping BaF2
2o
5-B
2o
3the specific inductivity of system glass-ceramic, but the resistance to breaking down field strength of this system only has 527Kv/cm, the thus lower ([EffectofBaF of energy storage density
2additiononcrystallizationkineticsanddielectricproperties ofB
2o
3-Nb
2o
5-SrO-BaOglass-ceramics, J.Am.CeramSoc, 2011,94 (2): 469]).This group adopts based on BaO-B early stage
2o
3-Al
2o
3-SiO
2as glassy phase main component, prepare ferroelectric niobates glass-ceramic ([Dielectricpropertiesandcharge – dischargebehaviorsinniobateglassceramicsforenergy-storag eapplications, JournalofAlloysandCompounds617 (2014) 418 – 422.]), but, because the composition of glass-based is too complicated, not only preparation technology is more complicated, and in Crystallization Process, be easy to form many impurity phases, thus affect the energy storage characteristic of glass-ceramic.
Chinese patent CN104671665A crown glass pottery disclosing low-dielectric loss and preparation method thereof, the composition of this glass-ceramic consists of: aBaO-bSrO-cNb
2o
5-dZnO-xSiO
2-yB
2o
3-zREO, wherein, a, b, c, d, x, y, z are the mol ratio between mol ratio is expressed as point, and REO represents rare earth oxide; And meet: 0≤a≤10.35,9.97≤b≤20.70,20.19≤c≤20.70,14.80≤d≤15.50,14.56≤x≤15.00,27.51≤y≤28.10,0≤z≤3.00.Be grouped into selection raw material according to the one-tenth of glass-ceramic, be mixed in proportion, high-temperature fusion; Uniform for melting glass precursor solution is poured in the metal die of preheating fast, cooling forming, stress relief annealing; The sheet glass obtained is carried out controlled crystallization treatment.This system principal crystalline phase is Ba
xsr
1-xnbO
3, glassy phase is ZnO-SiO
2-B
2o
3but because this system component is too complicated, easily uneven components is caused in Sample Preparation Procedure, and in Crystallization Process, the a lot of impurity phase of easy generation, thus cause the breaking down field strength of this series of samples lower, from the disruptive strength that this patent is reported, the disruptive strength of all samples all more than 200Kv/mm, well below the [(Ba involved by this patent
1-xsr
x)
2naNb
5o
15]
0.6-[SiO
2]
0.4disruptive strength value.
Summary of the invention
Object of the present invention be exactly provide to overcome defect that above-mentioned prior art exists a kind of improve the specific inductivity of glass-ceramic while the novel niobate glass-ceramic energy storage material also improving resistance to breaking down field strength and its preparation method and application.
Object of the present invention can be achieved through the following technical solutions:
Niobate glass-ceramic energy storage material, chemical constitution is [(Ba
1-xsr
x)
2naNb
5o
15]
0.6-[SiO
2]
0.4, wherein 0≤x≤1.
The span of x is preferably 0.1≤x≤0.5.
The span of x most preferably is 0.25.
The preparation method of novel niobate glass-ceramic energy storage material, adopts following steps:
(1) with analytically pure BaCO
3, SrCO
3, NaCO
3, Nb
2o
5, B
2o
3, Al
2o
3, SiO
2powder is raw material, gets the raw materials ready according to the formula of the chemical constitution of energy storage material;
(2) using dehydrated alcohol as dispersion agent, adopt agate ball and said components is placed in ball grinder ball milling, and the slurry mixed is dried;
(3) frit after drying is added high temperature melting in crucible, then by high-temperature fusant Quick pouring in the copper mould of prior preheating, the obtained transparent glass block without crystallization, puts into annealing furnace stress relief annealing by glass block;
(4) slicing machine is utilized to be thinly sliced by transparent glass block; Glass flake is put into annealing furnace and carries out Controlled Crystallization, the temperature rise rate of annealing furnace is 3-5 DEG C/min, and recrystallization temperature is 800-1100 DEG C, and soaking time is 1-3h, namely prepares niobate glass-ceramic energy storage material.
In step (2), the time of ball mill mixing is 10 ~ 20h.
Step (3) is in high temperature melting process, and the temperature rise rate of glass furnace is 1-2 DEG C/min, at 800 DEG C of insulation 3h, the temperature of high temperature melting is 1400 ~ 1600 DEG C, the time of high temperature melting is 2 ~ 5h, and copper mould is preheated to 500-650 DEG C in advance, preferably 600 DEG C; Then glass block is put into annealing furnace destressing, destressing holding temperature is 500-650 DEG C, preferably 600 DEG C; Soaking time is 3-5h, and insulation terminates rear furnace cooling.
