CN114854140A - Preparation method of calcium copper titanate nanowire/polystyrene composite material - Google Patents
Preparation method of calcium copper titanate nanowire/polystyrene composite material Download PDFInfo
- Publication number
- CN114854140A CN114854140A CN202210469281.XA CN202210469281A CN114854140A CN 114854140 A CN114854140 A CN 114854140A CN 202210469281 A CN202210469281 A CN 202210469281A CN 114854140 A CN114854140 A CN 114854140A
- Authority
- CN
- China
- Prior art keywords
- composite material
- calcium
- copper
- ccto
- nws
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 239000002070 nanowire Substances 0.000 title claims abstract description 62
- HAUBPZADNMBYMB-UHFFFAOYSA-N calcium copper Chemical compound [Ca].[Cu] HAUBPZADNMBYMB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 30
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 159000000007 calcium salts Chemical class 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 229920005669 high impact polystyrene Polymers 0.000 abstract description 54
- 239000004797 high-impact polystyrene Substances 0.000 abstract description 54
- 239000000463 material Substances 0.000 abstract description 20
- 239000003990 capacitor Substances 0.000 abstract description 11
- 238000004146 energy storage Methods 0.000 abstract description 6
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000000843 powder Substances 0.000 description 18
- 239000000945 filler Substances 0.000 description 17
- 239000000919 ceramic Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 230000007935 neutral effect Effects 0.000 description 15
- 238000001027 hydrothermal synthesis Methods 0.000 description 14
- 239000010936 titanium Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 5
- 229910002113 barium titanate Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 2
- WEUCVIBPSSMHJG-UHFFFAOYSA-N calcium titanate Chemical compound [O-2].[O-2].[O-2].[Ca+2].[Ti+4] WEUCVIBPSSMHJG-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012767 functional filler Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a calcium copper titanate nanowire/polystyrene composite material, belonging to the technical field of nano composite materials; dissolving calcium copper titanate nanowires and polystyrene in a solvent, stirring, drying, and demoulding to obtain the calcium copper titanate nanowires/polystyrene composite material; the CCTO-NWs/HIPS composite material prepared by the method has the advantages that the CCTO-NWs/HIPS composite material is obtained by fully mixing the calcium copper titanate nanowires and the high impact polystyrene in the solvent through a solution mixing method, compared with pure HIPS, the dielectric constant value of the CCTO-NWs/HIPS composite material prepared by the method is greatly improved, and meanwhile, lower dielectric loss is kept, so that the CCTO-NWs/HIPS composite material is an environment-friendly material and has wide application prospects in the fields of high energy storage capacitors, integrated circuits and the like.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to a preparation method of a calcium copper titanate nanowire/polystyrene composite material.
Background
The effective high-capacity energy storage technology is a key technology for the development of current smart power grids, hybrid electric vehicles, new energy power generation, pulse power systems and the like, the existing energy storage technology comprises a dielectric capacitor, a super capacitor, a fuel cell and the like, wherein the dielectric capacitor has incomparable advantages due to high power density and ultra-long cycle life generated by the rapid charge and discharge rate of the dielectric capacitor, and the dielectric capacitor is safer, more reliable and more environment-friendly due to no electrochemical reaction, so that the wide application of the dielectric capacitor in the field of power electronics is greatly promoted. The core of the dielectric capacitor is the dielectric material, and the high dielectric constant is one of the ways to obtain high energy storage performance. Some ferroelectric ceramics have high dielectric constants, but the single ceramic material is hard, the process is complex, the sintering energy consumption and the like, so that the ferroelectric ceramics and the polymer are compounded by using multiple elbows, and the ferroelectric ceramics and the polymer can be widely concerned by integrating the advantages of high dielectric of inorganic materials, high breakdown of the polymer, low loss, easiness in processing into films, realization of large-scale production and the like.
