A graphene oxide doped ternary inorganic-organic composite flexible energy storage capacitor
By using ternary inorganic-organic composite materials doped with graphene oxide, the problems of low dielectric constant and high dielectric loss in flexible capacitors have been solved, thus improving the performance of flexible energy storage capacitors with high dielectric constant and low loss.
Patent Information
- Application Number
- CN202310233038.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-03-13
- Publication Date
- 2025-12-05
- Estimated Expiration
- 2043-03-13
AI Technical Summary
Existing flexible capacitors are limited by their low dielectric constant in high energy density applications, and organic polymer materials have high dielectric loss, making it difficult to simultaneously meet the requirements of high dielectric constant and low loss.
A ternary inorganic-organic composite material doped with graphene oxide was used to prepare a graphene oxide-doped BCZT/PVDF composite material by means of a sol-gel method and a sacrificial template method. The doping amount of graphene oxide was controlled to improve the dielectric constant and reduce the dielectric loss.
With a lower ceramic filler content, the dielectric constant of the composite film is significantly improved, the dielectric loss is reduced, and the energy storage density and efficiency are significantly enhanced, meeting the high energy storage requirements of flexible capacitors.
Smart Images
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of inorganic-organic composite energy storage dielectric, and particularly relates to a ternary inorganic-organic composite flexible energy storage capacitor doped with graphene oxide. BACKGROUND
[0002] Energy storage materials and devices are one of the most popular research directions today. Compared with lithium ion batteries and supercapacitors, thin film capacitors have higher releasable energy density, higher operating voltage, fast charging and discharging, and long cycle life, and have important applications in many industries such as electronics, household appliances, communications, power, electrified railways, hybrid electric vehicles, wind power generation, and solar power generation. In recent years, it has attracted widespread attention from the academic and industrial communities.
[0003] To achieve the goal of high energy storage density of flexible capacitors, it is necessary to make it have both high dielectric constant and low dielectric loss. Organic polymer materials have good flexibility and high breakdown strength, but the lower dielectric constant hinders its application expansion. In the case of adding a small amount of graphene oxide, the high dielectric constant inorganic ceramic filler can be combined with organic polymer materials to increase the dielectric constant, form a flexible composite dielectric with high dielectric and low loss, and thus prepare a composite thin film capacitor with high flexibility, high dielectric constant and low loss.
[0004] The distribution morphology of fillers in polymers has a great influence on the performance of composite dielectrics. Small 3D structure ceramic particles are beneficial to the uniform distribution of ceramic fillers and the maintenance of high breakdown field strength of the composite material, and a small amount of graphene oxide filling can improve the dielectric of the composite material and play a role in regulating the energy storage performance. SUMMARY
[0005] The purpose of the present application is to provide a ternary inorganic-organic composite flexible energy storage capacitor doped with graphene oxide, which can improve the high dielectric constant while maintaining the flexibility of organic materials, reduce dielectric loss, and improve energy storage density to meet the application requirements of high energy storage of flexible capacitors.
[0006] To achieve the above purpose, the technical scheme adopted by the present application is as follows:
[0007] A ternary inorganic-organic composite flexible energy storage capacitor doped with graphene oxide, the chemical composition is xwt.% GO-Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 O3 / PVDF, wherein x = 0.25, 0.5, 0.75, 1 wt.%.
[0008] Further, the preparation of a ternary inorganic-organic composite flexible energy storage capacitor doped with graphene oxide includes the following steps:
[0009] (1) Preparation of sol by sol-gel method:
[0010] Take barium acetate and calcium acetate in a beaker according to the stoichiometric ratio of chemical composition, add water and glacial acetic acid and stir for 30 min, take another clean beaker and add appropriate amount of anhydrous ethanol and glacial acetic acid, then add zirconium n-butyl alcohol and titanium butyl alcohol dropwise, stir for 30 min, after the solutions in the two beakers are fully stirred, mix them, add a small amount of acetylacetone dropwise to the mixed solution, and stir the mixed solution uniformly to form a sol;
[0011] (2) Preparation of ceramic frame by sacrificial template method;
[0012] Add the prepared BCZT nano powder to the sol, then put the clean and dry cloth into the prepared sol, take it out after the cloth is fully immersed, and dry it; repeat twice; use a tablet press to process the dried cloth to make it flat, then clamp the cloth between two corundum pieces and place them in a muffle furnace for high temperature treatment;
[0013] (3) Preparation of GO-BCZT / PVDF:
[0014] Disperse different proportions of graphene oxide (GO) into N,N-dimethylformamide to prepare a graphene oxide dispersion solution, grind the prepared BCZT frame for 1 h, take the BCZT powder into a beaker, and add the graphene oxide dispersion solution dropwise, then ultrasonically oscillate under dry and constant temperature conditions to uniformly disperse the BCZT powder in the graphene oxide dispersion solution, and then continuously stir for 3 h;
[0015] (4) Take appropriate amount of PVDF powder and add it to the above solution, ultrasonically oscillate, then stir for 12 h, then take appropriate amount of mixed solution and flow it on a glass sheet, dry it at 60℃, then peel off the film from the glass sheet to obtain the GO-BCZT / PVDF composite material.
