CN115594501A - Sodium niobate-based energy storage ceramic with high breakdown electric field and two-step sintering method thereof - Google Patents

Sodium niobate-based energy storage ceramic with high breakdown electric field and two-step sintering method thereof Download PDF

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CN115594501A
CN115594501A CN202211381775.9A CN202211381775A CN115594501A CN 115594501 A CN115594501 A CN 115594501A CN 202211381775 A CN202211381775 A CN 202211381775A CN 115594501 A CN115594501 A CN 115594501A
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powder
sintering
temperature
electric field
energy storage
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冯耀
甄玉花
姜晓琳
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China University of Petroleum East China
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Abstract

The invention relates to a sodium niobate-based energy storage ceramic with a high breakdown electric field and a two-step sintering method, which can effectively overcome the defects of difficult sintering, difficult forming and low breakdown strength in the prior art. The invention uses the component Na 1‑3x/2 Bi 3x/2 Nb 1‑x Cu x O 3 (x =0,0.06,0.08,0.10,0.12) is a chemical proportioning equation, and high-purity Na is prepared by adopting a traditional solid-phase reaction method and a sintering process of a two-step sintering method 2 CO 3 Powder and Nb 2 O 5 Powder of Bi 2 O 3 Taking powder and CuO powder as raw materials; the sodium niobate based storage battery with high breakdown electric field and good energy storage characteristic is prepared by a series of steps of weighing, ball milling drying, presintering, secondary ball milling, tabletting, plastic discharging, sintering, electrode mounting and the likeThe energy ceramic is an improvement of sodium niobate-based energy storage ceramic in a sintering method. The energy storage ceramic with a high breakdown electric field is successfully obtained through the sintering process of the two-step sintering method, the breakdown electric field is 290kV/cm, the defects of difficult sintering, poor forming and poor compactness in the ceramic preparation process are effectively overcome, the method is simple to operate, and the method is high in universality.