When step (4) carries out Controlled Crystallization, the temperature rise rate of annealing furnace is 3-5 DEG C/min, and recrystallization temperature is 800-1100 DEG C, and soaking time is 2-3h, and insulation terminates rear furnace cooling.
Novel niobate glass-ceramic energy storage material can be applied in energy storage capacitor Material Field.Compared with prior art, the dielectric properties of glass-ceramic of the present invention are by glassy phase and the synergistic result of crystalline phase performance.The existence of glassy phase makes devitrified glass have higher breaking down field strength, and the formation of crystalline phase and the specific inductivity etc. of content on material have important impact.Glass-ceramic has higher breaking down field strength, and the specific inductivity etc. that how can improve material on the voltage endurance that maintenance is high becomes the difficult point of research.The present invention adopts based on SiO
2as glassy phase, with BaO (SrO)-Na
2o-Nb
2o
5as ceramic phase, glass block is prepared by the method for melt-spun, section prepares ferroelectric niobates glass-ceramic by the method for controlled crystallization later, by regulating the ratio of glassy phase and ceramic phase, utilize the thermodynamic property of glass, adopt the crystallization technique optimized, the glass of specific components is carried out Crystallizing treatment under certain condition, make even, fine and close flawless glassy phase originally form the ferroelectric ceramic(s) crystallite phase and the equally distributed matrix material of glassy phase that contain a large amount of high-k.Component 6Na
2o-18BaO-6SrO-30Nb
2o
5-40SiO
2glass through 1000 DEG C of crystallizatioies glass-ceramic sample after tested, under room temperature, the specific inductivity of this sample is 81, and breaking down field strength is 1212Kv/cm, by calculate, its energy storage density reaches 5.27J/cm
3.
Accompanying drawing explanation
Fig. 1 prepares the XRD spectrum of product after 1000 DEG C of crystallizatioies in embodiment 1-5;
Fig. 2 is that embodiment 2 prepares the XRD spectrum of product after differing temps crystallization;
Fig. 3 prepares product dielectric constant with temperature change curve after 1000 DEG C of crystallizatioies in embodiment 1-5;
Fig. 4 prepares the resistance to breaking down field strength of product after 1000 DEG C of crystallizatioies in embodiment 1-5;
Fig. 5 prepares the activation energy of product after 1000 DEG C of crystallizatioies and breaking down field strength in embodiment 1-5.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1 (x=0)
The niobate glass-ceramic 6Na of high energy storage density
2o-24BaO-30Nb
2o
5-40SiO
2
(1) with analytically pure BaCO
3, NaCO
3, Nb
2o
5, SiO
2powder is raw material, according to the chemical composition 6Na of design
2o-24BaO-30Nb
2o
5-40SiO
2weigh the quality of good each component, sample total mass is 80-100 gram.
(2) select dehydrated alcohol as dispersion agent, adopt agate ball ball milling in tetrafluoroethylene ball grinder, rotating speed is that 50-60 turns/min, is dried by the slurry mixed.The time of ball milling is 20 ~ 30h, and ratio of grinding media to material during ball milling is (1.0 ~ 1.5): 1.
(3) frit after oven dry is added high temperature melting in crucible, the temperature of High Temperature Furnaces Heating Apparatus temperature rise rate high temperature melting is 1400 DEG C, and the time of high temperature melting is 5h.Then by high-temperature fusant Quick pouring in the copper mould of prior preheating, the obtained transparent glass block without crystallization, puts into annealing furnace stress relief annealing by glass block.The temperature of the prior preheating of copper mould is 500 DEG C; Then glass block is put into annealing furnace destressing, destressing holding temperature is 500 DEG C; Soaking time is 5h; It is furnace cooling that insulation terminates the rear type of cooling.
(4) utilize slicing machine that transparent glass block is cut into the thin slice that thickness is 1.0mm; Glass flake is put into annealing furnace and carries out Controlled Crystallization, the temperature rise rate of annealing furnace is 3 DEG C/min, and recrystallization temperature is 1000 DEG C, and soaking time is 2 hours, and it is furnace cooling that insulation terminates the rear type of cooling, finally obtains niobate glass-ceramic sample.
The XRD figure spectrum of the ceramics sample obtained by the present embodiment is as shown in x=0 curve in Fig. 1, dielectric properties as shown in x=0 curve in Fig. 3, resistance to sparking can as shown in x=0 curve in Fig. 4, through 1000 DEG C of crystallizatioies this glass-ceramic sample after tested, under room temperature, the specific inductivity of this sample is 78, breaking down field strength is 1075kV/cm, by calculating, its energy storage density reaches 3.99J/cm
3.