[0016] The high temperature treatment temperature of the BCZT ceramic frame is 1200℃, the heat treatment time is 3h, the temperature rising speed is 1℃ / min from 50 to 1200℃, and the temperature is kept at 200℃, 300℃ and 400℃ for 2h respectively.
[0017] The ratio of graphene oxide to PVDF in step 3) is 0.25wt.%, 0.5wt.%, 0.75wt.% and 1wt.%.
[0018] The ratio of BCZT to PVDF in step 3) is 10wt.%.
[0019] Further, based on the GO-BCZT / PVDF composite material, a silver paste electrode is coated on the surface of the composite material to prepare a flexible capacitor.
[0020] The technical effects achieved by the present application include:
[0021] The present application provides a graphene oxide doped ternary inorganic-organic composite flexible energy storage capacitor, the performance of the flexible energy storage capacitor can be controlled by controlling the doping amount of graphene oxide, and the performance is optimal when the graphene oxide doping amount is 0.5 wt.% under a lower ceramic filler content (10 wt.%), the dielectric loss of the composite film is lowest at 0.115 at a frequency of 1 kHz, the dielectric constant of the composite film reaches 11.36 at 1 kHz, and the effective energy storage density of the composite film is highest at 3.918 J / cm under an electric field of 580 kV / cm 3 , and the corresponding energy storage efficiency is 53.9%.
[0022] The present application provides a composite dielectric preparation method, which is simple, improves the dielectric constant of the composite material under a lower filler content (10 wt.%), and provides a new idea for improving the dielectric performance of the composite material. BRIEF DESCRIPTION OF DRAWINGS
[0023] Figure 1 is provided in the present application examples 1-3: GO-Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 XRD image of GO-Ba
[0024] Figure 2 is GO-Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 O3 / PVDF frame, powder after grinding and GO-Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 SEM image of GO-Ba
[0025] Figure 3 is provided in the present application examples 1-3: GO-Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 Dielectric performance curve of GO-Ba
[0026] Figure 4 is provided in the present application examples 1-3: GO-Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9O3 / PVDF flexible energy storage capacitor under the electric field intensity of 580 kV / cm; DETAILED DESCRIPTION
[0027] The application will be further described in conjunction with specific examples, which are intended to explain but not limit the application.
[0028] Example 1
[0029] A kind of graphene oxide doped ternary inorganic organic composite flexible energy storage capacitor, comprising the following steps:
[0030] 1. Sol-gel method for preparing sol
[0031] According to the chemical composition, respectively take barium acetate, calcium acetate in beaker, add water, glacial acetic acid stirring 30 min. Take another clean beaker and add appropriate amount of anhydrous ethanol and glacial acetic acid, then drop zirconium n-butyl alcohol and butyl titanate, stirring 30 min, after the solution of two beakers is stirred fully, mix them, drop a little acetylacetone into the mixed solution, stir the mixed solution uniformly to form sol.
[0032] 2. Sacrificial template method for preparing ceramic frame
[0033] Add the prepared BCZT nano powder to the sol, then put the clean and dry cloth into the prepared sol, take it out after the cloth is fully immersed, and dry it. Repeat twice. Process the dried cloth with a tablet press to make it flat, then clamp the cloth between two corundum pieces and place them in a muffle furnace for high temperature treatment.