Description

Sodium niobate-based energy storage ceramic with high breakdown electric field and two-step sintering method thereof
Technical Field
The invention relates to a preparation method of sodium niobate-based energy storage ceramic, in particular to a preparation method of energy storage ceramic prepared by a two-step sintering method, belonging to the technical field of energy storage material application.
Background
Dielectric energy storage capacitors have the advantages of high power density, fast charge and discharge speed, long cycle life and the like, and are receiving more and more attention in the fields of power technology, intelligent electric cars, laser systems, advanced electronic elements and the like. Ceramic based dielectric capacitors have become one of the most promising materials due to their superior electrical and mechanical properties compared to other types of capacitors. The lead-based ceramic material has attracted much attention as a material for the past relatively popular because of its excellent performance and practical application prospect. However, lead pollution seriously affects deterioration of the natural environment and human survival. Thus, energy storage applications for lead-free ceramic materials are also being increasingly investigated. Compared with other mature energy storage materials (batteries, super capacitors and the like), the dielectric ceramic material has the advantages of excellent mechanical property, high power density, good thermal conductivity, high charging and discharging speed and the like.
At present, research focuses on lead-free energy storage materials, such as barium titanate, sodium bismuth titanate, sodium niobate and the like, wherein the sodium niobate-based material has great advantages in a plurality of lead-free energy storage materials due to high saturation polarization, double hysteresis lines and residual polarization of almost 0, but the problems of difficult sintering, difficult molding, low breakdown electric field and the like exist, so that the improvement of the energy storage performance is limited. The major factor of the influence is the threshold value problem of the breakdown electric field, and how to greatly improve the breakdown electric field is a problem which needs to be solved urgently.
The breakdown electric field of the ceramic material is mainly related to the grain size, the density and the test conditions of the ceramic material, wherein the influence of the grain size and the density is the most important. The method is very suitable and effective for obtaining the ceramic material with small grain size and high density by improving the sintering process, and the purpose of sintering under the premise of not growing the grains is realized by using a two-step sintering method to perform sectional control on the growth of the grains, namely by reasonably controlling the temperature change and inhibiting the migration of grain boundaries. Based on the above, the use of the two-step sintering method can effectively improve the breakdown strength of the ceramic.
Disclosure of Invention
The invention aims to provide a preparation method of energy storage ceramic with high breakdown electric field and a two-step sintering method thereof, which can effectively solve the problems of difficult sintering, low breakdown field strength and complex preparation process in the prior art.
In order to achieve the purpose, the technical solution of the invention is as follows: the preparation method of the energy storage ceramic with high breakdown electric field is characterized by comprising the following steps
1. A process for preparing the energy-accumulating sodium niobate ceramics with high breakdown field by two-step sintering method uses Na as component 1-3x/2 Bi 3x/2 Nb 1-x Cu x O 3 (x =0,0.06,0.08,0.10,0.12) is a chemical proportioning equation, a traditional solid phase reaction method is combined with a novel two-step sintering process, and high-purity Na is used 2 CO 3 Powder and Nb 2 O 5 Powder of Bi 2 O 3 The method is characterized by comprising the following steps of:
(1) Calculating the mass of each raw material according to the molar ratio of x =0,0.06,0.08,0.10 and 0.12, and weighing Na 2 CO 3 Powder and Nb 2 O 5 Powder of Bi 2 O 3 Powder and CuO powder; na (Na) 2 CO 3 The purity of the powder is more than or equal to 99.5 percent; nb 2 O 5 The purity of the powder is more than or equal to 99.9 percent; bi 2 O 3 The purity of the powder is more than or equal to 99.00 percent; the purity of the CuO powder is more than or equal to 99 percent;
(2) Weighing Na in the step (1) 2 CO 3 And Nb 2 O 5 The powder is subjected to mixing and ball milling to obtain matrix powder, the process adopts wet ball milling mixing, the ball milling medium is zirconium balls and absolute ethyl alcohol (the mass ratio of the zirconium balls to the powder to the absolute ethyl alcohol is 5;
(3) Sequentially drying the matrix powder obtained in the step (2) (drying by using an air-blast drying oven at the temperature of 80 ℃ for 12 hours) and presintering (presintering by using a muffle furnace at the temperature of 850 ℃ for 4 hours) to obtain a prefabricated main matrix NaNbO 3 Powder material;
(4) The main matrix NaNbO obtained in the step (3) 3 Powder and Bi mixed according to the proportion 2 O 3 Performing secondary ball milling on the powder and the CuO powder, wherein the ball milling method and parameters adopted in the process are consistent with those in the step 2);
(5) Drying the ball-milling powder obtained in the step (4) in sequence (the drying temperature is 80 ℃, and the time is 12 hours) to obtain powder which is prefabricated and uniformly mixed, and waiting for tabletting for later use;
(6) Granulating and tabletting the dried powder obtained in the step (5), and adding 5wt% of pva solution into the prefabricated mixed dry powder for granulation treatment to obtain powder particles; wherein the mass ratio of the prefabricated mixed dry powder to the pva solution is 0.15; after the granulation treatment is finished, sieving the formed powder particles, and selecting the powder particles between 60 meshes and 100 meshes for tabletting; pressing the sieved powder particles under 200Mpa uniaxially into cylinders with diameter of 12mm and thickness of 1.5 mm;
(7) And (3) placing the sample pressed in the step (6) at 600 ℃ for plastic removal, wherein the plastic removal process comprises the following steps: heating the muffle furnace to 600 ℃ at the speed of 5 ℃/min, carrying out heat preservation and calcination for 1.5h, and then naturally cooling to room temperature;
(8) And (3) embedding the sample subjected to plastic removal in the step (7) into a 20ml crucible, and performing dense sintering in an air atmosphere by using a two-step sintering method, wherein in the process, the muffle furnace is heated to 1150 ℃ at the speed of 5 ℃/min, the temperature is kept for 2min, and then the temperature is reduced to 1000 ℃ at the speed of 10 ℃/min, and the blank is subjected to constant-temperature calcination for 2.5h to obtain the dense and regular sodium niobate-based ceramic.