Embodiment 2 (x=0.25)
The niobate glass-ceramic 6Na of high energy storage density
2o-18BaO-6SrO-30Nb
2o
5-40SiO
2
(1) with analytically pure BaCO
3, SrCO
3, NaCO
3, Nb
2o
5, B
2o
3, Al
2o
3, SiO
2powder is raw material, according to the chemical composition 6Na of design
2o-18BaO-6SrO-30Nb
2o
5-40SiO
2weigh the quality of good each component, sample total mass is 80-100 gram.
(2) select dehydrated alcohol as dispersion agent, adopt agate ball ball milling in tetrafluoroethylene ball grinder, rotating speed is that 50-60 turns/min, is dried by the slurry mixed.The time of ball milling is 20 ~ 30h, and ratio of grinding media to material during ball milling is (1.0 ~ 1.5): 1.
(3) frit after oven dry is added high temperature melting in crucible, the temperature of High Temperature Furnaces Heating Apparatus temperature rise rate high temperature melting is 1500 DEG C, and the time of high temperature melting is 5h.Then by high-temperature fusant Quick pouring in the copper mould of prior preheating, the obtained transparent glass block without crystallization, puts into annealing furnace stress relief annealing by glass block.The temperature of the prior preheating of copper mould is 600 DEG C; Then glass block is put into annealing furnace destressing, destressing holding temperature is 600 DEG C; Soaking time is 4h; It is furnace cooling that insulation terminates the rear type of cooling.
(4) utilize slicing machine that transparent glass block is cut into the thin slice that thickness is 1.0mm; Glass flake is put into annealing furnace and carries out Controlled Crystallization, the temperature rise rate of annealing furnace is 4 DEG C/min, and recrystallization temperature is 1000 DEG C, and soaking time is 2 hours, and it is furnace cooling that insulation terminates the rear type of cooling, finally obtains niobate glass-ceramic sample.
The XRD figure spectrum of the ceramics sample obtained by the present embodiment is as shown in Fig. 2 curve, dielectric properties as shown in x=0.25 curve in Fig. 3, resistance to sparking can as shown in x=0.25 curve in Fig. 4, through 1000 DEG C of crystallizatioies this glass-ceramic sample after tested, under room temperature, the specific inductivity of this sample is 81, breaking down field strength is 1212kV/cm, by calculating, its energy storage density reaches 5.27J/cm
3.
Embodiment 3 (x=0.50)
The niobate glass-ceramic 6Na of high energy storage density
2o-12BaO-12SrO-30Nb
2o
5-40SiO
2
(1) with analytically pure BaCO
3, SrCO
3, NaCO
3, Nb
2o
5, SiO
2powder is raw material, according to the chemical composition 6Na of design
2o-12BaO-12SrO-30Nb
2o
5-40SiO
2weigh the quality of good each component, sample total mass is 80-100 gram.
(2) select dehydrated alcohol as dispersion agent, adopt agate ball ball milling in tetrafluoroethylene ball grinder, rotating speed is that 50-60 turns/min, is dried by the slurry mixed.The time of ball milling is 20 ~ 30h, and ratio of grinding media to material during ball milling is (1.0 ~ 1.5): 1.
(3) frit after oven dry is added high temperature melting in crucible, the temperature of High Temperature Furnaces Heating Apparatus temperature rise rate high temperature melting is 1600 DEG C, and the time of high temperature melting is 2h.Then by high-temperature fusant Quick pouring in the copper mould of prior preheating, the obtained transparent glass block without crystallization, puts into annealing furnace stress relief annealing by glass block.The temperature of the prior preheating of copper mould is 650 DEG C; Then glass block is put into annealing furnace destressing, destressing holding temperature is 650 DEG C, and soaking time is 3h; It is furnace cooling that insulation terminates the rear type of cooling.
(4) utilize slicing machine that transparent glass block is cut into the thin slice that thickness is 1.0mm; Glass flake is put into annealing furnace and carries out Controlled Crystallization, the temperature rise rate of annealing furnace is 5 DEG C/min, and recrystallization temperature is 1100 DEG C, and soaking time is 2 hours, and it is furnace cooling that insulation terminates the rear type of cooling, finally obtains niobate glass-ceramic sample.