[0034] 3. Preparation of GO-BCZT / PVDF
[0035] 0.25wt.% of graphene oxide (GO) is dispersed in N,N-dimethylformamide to prepare a graphene oxide dispersion liquid. Grind the prepared BCZT frame for a certain time, take the BCZT powder in a beaker, and drop the graphene oxide dispersion liquid into it. After the dropping is completed, ultrasonic oscillation is carried out under dry and constant temperature conditions to make the BCZT powder uniformly dispersed in the graphene oxide dispersion liquid, and then continuous stirring is carried out for 3h.
[0036] An appropriate amount of PVDF powder is added to the above solution, after ultrasonic oscillation, stirring for 12h, then an appropriate amount of mixed solution is flowed on a glass sheet, and after drying at 60℃, the film is peeled off from the glass sheet to obtain a GO-BCZT / PVDF composite material.
[0037] 4. The heat treatment temperature of the BCZT ceramic frame described in step 3 is 1200℃, and the heat treatment time is 3h; the temperature rising speed is 1℃ / min at 50-1200℃, and the temperature is kept at 200℃, 300℃ and 400℃ respectively for 2h.
[0038] 5. The GO-BCZT / PVDF flexible energy storage capacitor obtained in step 3 is coated with a silver paste electrode to prepare a flexible capacitor.
[0039] The dielectric loss of the composite film is lowest at 0.146 at a frequency of 1 kHz, the dielectric constant of the composite film reaches 9.11 at 1 kHz, and the effective energy storage density of the composite film is highest at 3.236 J / cm at an electric field of 580 kV / cm 3 The corresponding energy storage efficiency is 50.37%.
[0040] Example 2
[0041] A graphene oxide doped ternary inorganic-organic composite flexible energy storage capacitor, comprising the following steps:
[0042] 1. Preparation of sol by sol-gel method
[0043] Barium acetate and calcium acetate are taken in a beaker according to the stoichiometric ratio of chemical composition, water and glacial acetic acid are added and stirred for 30 min. Another clean beaker is taken and an appropriate amount of anhydrous ethanol and glacial acetic acid is added, then zirconium n-butoxide and butyl titanate are added dropwise and stirred for 30 min. After the solutions in the two beakers are stirred thoroughly, they are mixed, a small amount of acetylacetone is added dropwise to the mixed solution, and the mixed solution is stirred uniformly to form a sol.
[0044] 2. Preparation of ceramic frame by sacrificial template method
[0045] BCZT nanopowder prepared in advance is added to the sol, and a clean and dry cloth is placed in the prepared sol. After the cloth is completely immersed, it is taken out and dried. The process is repeated twice. The dried cloth is processed with a tablet press to make it flat, then the cloth is clamped between two corundum pieces and placed in a muffle furnace for high temperature treatment.
[0046] 3. Preparation of GO-BCZT / PVDF
[0047] 0.5wt.% of graphene oxide (GO) is dispersed in N,N-dimethylformamide to prepare a graphene oxide dispersion. The prepared BCZT frame is ground for a certain time, and the BCZT powder is taken in a beaker. The graphene oxide dispersion is added dropwise, and after the addition is completed, ultrasonic oscillation is carried out under dry and constant temperature conditions to make the BCZT powder uniformly dispersed in the graphene oxide dispersion, and then continuous stirring is carried out for 3h.
[0048] An appropriate amount of PVDF powder is added to the above solution, and after ultrasonic oscillation, stirring is carried out for 12h. Then an appropriate amount of mixed solution is flowed on a glass sheet, and after drying at 60℃, the film is peeled off from the glass sheet to obtain a GO-BCZT / PVDF composite material.
[0049] 4. The heat treatment temperature of the BCZT ceramic frame prepared in step 3 is 1200℃, and the heat treatment time is 3h; the temperature rising speed is 1℃ / min at 50-1200℃, and the holding time is 2h at 200℃, 300℃ and 400℃, respectively.
[0050] 5. The GO-BCZT / PVDF flexible energy storage capacitor is prepared by coating silver paste electrode on the surface of the GO-BCZT / PVDF flexible energy storage capacitor obtained in step 3.
[0051] The dielectric loss of the composite film is lowest at 0.115 at a frequency of 1kHz, the dielectric constant of the composite film reaches 9.75 at 1kHz, and the effective energy storage density of the composite film is highest at 3.918J / cm at an electric field of 580kV / cm. 3 The corresponding energy storage efficiency is 53.90%.