The invention has the beneficial effects that: the method for preparing the sodium niobate-based ceramic material by using the two-step sintering method can complete the sintering process at about 1000 ℃, thereby excellently avoiding the problems of volatilization of substances and difficult forming at high temperature and ensuring the acquisition of the ceramic material with high density, small grain size and high breakdown electric field; the method is simple and easy to operate in the using process, can well improve the efficiency, and is high in universality and easy to widely use.
Drawings
FIG. 1 is a flow chart of the preparation of the sodium niobate-based ceramic material
FIG. 2 is a schematic diagram of a two-step sintering process
FIG. 3 (a-e) SEM images of sodium niobate-based ceramic materials with increasing doping component content
FIG. 4 is a graph of grain size and breakdown field of a sodium niobate-based ceramic material as a function of increasing doping composition
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
The first embodiment is as follows:
a preparation method of sodium niobate energy storage ceramic with high breakdown electric field by using a two-step sintering method comprises the following steps:
(1) Calculating the mass of each raw material according to the molar ratio of x =0,0.06,0.08,0.10 and 0.12, and weighing Na 2 CO 3 Powder and Nb 2 O 5 Powder of Bi 2 O 3 Powder and CuO powder; na (Na) 2 CO 3 The purity of the powder is more than or equal to 99.5 percent; nb 2 O 5 The purity of the powder is more than or equal to 99.9 percent; bi 2 O 3 The purity of the powder is more than or equal to 99.00 percent; the purity of the CuO powder is more than or equal to 99 percent, and all the raw materials are purchased from Chinese medicines;
(2) Weighing Na in the step (1) 2 CO 3 And Nb 2 O 5 Carrying out mixing and ball milling on the powder to obtain matrix powder, wherein a wet ball milling mixing process is adopted, a ball milling medium is zirconium balls and absolute ethyl alcohol (the mass ratio of the zirconium balls to the powder to the absolute ethyl alcohol is 5; the ball milling rotation speed is 300r/min in the ball milling process, the ball milling device is arranged on a flat ground, the ball milling tanks are oppositely arranged, and the quality of the powder loaded in each ball milling tank is ensured to be consistent with that of the alcohol;
(3) Sequentially drying the matrix powder obtained in the step (2) (drying by using an air-blast drying oven at the temperature of 80 ℃ for 12 hours) and presintering (presintering by using a muffle furnace at the temperature of 850 ℃ for 4 hours) to obtain a prefabricated main matrix NaNbO 3 Powder lot; the tray is used as a container in the drying process to achieve the effect of uniform drying and no deposition, and the tray is pressed into the shape with the diameter of 1cm and the thickness of 10mm in the pre-sintering processThe large cylindrical sample achieves the effect of full sintering diffusion;
(4) The main matrix NaNbO obtained in the step (3) 3 Powder and Bi mixed according to the mixing ratio 2 O 3 Performing secondary ball milling on the powder and the CuO powder, wherein the ball milling method and parameters adopted in the process are consistent with those in the step 2);
(5) Drying the ball-milling powder obtained in the step (4) in sequence (the drying temperature is 80 ℃, and the time is 12 hours) to obtain powder which is prefabricated and uniformly mixed, and waiting for tabletting for later use;
(6) Granulating and tabletting the dried powder obtained in the step (5), and adding 5wt% of pva solution into the prefabricated mixed dry powder for granulation treatment to obtain powder particles; wherein the mass ratio of the prefabricated mixed dry powder to the pva solution is 0.15; after the granulation treatment is finished, sieving the formed powder particles, and selecting the powder particles between 60 meshes and 100 meshes for tabletting; pressing the sieved powder particles under 200Mpa uniaxially into cylinders with diameter of 12mm and thickness of 1.5 mm; when preparing a 5wt% pva aqueous solution, heating the pva aqueous solution in a water bath kettle for 3 hours at constant temperature to obtain the pva aqueous solution;
(7) And (3) placing the sample pressed in the step (6) at 600 ℃ for plastic removal, wherein the plastic removal operation is as follows: heating the muffle furnace to 600 ℃ at the speed of 5 ℃/min, carrying out heat preservation and calcination for 1.5h, and then naturally cooling to room temperature;
(8) Placing the sample subjected to plastic removal in the step (7) in a 20ml crucible by powder embedding, and performing dense sintering by using a two-step sintering method in an air atmosphere, wherein in the process, firstly, a muffle furnace is heated to 1150 ℃ at the speed of 5 ℃/min, the temperature is kept for 2min, and then, the temperature is reduced to 1000 ℃ at the speed of 10 ℃/min, and a blank is calcined at constant temperature for 2.5h to obtain the dense and regular sodium niobate-based ceramic; note that the sintering parameters were optimized according to actual experimental conditions and systems using a two-step sintering process.
An overview of the experimental flow according to the first embodiment can be observed from fig. 1; fig. 2 is a schematic view of the two-step sintering process proposed by the present invention, and it can be observed that it is mainly divided into three temperature intervals: the temperature is increased to a temperature higher than the sintering temperature for sintering for a very short time, and the temperature is quickly reduced to a more proper temperature for heat preservation sintering for a longer time and natural cooling. Fig. 3 is an SEM image of the ceramic material as a function of the doping composition at the optimum sintering temperature, from which it is clearly observed that as a function of the doping composition, the grain size gradually decreases and the density gradually increases, reaching the optimum value at x =0.10 composition, the grain size being the smallest and the density being better, which demonstrates the successful use of the two-step sintering process. Fig. 4 is a graph showing the relationship between the breakdown electric field and the grain size, and it can be seen that the grain size and the breakdown electric field of the sample show an inverse relationship with the increase of the doping component, the grain size is 0.72 μm at the minimum and the breakdown electric field is 290kV/cm at the maximum at x =0.10, which is also sufficient to prove the successful use of the two-step sintering method.
The present invention can be realized by various raw materials and interval changes of the raw materials and interval changes of process parameters (such as temperature, time, etc.), and embodiments are not listed here. The sodium niobate-based ceramic with high breakdown electric field successfully prepared by the two-step sintering method has wide requirements in the fields of electric power technology, intelligent electric vehicles, laser systems, advanced electronic components and the like, has good application prospect in the field of capacitor energy storage due to the characteristics of no toxicity, no harm and environmental friendliness, and has good economic and social benefits.