At present, the filling material in the ceramic/polymer high dielectric composite material is generally selected from barium titanate (BaTiO) with a perovskite structure and higher dielectric constant and lower dielectric loss 3 ) Lead titanate (PbTiO) 3 ) Copper calcium titanate (CaCu) system, or recently reported 3 Ti 4 O 12 CCTO) ferroelectric ceramic powder, the dielectric constant of the composite material can be increased usually several times to ten and several times that of the polymer matrix. However, the amount of the ceramic particles added in such composite materials is often high, and even when the volume fraction of the ceramic particles reaches 70% or more, the dielectric constant of the composite material at normal temperature is generally difficult to exceed 100. Excessive ceramic addition in the composite material easily causes increase of dielectric loss, and reduction of processability, mechanical properties and puncture resistance. Recent research shows that ceramic nano-fillers with large length-diameter ratio, such as one-dimensional nano-fibers and two-dimensional nano-sheets, can form a large number of micro-capacitors in a matrix, and the mutual overlapping can increase the path curvature formed by electric branches during breakdown, so that the ceramic nano-fillers are more suitable for improving the dielectric constant and the breakdown field strength compared with spherical nano-particles, and thus the comprehensive performance can be improved in a leap manner. At present, the commercialized products of the nanowire ceramics are few, and images are difficult to obtain in real timeAnd fillers having various particle diameters and stable properties such as ceramic particles.
CaCu 3 Ti 4 O 12 (CCTO) is a ceramic material with high dielectric constant, the huge dielectric property of the CCTO is firstly discovered by Subramanian of DuPont laboratories in 2000, and the dielectric constant of the CCTO ceramic can exceed 10 at normal temperature 4 . The CCTO has attractive application potential in capacitors and electronic equipment because of stable chemical properties and good temperature stability and keeps lower dielectric loss in a wider frequency range. However, at present, the CCTO is less in commercial products, and especially, CCTO nanowires (CCTO-NWs) with more excellent dielectric properties are basically not commercial products. High Impact Polystyrene (HIPS) is a low cost polymer with the characteristics of easy processing, good toughness, excellent environmental protection and the like. Chinese patent CN101712784B describes a core-shell structured filler/polymer composite material, in which the core-shell filler is formed by coating ceramic particles with metal, the ceramic particles include Copper Calcium Titanate (CCTO), Barium Titanate (BT), and Barium Strontium Titanate (BST), the metal includes silver, cobalt, copper, and aluminum, and the polymer is one of polyvinylidene fluoride (PVDF) and its copolymer, polypropylene (PP), Polyethylene (PE), and polymethyl methacrylate (PMMA). In the embodiment, the BT @ Ag/PVDF composite material is prepared, the maximum value of the dielectric constant is 183, the dielectric constant is improved by 80% compared with the composite material simply added with BT filler, but the dielectric loss is about 0.2 and is still large.
At present, a preparation scheme of a composite material which takes HIPS as a matrix and CCTO-NWs as a filler is not found.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a calcium copper titanate nanowire/polystyrene composite material.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a calcium copper titanate nanowire/polystyrene composite material, which comprises the following steps: dissolving the calcium copper titanate nanowires and polystyrene in a solvent, stirring, drying, and demoulding to obtain the calcium copper titanate nanowire/polystyrene composite material.
Further, the preparation method of the copper calcium titanate nanowire is a two-step hydrothermal method, and specifically comprises the following steps:
(1) heating titanium dioxide and sodium hydroxide solution to obtain a precursor sodium titanate nanowire;
(2) and mixing and heating the sodium titanate nanowire with copper salt, calcium salt and ammonia water, calcining, soaking in acid, washing and drying to obtain the copper calcium titanate nanowire.
Further, in the step (1), the heating temperature is 180-240 ℃, and the time is 12-36 hours; the concentration of the sodium hydroxide solution is 6 mol/L; in the step (2), the heating temperature is 140-160 ℃, the time is 1-10 h, and the calcining is specifically carried out by heating to 700-900 ℃ at the speed of 30-50 ℃/min and keeping the temperature for 1-6 h.
Further, in the step (1), the molar ratio of the titanium dioxide to the sodium hydroxide is 3: 2; in the step (2), the copper salt is copper nitrate, the calcium salt is calcium nitrate, and the molar ratio of the sodium titanate nanowire to the copper salt to the calcium salt is 4: 12: 3; the acid is hydrochloric acid with the concentration of 0.1-1.0M, and the soaking time is 5-10 h.