[0052] Example 3
[0053] A kind of graphene oxide doped ternary inorganic organic composite flexible energy storage capacitor, comprising the following steps:
[0054] 1. Sol-gel method for preparing sol
[0055] According to the chemical composition metering ratio, barium acetate and calcium acetate are taken in a beaker, water and glacial acetic acid are added and stirred for 30min. Another clean beaker is taken and an appropriate amount of anhydrous ethanol and glacial acetic acid are added, then zirconium n-butyl alcohol and butyl titanate are added dropwise and stirred for 30min. After the solutions in the two beakers are fully stirred, they are mixed, a small amount of acetylacetone is added dropwise to the mixed solution, and the mixed solution is stirred uniformly to form a sol.
[0056] 2. Sacrificial template method for preparing ceramic frame
[0057] BCZT nano-powder prepared in advance is added to the sol, and a clean and dry cloth is placed in the prepared sol. After the cloth is completely immersed, it is taken out and dried. The process is repeated twice. The dried cloth is processed with a tablet press to make it flat, then the cloth is clamped between two corundum pieces and placed in a muffle furnace for high temperature treatment.
[0058] 3. Preparation of GO-BCZT / PVDF
[0059] 0.75wt.% of graphene oxide (GO) is dispersed in N,N-dimethylformamide to prepare a graphene oxide dispersion liquid. The prepared BCZT frame is ground for a certain time, and the BCZT powder is taken in a beaker. The graphene oxide dispersion liquid is added dropwise, and after the addition is completed, ultrasonic oscillation is carried out under dry and constant temperature conditions to make the BCZT powder uniformly dispersed in the graphene oxide dispersion liquid, and then continuous stirring is carried out for 3h.
[0060] An appropriate amount of PVDF powder is added into the above solution, and after ultrasonic oscillation, stirring for 12 h, then an appropriate amount of mixed solution is taken to flow film on glass sheet, and after drying at 60℃, the film is peeled off from the glass sheet to obtain GO-BCZT / PVDF composite material.
[0061] 4. The heat treatment temperature of the BCZT ceramic frame of step 3 is 1200℃, and the heat treatment time is 3h; the temperature rising speed is 1℃ / min at 50-1200℃, and the temperature is kept at 200℃, 300℃ and 400℃ respectively for 2h.
[0062] 5. The silver paste electrode is coated on the surface of the GO-BCZT / PVDF flexible energy storage capacitor obtained in step 3 to prepare a flexible capacitor.
[0063] The dielectric loss of the composite film is lowest at 0.181 at 1kHz, the dielectric constant of the composite film reaches 11.36 at 1kHz, and the effective energy storage density of the composite film is highest at 3.066J / cm at 580kV / cm electric field. 3 The corresponding energy storage efficiency is 50.36%.
[0064] Example 4
[0065] A graphene oxide doped ternary inorganic-organic composite flexible energy storage capacitor, comprising the following steps:
[0066] 1. Preparation of sol by sol-gel method
[0067] According to the stoichiometric ratio of chemical composition, barium acetate and calcium acetate are taken in a beaker, water and glacial acetic acid are added and stirred for 30 min. Another clean beaker is taken and an appropriate amount of anhydrous ethanol and glacial acetic acid are added, then zirconium n-butyl alcohol and titanium butyl alcohol are added dropwise, and stirred for 30 min. After the solutions in the two beakers are stirred sufficiently, they are mixed, a small amount of acetylacetone is added dropwise, and the mixed solution is stirred uniformly to form a sol.
[0068] 2. Preparation of ceramic frame by sacrificial template method
[0069] BCZT nano-powder prepared in advance is added into the sol, and a clean and dry cloth is put into the prepared sol. After the cloth is completely immersed, it is taken out and dried. The process is repeated twice. The dried cloth is processed by a tablet press to make its shape flat, and then the cloth is clamped between two corundum sheets and placed in a muffle furnace for high temperature treatment.
[0070] 3. Preparation of GO-BCZT / PVDF
[0071] 1wt.% of graphene oxide (GO) is dispersed into N,N-dimethylformamide to prepare a graphene oxide dispersion solution, the burned BCZT frame is ground for a certain time, the BCZT powder is taken in a beaker, the graphene oxide dispersion solution is added dropwise, after the dropwise addition is completed, ultrasonic oscillation is performed under dry constant temperature conditions, the BCZT powder is uniformly dispersed in the graphene oxide dispersion solution, and then continuous stirring is performed for 3h.