Claims (1)

1. A process for preparing the energy-accumulating sodium niobate ceramic with high breakdown electric field by two-step sintering method uses Na as component 1-3x/ 2 Bi 3x/2 Nb 1-x Cu x O 3 (x =0,0.06,0.08,0.10,0.12) is a chemical proportioning equation, a traditional solid phase reaction method is combined with a novel two-step sintering process, and high-purity Na is used 2 CO 3 Powder and Nb 2 O 5 Powder of Bi 2 O 3 The method is characterized by comprising the following steps of:
(1) Calculating the mass of each raw material according to the molar ratio of x =0,0.06,0.08,0.10 and 0.12, and weighing Na 2 CO 3 Powder and Nb 2 O 5 Powder of Bi 2 O 3 Powder and CuO powder; na (Na) 2 CO 3 The purity of the powder is more than or equal to 99.5 percent; nb 2 O 5 The purity of the powder is more than or equal to 99.9 percent; bi 2 O 3 The purity of the powder is more than or equal to 99.00 percent; the purity of the CuO powder is more than or equal to 99 percent;
(2) Weighing Na in the step (1) 2 CO 3 And Nb 2 O 5 Carrying out mixing and ball milling on the powder to obtain matrix powder, wherein wet ball milling mixing is adopted in the process, a ball milling medium is zirconium balls and absolute ethyl alcohol (the mass ratio of the zirconium balls to the powder to the absolute ethyl alcohol is 5;
(3) Sequentially drying the matrix powder obtained in the step (2) (drying by using an air-blast drying oven at the temperature of 80 ℃ for 12 hours) and presintering (presintering by using a muffle furnace at the temperature of 850 ℃ for 4 hours) to obtain a prefabricated main matrix NaNbO 3 Powder material;
(4) The main matrix NaNbO obtained in the step (3) 3 Powder and Bi mixed according to the mixing ratio 2 O 3 Performing secondary ball milling on the powder and the CuO powder, wherein the ball milling method and parameters adopted in the process are consistent with those in the step 2);
(5) Drying the ball-milling powder obtained in the step (4) in sequence (the drying temperature is 80 ℃, and the time is 12 hours) to obtain powder which is prefabricated and uniformly mixed, and waiting for tabletting for later use;
(6) Granulating and tabletting the dried powder obtained in the step (5), and adding 5wt% of pva solution into the prefabricated mixed dry powder for granulation treatment to obtain powder particles; wherein the mass ratio of the prefabricated mixed dry powder to the pva solution is 0.15; after the granulation treatment is finished, sieving the formed powder particles, and selecting the powder particles with 60-100 meshes for tabletting; pressing the sieved powder particles under 200Mpa uniaxially into cylinders with diameter of 12mm and thickness of 1.5 mm;
(7) Placing the sample pressed in the step (6) at 600 ℃ for plastic removal, wherein the plastic removal process comprises the following steps: heating the muffle furnace to 600 ℃ at the speed of 5 ℃/min, keeping the temperature, calcining for 1.5h, and naturally cooling to room temperature;
(8) And (3) embedding the sample subjected to plastic removal in the step (7) into a 20ml crucible, and performing dense sintering in an air atmosphere by using a two-step sintering method, wherein in the process, the muffle furnace is heated to 1150 ℃ at the speed of 5 ℃/min, the temperature is kept for 2min, and then the temperature is reduced to 1000 ℃ at the speed of 10 ℃/min, and the blank is subjected to constant-temperature calcination for 2.5h to obtain the dense and regular sodium niobate-based ceramic.
CN202211381775.9A 2022-11-07 2022-11-07 Sodium niobate-based energy storage ceramic with high breakdown electric field and two-step sintering method thereof Pending CN115594501A (en)

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