The CCTO-NWs synthesized by the two-step hydrothermal method has simple process and low cost, and the nano wire with specific diameter and length can be obtained by controlling process parameters.
The diameter of the copper calcium titanate nanowire obtained by the two-step hydrothermal method is 50-200nm, and the length of the copper calcium titanate nanowire is 6-35 mu m.
Further, the solvent is N, N-dimethylacetamide; the volume of the copper calcium titanate nanowire is 50% or less of the total volume of the copper calcium titanate nanowire and the polystyrene.
Further, the stirring is carried out at the temperature of 20-30 ℃; and carrying out ultrasonic treatment for 0.5-5 h after stirring.
Further, the drying temperature is 50-80 ℃, and the drying time is 0.5-5 h.
Further, the stripping was performed in ice water.
The invention also provides the copper calcium titanate nanowire/polystyrene composite material prepared by the preparation method.
The principle of the invention is as follows: the dielectric properties of the polymer-based composite material are closely related to the compatibility of the matrix, the filler and the interface between the matrix and the filler. The functional filler is a key component, and the structure, the appearance, the surface performance and the like of the functional filler play decisive roles. The CCTO-NWs prepared by the method has high length-diameter ratio, is beneficial to mutual overlapping in the composite material, can increase the path curvature formed by electric branches during breakdown so as to improve the breakdown field strength, can make the seepage threshold of the composite material lower by using the CCTO-NWs as a filler, and improves the dielectric constant of the composite material under the condition of keeping lower dielectric loss, thereby obtaining the CCTO-NWs/HIPS composite material with excellent comprehensive performance.
According to the invention, researches are carried out on the aspects of preparation process of ceramic nanowires, preparation process of composite materials, morphology and distribution state of modified fillers, interface design and control and the like, firstly, common easily-obtained and low-cost raw materials are adopted, linear calcium copper titanate is prepared by a two-step hydrothermal method, and the length-diameter ratio of the nanowires can be controlled by adjusting reaction temperature and reaction time; the prepared CCTO-NWs is used as a filler, HIPS is used as a matrix, the volume ratio of the filler to the matrix is adjusted, and the CCTO-NWs/HIPS composite dielectric material is prepared.
Compared with the prior art, the invention has the following beneficial effects:
compared with CCTO nano particles, the linear filler has larger specific surface area than the particle filler, the nano wires and the polymer are compounded to increase the contact interface between the filler and the matrix, the interface proportion is increased to make the interface polarization more obvious, which is beneficial to improving the dielectric constant, and meanwhile, the composite material prepared by the invention has excellent performance in the aspects of improving the breakdown field strength and reducing the dielectric loss, thereby effectively improving the dielectric constant and simultaneously keeping the lower dielectric loss. Moreover, CCTO-NWs can enable the composite material to reach the percolation threshold value under lower addition amount, and can obviously improve the mechanical property of the dielectric material.
The CCTO-NWs/HIPS composite material is obtained by fully mixing the calcium copper titanate nanowires and the high impact polystyrene in the solvent by a solution mixing method, and compared with pure HIPS, the composite material prepared by the method has the advantages that the dielectric constant is increased to 74.15 from 4.21 of the pure HIPS at 1Hz, and the dielectric loss is kept to be lower (0.127); at 100Hz, the dielectric constant increased from 3.42 for pure HIPS to 61.63 while maintaining a low dielectric loss (0.072). The composite material is favorable for meeting the demand of the current electronic device on a high dielectric constant dielectric material, promotes the development of the electronic device towards a higher energy storage density direction, is an environment-friendly material, and has wide application prospects in the fields of high energy storage capacitors, integrated circuits and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
In FIG. 1, (a) to (e) are scanning electron micrographs of CCTO-NWs prepared in examples 1 to 5, respectively;
FIG. 2 is an X-ray diffraction pattern of CCTO-NWs prepared in examples 1 to 5;
in FIG. 3, (a) to (f) are respectively the cross-sectional scanning electron microscope images of the pure HIPS and the CCTO-NWs/HIPS composite materials prepared in examples 1 to 5 (corresponding to examples 1 to 5 in the figure);
FIG. 4 is a graph showing the relationship between dielectric constant and dielectric loss at room temperature and frequency of the CCTO-NWs/HIPS composite material and pure HIPS prepared in examples 1 to 5 (corresponding to examples 1 to 5 in the graph).