[0072] An appropriate amount of PVDF powder is weighed and added into the above solution, after ultrasonic oscillation, stirring is performed for 12h, then an appropriate amount of the mixed solution is flowed on a glass sheet to form a film, the film is peeled off from the glass sheet after drying at 60°C to obtain a GO-BCZT / PVDF composite material.
[0073] 4. The heat treatment temperature of the BCZT ceramic frame in step 3 is 1200°C, the heat treatment time is 3h, the temperature rising speed is 1°C / min at 50-1200°C, and the temperature is kept at 200°C, 300°C and 400°C respectively for 2h.
[0074] 5. The surface of the GO-BCZT / PVDF flexible energy storage capacitor obtained in step 3 is coated with a silver paste electrode to prepare a flexible capacitor.
[0075] The dielectric loss of the composite film is lowest at 0.320 at a frequency of 1kHz, the dielectric constant of the composite film reaches 12.67 at 1kHz, the effective energy storage density of the composite film is highest at 3.488J / cm under an electric field of 580kV / cm 3 , and the corresponding energy storage efficiency is 58.86%.
Claims
1. A graphene oxide-doped ternary inorganic-organic composite flexible energy storage capacitor, characterized in that, based on x wt.%GO-Ba 0.85 Ca 0.15 Zr 0.1 Ti 0.9 O3 / PVDF (GO-BCZT / PVDF), where x =0.25, 0.5, 0.75, 1 wt.%, GO-BCZT / PVDF preparation includes the following steps: (1) Sol-gel method for preparing sol: According to the stoichiometric ratio of chemical composition, take barium acetate and calcium acetate into beakers, add water and glacial acetic acid and stir for 30 minutes. Take another clean beaker and add an appropriate amount of anhydrous ethanol and glacial acetic acid, then add zirconium butoxide and tetrabutyl titanate dropwise and stir for 30 minutes. After the solutions in the two beakers are thoroughly stirred, mix the two and add a small amount of acetylacetone dropwise to the mixture. Stir the mixture evenly to form a sol. (2) Preparation of BCZT ceramic framework by sacrificial template method; Add the pre-prepared BCZT nanoparticles to the sol, then put the clean and dry cloth into the prepared sol. After the cloth is completely submerged, take it out and dry it. Repeat this process twice. Use a tablet press to flatten the dried cloth. Then sandwich the cloth between two corundum sheets and place it in a muffle furnace for high-temperature treatment. (3) Preparation of GO-BCZT / PVDF: Different proportions of graphene oxide (GO) were dispersed in N,N-dimethylformamide to prepare a graphene oxide dispersion. The sintered BCZT framework was ground for 1 hour. BCZT powder was placed in a beaker, and the graphene oxide dispersion was added dropwise. After the addition was complete, the mixture was ultrasonically vibrated under dry and constant temperature conditions to ensure that the BCZT powder was uniformly dispersed in the graphene oxide dispersion. Then, the mixture was stirred continuously for 3 hours. An appropriate amount of PVDF powder was weighed and added to the above solution. After ultrasonic vibration, the mixture was stirred for 12 hours. Then, an appropriate amount of the mixed solution was flowed onto a glass slide. After drying at 60°C, the film was peeled off from the glass slide to obtain the GO-BCZT / PVDF composite material. (4) A flexible capacitor was prepared by coating a silver paste electrode on the surface of the GO-BCZT / PVDF composite material.
2. The graphene oxide-doped ternary inorganic-organic composite flexible energy storage capacitor according to claim 1, characterized in that, In step 2, the high-temperature treatment temperature of the BCZT ceramic frame is 1200℃, the heat treatment time is 3h, the heating rate from 50 to 1200℃ is 1℃ / min, and the temperature is held at 200℃, 300℃, and 400℃ for 2h respectively.
3. The graphene oxide-doped ternary inorganic-organic composite flexible energy storage capacitor according to claim 1, characterized in that, The ratio of graphene oxide to PVDF in step 3) is 0.25 wt.%, 0.5 wt.%, 0.75 wt.%, and 1 wt.%.
4. The graphene oxide-doped ternary inorganic-organic composite flexible energy storage capacitor according to claim 1, characterized in that, In step 3), the ratio of BCZT to PVDF is 10 wt.%.