The XRD figure spectrum of the ceramics sample obtained by the present embodiment is as shown in x=0.50 curve in Fig. 1, dielectric properties as shown in x=0.50 curve in Fig. 3, resistance to sparking can as shown in x=0.50 curve in Fig. 4, through 1000 DEG C of crystallizatioies this glass-ceramic sample after tested, under room temperature, the specific inductivity of this sample is 93, breaking down field strength is 963kV/cm, by calculating, its energy storage density reaches 3.81J/cm
3.
Embodiment 4 (x=0.75)
The niobate glass-ceramic 6Na of high energy storage density
2o-6BaO-18SrO-30Nb
2o
5-40SiO
2
(1) with analytically pure BaCO
3, SrCO
3, NaCO
3, Nb
2o
5, SiO
2powder is raw material, according to the chemical composition 6Na of design
2o-6BaO-18SrO-30Nb
2o
5-40SiO
2weigh the quality of good each component, sample total mass is 80-100 gram.
(2) select dehydrated alcohol as dispersion agent, adopt agate ball ball milling in tetrafluoroethylene ball grinder, rotating speed is that 50-60 turns/min, is dried by the slurry mixed.The time of ball milling is 20 ~ 30h, and ratio of grinding media to material during ball milling is (1.0 ~ 1.5): 1.
(3) frit after oven dry is added high temperature melting in crucible, the temperature of High Temperature Furnaces Heating Apparatus temperature rise rate high temperature melting is 1600 DEG C, and the time of high temperature melting is 5h.Then by high-temperature fusant Quick pouring in the copper mould of prior preheating, the obtained transparent glass block without crystallization, puts into annealing furnace stress relief annealing by glass block.The temperature of the prior preheating of copper mould is 650 DEG C, then glass block is put into annealing furnace destressing, and destressing holding temperature is 600 DEG C; Soaking time is 5h; It is furnace cooling that insulation terminates the rear type of cooling.
(4) utilize slicing machine that transparent glass block is cut into the thin slice that thickness is 1.0mm; Glass flake is put into annealing furnace and carries out Controlled Crystallization, the temperature rise rate of annealing furnace is 5 DEG C/min, and recrystallization temperature is 1000 DEG C, and soaking time is 2 hours, and it is furnace cooling that insulation terminates the rear type of cooling, finally obtains niobate glass-ceramic sample.
The XRD figure spectrum of the ceramics sample obtained by the present embodiment is as shown in x=0.75 curve in Fig. 1, dielectric properties as shown in x=0.75 curve in Fig. 3, resistance to sparking can as shown in x=0.75 curve in Fig. 4, through 1000 DEG C of crystallizatioies this glass-ceramic sample after tested, under room temperature, the specific inductivity of this sample is 72, breaking down field strength is 820kV/cm, by calculating, its energy storage density reaches 2.14J/cm
3.
Embodiment 5 (x=1)
The niobate glass-ceramic 6Na of high energy storage density
2o-24SrO-30Nb
2o
5-40SiO
2
(1) with analytically pure SrCO
3, NaCO
3, Nb
2o
5, SiO
2powder is raw material, according to the chemical composition 6Na of design
2o-24SrO-30Nb
2o
5-40SiO
2weigh the quality of good each component, sample total mass is 80-100 gram.
(2) select dehydrated alcohol as dispersion agent, adopt agate ball ball milling in tetrafluoroethylene ball grinder, rotating speed is that 50-60 turns/min, is dried by the slurry mixed.The time of ball milling is 20 ~ 30h, and ratio of grinding media to material during ball milling is (1.0 ~ 1.5): 1.
(3) frit after oven dry is added high temperature melting in crucible, the temperature of High Temperature Furnaces Heating Apparatus temperature rise rate high temperature melting is 1500 DEG C, and the time of high temperature melting is 4h.Then by high-temperature fusant Quick pouring in the copper mould of prior preheating, the obtained transparent glass block without crystallization, puts into annealing furnace stress relief annealing by glass block.The temperature of the prior preheating of copper mould is 500 DEG C; Then glass block is put into annealing furnace destressing, destressing holding temperature is 650 DEG C; Soaking time is 4h; It is furnace cooling that insulation terminates the rear type of cooling.
(4) utilize slicing machine that transparent glass block is cut into the thin slice that thickness is 1.0mm; Glass flake is put into annealing furnace and carries out Controlled Crystallization, the temperature rise rate of annealing furnace is 4 DEG C/min, and recrystallization temperature is 1100 DEG C, and soaking time is 2 hours, and it is furnace cooling that insulation terminates the rear type of cooling, finally obtains niobate glass-ceramic sample.