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
The preparation method of the copper calcium titanate nanowire/polystyrene composite material comprises the following steps:
1. the CCTO-NWs is prepared by a two-step hydrothermal method, and the method comprises the following steps:
(1) 50.3g of TiO were weighed 2 Uniformly dispersing the mixture in 70mL of 6M NaOH solution by stirring, transferring the mixed solution into 100mL of a reaction kettle lining after uniform stirring, carrying out hydrothermal reaction at 180 ℃ for 24 hours, washing the reaction kettle lining with deionized water to be neutral, and drying the reaction kettle lining to obtain titaniumSodium acid nanowire (Na) 2 Ti 3 O 7 A nanowire).
(2) 1.2g of Na 2 Ti 3 O 7 Uniformly mixing and stirring the nanowire, 2.9g of copper nitrate trihydrate and 0.7g of calcium nitrate tetrahydrate; slowly adding 1mL of 25 wt% ammonia water, stirring for 0.5 h, and placing in a reaction kettle for reaction at 150 ℃ for 10 h.
(3) And (3) washing the product obtained in the step (2) with deionized water to be neutral, drying, putting the product into a crucible, heating the product to 700 ℃ at the speed of 30 ℃/min in a muffle furnace, keeping the temperature for 6 hours, soaking the product in 0.1M hydrochloric acid for 10 hours, washing the product with deionized water to be neutral, and drying to obtain the CCTO-NWs.
2. The CCTO-NWs/HIPS composite film is prepared by adopting a solution mixing method, and the method comprises the following specific steps:
(1) 1.89 g of HIPS (polystyrene) was weighed into N, N-dimethylacetamide, and dissolved by stirring.
(2) 0.59 g of CCTO-NWs powder (the CCTO-NWs powder accounts for 10 percent of the total volume of the HIPS and the CCTO-NWs powder) is weighed and added into the solution obtained in the step (1), and the mixture is fully and uniformly stirred.
(3) And (3) carrying out ultrasonic treatment on the solution obtained in the step (2) for 0.5 hour, adding ice blocks while carrying out ultrasonic treatment, keeping the water temperature at 25 ℃, and mixing the solution more uniformly to obtain the composite material solution.
(4) And (4) pouring the composite material solution obtained in the step (3) into a culture dish, and putting the culture dish into a vacuum drying oven to dry for 5 hours at the temperature of 50 ℃.
(5) Putting the culture dish into ice water, performing demoulding treatment on the material, washing the material with distilled water, and drying to obtain the CCTO-NWs/HIPS composite material.
The CCTO-NWs/HIPS composite material prepared by the embodiment is subjected to copper plating treatment, and the dielectric property is tested after polarization at 50 ℃.
Example 2
The preparation method of the copper calcium titanate nanowire/polystyrene composite material comprises the following steps:
1. the CCTO-NWs is prepared by a two-step hydrothermal method, and the method comprises the following steps:
(1) 50.3g of TiO were weighed 2 Uniformly dispersing the mixture in 70mL of 6M NaOH solution by stirring, and then uniformly stirringTransferring the mixed solution into a 100mL reaction kettle lining, carrying out hydrothermal reaction at 200 ℃ for 12 hours, washing the reaction kettle to be neutral by using deionized water, and drying the reaction kettle to obtain Na 2 Ti 3 O 7 A nanowire.
(2) 1.2g of Na 2 Ti 3 O 7 Uniformly mixing and stirring the nanowires, 2.9g of copper nitrate trihydrate and 0.7g of calcium nitrate tetrahydrate; slowly adding 1mL of 28 wt% ammonia water, stirring for 1 hour, and reacting at 140 ℃ for 7 hours in the reaction kettle.
(3) And (3) washing the product obtained in the step (2) with deionized water to be neutral, drying, putting the product into a crucible, heating the product to 750 ℃ in a muffle furnace at a speed of 35 ℃/min, keeping the temperature for 6 hours, soaking the product in 0.3M hydrochloric acid for 8 hours, washing the product with deionized water to be neutral, and drying to obtain the CCTO-NWs.
2. The CCTO-NWs/HIPS composite film is prepared by adopting a solution mixing method, and the method comprises the following steps:
(1) 1.68 g of HIPS was weighed into N, N-dimethylacetamide and dissolved by stirring.
(2) And (2) adding 1.19 g of CCTO-NWs powder (the CCTO-NWs powder accounts for 20 percent of the total volume of the HIPS and the CCTO-NWs powder) into the solution obtained in the step (1), and fully and uniformly stirring.
(3) And (3) carrying out ultrasonic treatment on the solution obtained in the step (2) for 1 hour, adding ice blocks while carrying out ultrasonic treatment, keeping the water temperature at 20 ℃, and mixing the solution more uniformly to obtain the composite material solution.
(4) And (4) pouring the composite material solution obtained in the step (3) into a culture dish, and putting the culture dish into a vacuum drying oven to dry for 3 hours at the temperature of 60 ℃.
(5) Putting the culture dish into ice water, performing demoulding treatment on the material, washing the material with distilled water, and drying to obtain the CCTO-NWs/HIPS composite material.
The CCTO-NWs/HIPS composite material prepared by the embodiment is subjected to copper plating treatment, and the dielectric property is tested after polarization at 60 ℃.
Example 3
The preparation method of the copper calcium titanate nanowire/polystyrene composite material comprises the following steps:
1. the CCTO-NWs is prepared by a two-step hydrothermal method, and the method specifically comprises the following steps:
(1) balance50.3g of TiO was taken 2 Uniformly dispersing the mixture in 70mL of 6M NaOH solution by stirring, transferring the mixed solution into a 100mL reaction kettle lining, carrying out hydrothermal reaction at 240 ℃ for 36 hours, washing the reaction kettle lining with deionized water to be neutral, and drying the reaction kettle lining to obtain Na 2 Ti 3 O 7 A nanowire.
(2) 1.2g of Na 2 Ti 3 O 7 Uniformly mixing and stirring the nanowires, 2.9g of copper nitrate trihydrate and 0.7g of calcium nitrate tetrahydrate; slowly adding 1mL of 25 wt% ammonia water, stirring for 0.5 h, and placing in a reaction kettle for reaction at 160 ℃ for 1 h.
(3) And (3) washing the product obtained in the step (2) with deionized water to be neutral, drying, putting the product into a crucible, heating the product to 800 ℃ in a muffle furnace at a speed of 40 ℃/min, keeping the temperature for 2 hours, soaking the product in 0.2M hydrochloric acid for 5 hours, washing the product with deionized water to be neutral, and drying to obtain the CCTO-NWs.
2. The CCTO-NWs/HIPS composite film is prepared by adopting a solution mixing method, and the method comprises the following steps:
(1) 1.47 g of HIPS was weighed into N, N-dimethylacetamide, and dissolved by stirring.
(2) And (2) adding 1.78 g of CCTO-NWs powder (the CCTO-NWs powder accounts for 30 percent of the total volume of the HIPS and the CCTO-NWs powder) into the solution obtained in the step (1), and fully and uniformly stirring.
(3) And (3) carrying out ultrasonic treatment on the solution obtained in the step (2) for 2 hours, adding ice blocks while carrying out ultrasonic treatment, keeping the water temperature at 24 ℃, and mixing the solution more uniformly to obtain the composite material solution.
(4) And (4) pouring the composite material solution obtained in the step (3) into a culture dish, and putting the culture dish into a vacuum drying oven to dry for 3 hours at 70 ℃.
(5) Putting the culture dish into ice water, performing demoulding treatment on the material, washing the material with distilled water, and drying to obtain the CCTO-NWs/HIPS composite material.
The CCTO-NWs/HIPS composite material prepared by the embodiment is subjected to copper plating treatment, and the dielectric property is tested after polarization at 70 ℃.