The XRD figure spectrum of the ceramics sample obtained by the present embodiment is as shown in x=1 curve in Fig. 1, dielectric properties as shown in x=0.75 curve in Fig. 3, resistance to sparking can as shown in x=1 curve in Fig. 4, through 1000 DEG C of crystallizatioies this glass-ceramic sample after tested, under room temperature, the specific inductivity of this sample is 65, breaking down field strength is 713kV/cm, by calculating, its energy storage density reaches 1.46J/cm
3.
Table 1 prepares the energy storage density of product after 1000 DEG C of crystallizatioies in embodiment 1-5
Specific inductivity | Breaking down field strength (Kv/cm) | Energy storage density (J/cm 3) | |
X=0 | 78 | 1075 | 3.99 |
X=0.25 | 81 | 1212 | 5.27 |
X=0.50 | 93 | 963 | 3.81 |
X=0.75 | 72 | 820 | 2.14 |
X=1 | 65 | 713 | 1.46 |
Claims (9)
1. a novel niobate glass-ceramic energy storage material, is characterized in that, the chemical constitution of this energy storage material is [(Ba
1-xsr
x)
2naNb
5o
15]
0.6-[SiO
2]
0.4, wherein 0≤x≤1.
2. one according to claim 1 novel niobate glass-ceramic energy storage material, is characterized in that, the span of x is preferably 0.1≤x≤0.5.
3. one according to claim 1 novel niobate glass-ceramic energy storage material, is characterized in that, the span of x most preferably is 0.25.
4. the preparation method of a kind of novel niobate glass-ceramic energy storage material as claimed in claim 1, is characterized in that, the method adopts following steps:
(1) with analytically pure BaCO
3, SrCO
3, NaCO
3, Nb
2o
5, SiO
2powder is raw material, gets the raw materials ready according to the formula of the chemical constitution of energy storage material;
(2) using dehydrated alcohol as dispersion agent, adopt agate ball and said components is placed in ball grinder ball milling, and the slurry mixed is dried;
(3) frit after drying is added high temperature melting in crucible, then by high-temperature fusant Quick pouring in the copper mould of prior preheating, the obtained transparent glass block without crystallization, puts into annealing furnace stress relief annealing by glass block;
(4) slicing machine is utilized to be thinly sliced by transparent glass block; Glass flake is put into annealing furnace and carries out Controlled Crystallization, the temperature rise rate of annealing furnace is 3-5 DEG C/min, and recrystallization temperature is 800-1100 DEG C, and soaking time is 1-3h, namely prepares niobate glass-ceramic energy storage material.
5. the preparation method of a kind of novel niobate glass-ceramic energy storage material according to claim 4, is characterized in that, in step (2), the time of ball mill mixing is 10 ~ 20h.
6. the preparation method of a kind of novel niobate glass-ceramic energy storage material according to claim 4, it is characterized in that, step (3) is in high temperature melting process, the temperature rise rate of glass furnace is 1-2 DEG C/min, at 800 DEG C of insulation 3h, the temperature of high temperature melting is 1400 ~ 1600 DEG C, and the time of high temperature melting is 2 ~ 5h.
7. the preparation method of a kind of novel niobate glass-ceramic energy storage material according to claim 4, it is characterized in that, the copper mould in step (3) is preheated to 500-650 DEG C in advance, preferably 600 DEG C; Then glass block is put into annealing furnace destressing, destressing holding temperature is 500-650 DEG C, preferably 600 DEG C; Soaking time is 3-5h, and insulation terminates rear furnace cooling.
8. the preparation method of a kind of novel niobate glass-ceramic energy storage material according to claim 4, it is characterized in that, when step (4) carries out Controlled Crystallization, the temperature rise rate of annealing furnace is 3-5 DEG C/min, recrystallization temperature is 800-1100 DEG C, soaking time is 2-3h, and insulation terminates rear furnace cooling.
9. a novel niobate glass-ceramic energy storage material as claimed in claim 1 is as the application of energy storage capacitor material.
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CN108840570A (en) * | 2018-07-18 | 2018-11-20 | 陕西科技大学 | Containing NaNbO3The Na of phase2O-K2O-Nb2O5-SiO2Low-dielectric loss energy storage glass ceramics |
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CN114685050A (en) * | 2022-04-28 | 2022-07-01 | 电子科技大学 | High-energy-storage-efficiency silicon niobate microcrystalline glass material and preparation method thereof |
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CN113666742A (en) * | 2021-08-30 | 2021-11-19 | 南京大学 | Material and method for realizing relaxation-normal ferroelectric phase transition by doping |
CN114685050A (en) * | 2022-04-28 | 2022-07-01 | 电子科技大学 | High-energy-storage-efficiency silicon niobate microcrystalline glass material and preparation method thereof |
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