Example 4
The preparation method of the copper calcium titanate nanowire/polystyrene composite material comprises the following steps:
1. the CCTO-NWs is prepared by a two-step hydrothermal method, and the method comprises the following steps:
(1) 50.3g of TiO were weighed 2 Uniformly stirring and dispersing the mixture in 70mL of 6M NaOH solution, transferring the mixed solution into a 100mL reaction kettle lining, carrying out hydrothermal reaction at 240 ℃ for 12 hours, washing the reaction kettle lining with deionized water to be neutral, and drying the reaction kettle lining to obtain Na 2 Ti 3 O 7 A nanowire.
(2) 1.2g of Na 2 Ti 3 O 7 Uniformly mixing and stirring the nanowires, 2.9g of copper nitrate trihydrate and 0.7g of calcium nitrate tetrahydrate; slowly adding 2mL of 25 wt% ammonia water, stirring for 2 hours, and placing in a reaction kettle for reaction at 140 ℃ for 3 hours.
(3) And (3) washing the product obtained in the step (2) with deionized water to be neutral, drying, putting the product into a crucible, heating the product to 900 ℃ in a muffle furnace at a speed of 50 ℃/min, keeping the temperature for 1 hour, soaking the product in 1M hydrochloric acid for 5 hours, washing the product with deionized water to be neutral, and drying to obtain the CCTO-NWs.
2. The CCTO-NWs/HIPS composite film is prepared by adopting a solution mixing method, and the method comprises the following steps:
(1) 1.26 g of HIPS was weighed into N, N-dimethylacetamide and dissolved by stirring.
(2) 2.37 g of CCTO-NWs powder (the CCTO-NWs powder accounts for 40 percent of the total volume of the HIPS and the CCTO-NWs powder) is weighed and added into the solution obtained in the step (1), and the mixture is fully and uniformly stirred.
(3) And (3) carrying out ultrasonic treatment on the solution obtained in the step (2) for 3 hours, adding ice blocks while carrying out ultrasonic treatment, keeping the water temperature at 30 ℃, and mixing the solution more uniformly to obtain the composite material solution.
(4) And (4) pouring the composite material solution obtained in the step (3) into a culture dish, and putting the culture dish into a vacuum drying oven to dry for 1 hour at the temperature of 80 ℃.
(5) Putting the culture dish into ice water, performing demoulding treatment on the material, washing the material with distilled water, and drying to obtain the CCTO-NWs/HIPS composite material.
The CCTO-NWs/HIPS composite material prepared by the embodiment is subjected to copper plating treatment, and the dielectric property is tested after polarization at 80 ℃.
Example 5
The preparation method of the copper calcium titanate nanowire/polystyrene composite material comprises the following steps:
1. the CCTO-NWs is prepared by a two-step hydrothermal method, and the method comprises the following steps:
(1) 50.3g of TiO were weighed 2 Uniformly stirring and dispersing the mixture in 70mL of 6M NaOH solution, transferring the mixed solution into a 100mL reaction kettle lining, carrying out hydrothermal reaction at 220 ℃ for 24 hours, washing the reaction kettle lining with deionized water to be neutral, and drying the reaction kettle lining to obtain Na 2 Ti 3 O 7 A nanowire.
(2) 1.2g of Na 2 Ti 3 O 7 Uniformly mixing and stirring the nanowires, 2.9g of copper nitrate trihydrate and 0.7g of calcium nitrate tetrahydrate; slowly adding 1mL of 28 wt% ammonia water, stirring for 2 hours, and placing in a reaction kettle for reaction at 155 ℃ for 8 hours.
(3) And (3) washing the product obtained in the step (2) with deionized water to be neutral, drying, putting the product into a crucible, heating the product to 800 ℃ in a muffle furnace at a speed of 45 ℃/min, keeping the temperature for 3 hours, soaking the product in 0.7M hydrochloric acid for 8 hours, washing the product with deionized water to be neutral, and drying to obtain the CCTO-NWs.
2. The CCTO-NWs/HIPS composite film is prepared by adopting a solution mixing method, and the method comprises the following steps:
(1) 1.05 g of HIPS was weighed into N, N-dimethylacetamide and dissolved by stirring.
(2) And (2) weighing 2.96 g of CCTO-NWs powder (the CCTO-NWs powder accounts for 50 percent of the total volume of the HIPS and the CCTO-NWs powder) and adding the powder into the solution obtained in the step (1), and fully and uniformly stirring the powder.
(3) And (3) carrying out ultrasonic treatment on the solution obtained in the step (2) for 5 hours, adding ice blocks while carrying out ultrasonic treatment, keeping the water temperature at 28 ℃, and mixing the solution more uniformly to obtain the composite material solution.
(4) And (4) pouring the composite material solution obtained in the step (3) into a culture dish, and putting the culture dish into a vacuum drying oven to dry for 2 hours at the temperature of 80 ℃.
(5) Putting the culture dish into ice water, performing demoulding treatment on the material, washing the material with distilled water, and drying to obtain the CCTO-NWs/HIPS composite material.
The CCTO-NWs/HIPS composite material prepared by the embodiment is subjected to copper plating treatment, and the dielectric property is tested after polarization at 80 ℃.
The scanning electron micrographs of the CCTO-NWs prepared in the examples 1 to 5 are respectively shown in FIGS. 1(a) to (e), and it can be seen from the images that the CCTO-NWs prepared in the examples have diameters of 50 to 200nm, lengths of 6 to 35 μm and uniform dispersion.
The X-ray diffraction pattern of the CCTO-NWs prepared in examples 1 to 5 is shown in FIG. 2, and it can be seen that no impurity peaks except the CCTO-NWs appear, indicating that the prepared CCTO-NWs is pure phase.
The sectional scanning electron microscope images of the adopted HIPS and the CCTO-NWs/HIPS composite material prepared in the embodiments 1-5 (corresponding to the examples 1-5 in the figure) are respectively shown in the figures 3(a) to (f), and it can be seen from the figures that in the composite material, the CCTO-NWs and the HIPS are fully mixed, and the filler is uniformly distributed in the matrix.
HIPS was copper plated and tested for dielectric properties. The dielectric constant and the relationship between the dielectric loss and the frequency of the HIPS and the CCTO-NWs/HIPS composite materials prepared in the embodiments 1-5 (corresponding to the examples 1-5 in the figure) and tested at room temperature are shown in FIG. 4, wherein the dielectric constant and the dielectric loss of each material at 1Hz and 100Hz are shown in Table 1:
TABLE 1
Comparative example 1
The difference from example 1 is that the HIPS in step 1(1) of example 1 was replaced with polyvinylidene fluoride.
Comparative example 2
The difference from example 1 is that step 2(2) of example 1, CCTO-NWs, was replaced with CCTO nanoparticles.
Comparative example 3
The difference from example 1 is that step (5) is: and (4) carrying out hot pressing on the film obtained in the step (4) for 5min at 180 ℃ under 10MPa by using a tablet press to form the CCTO-NWs/HIPS composite material.
Carrying out copper plating treatment on the composite material finally prepared in the comparative examples 1-3, testing the dielectric property at room temperature after polarization at 50 ℃, wherein the dielectric constants of the materials prepared in the comparative examples 1-3 at 1Hz are 12.32, 9.42 and 8.89 respectively, and the dielectric losses are 0.031, 0.047 and 0.028 respectively; the dielectric constants at 100Hz were 10.42, 8.53 and 6.87, respectively, and the dielectric losses were 0.026, 0.039 and 0.021, respectively.
The above description is only for the preferred embodiment of the present invention, and the protection scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention, the technical solution and the inventive concept of the present invention equivalent or change within the technical scope of the present invention.
Claims (9)
1. The preparation method of the calcium copper titanate nanowire/polystyrene composite material is characterized by comprising the following steps: dissolving the calcium copper titanate nanowires and polystyrene in a solvent, stirring, drying, and demoulding to obtain the calcium copper titanate nanowire/polystyrene composite material.
2. The method for preparing the calcium copper titanate nanowire/polystyrene composite material according to claim 1, wherein the method for preparing the calcium copper titanate nanowire comprises the following steps:
(1) heating titanium dioxide and sodium hydroxide solution to obtain a precursor sodium titanate nanowire;
(2) and mixing and heating the sodium titanate nanowire with copper salt, calcium salt and ammonia water, calcining, soaking in acid, washing and drying to obtain the copper calcium titanate nanowire.
3. The preparation method of the calcium copper titanate nanowire/polystyrene composite material according to claim 2, wherein in the step (1), the heating temperature is 180-240 ℃ and the time is 12-36 h; in the step (2), the heating temperature is 140-160 ℃, the time is 1-10 h, the calcining temperature is 700-900 ℃, and the time is 1-6 h.
4. The method for preparing the calcium copper titanate nanowire/polystyrene composite material according to claim 2, wherein in the step (1), the molar ratio of the titanium dioxide to the sodium hydroxide is 3: 2; in the step (2), the copper salt is copper nitrate, the calcium salt is calcium nitrate, and the molar ratio of the sodium titanate nanowire to the copper salt to the calcium salt is 4: 12: 3; the acid is hydrochloric acid with the concentration of 0.1-1.0M, and the soaking time is 5-10 h.
5. The method for preparing the calcium copper titanate nanowire/polystyrene composite material according to claim 1, wherein the solvent is N, N-dimethylacetamide; the volume of the copper calcium titanate nanowire is 50% or less of the total volume of the copper calcium titanate nanowire and the polystyrene.
6. The preparation method of the calcium copper titanate nanowire/polystyrene composite material as claimed in claim 1, wherein the stirring is performed at 20-30 ℃; and carrying out ultrasonic treatment for 0.5-5 h after stirring.
7. The preparation method of the calcium copper titanate nanowire/polystyrene composite material as claimed in claim 1, wherein the drying temperature is 50-80 ℃ and the drying time is 0.5-5 h.
8. The method for preparing the calcium copper titanate nanowire/polystyrene composite material according to claim 1, wherein the stripping is performed in ice water.
9. The calcium copper titanate nanowire/polystyrene composite material prepared by the preparation method according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210469281.XA CN114854140B (en) | 2022-04-28 | 2022-04-28 | Preparation method of copper calcium titanate nanowire/polystyrene composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210469281.XA CN114854140B (en) | 2022-04-28 | 2022-04-28 | Preparation method of copper calcium titanate nanowire/polystyrene composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114854140A true CN114854140A (en) | 2022-08-05 |
| CN114854140B CN114854140B (en) | 2024-03-01 |
Family
ID=82634839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210469281.XA Active CN114854140B (en) | 2022-04-28 | 2022-04-28 | Preparation method of copper calcium titanate nanowire/polystyrene composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114854140B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396548A (en) * | 2013-08-14 | 2013-11-20 | 武汉一海数字工程有限公司 | Preparation method of high-dielectric polyimide/calcium copper titanate nanowire composite material |
| CN107573645A (en) * | 2017-09-06 | 2018-01-12 | 深圳市峰泳科技有限公司 | A kind of built-in high-k flexible resin composite and its preparation method and application |
| CN108017861A (en) * | 2017-10-09 | 2018-05-11 | 南通洪明电工科技有限公司 | A kind of polymer-based dielectric composite material of coated with silica CaCu 3 Ti 4 O nanofiber and preparation method thereof |
| CN108300153A (en) * | 2017-10-13 | 2018-07-20 | 深圳市峰泳科技有限公司 | High energy storage density dielectric substance and preparation method thereof |
| CN111171514A (en) * | 2018-11-09 | 2020-05-19 | 深圳先进技术研究院 | Low dielectric composite material, preparation method and application thereof, and method for reducing dielectric constant of polymer |
-
2022
- 2022-04-28 CN CN202210469281.XA patent/CN114854140B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396548A (en) * | 2013-08-14 | 2013-11-20 | 武汉一海数字工程有限公司 | Preparation method of high-dielectric polyimide/calcium copper titanate nanowire composite material |
| CN107573645A (en) * | 2017-09-06 | 2018-01-12 | 深圳市峰泳科技有限公司 | A kind of built-in high-k flexible resin composite and its preparation method and application |
| CN108017861A (en) * | 2017-10-09 | 2018-05-11 | 南通洪明电工科技有限公司 | A kind of polymer-based dielectric composite material of coated with silica CaCu 3 Ti 4 O nanofiber and preparation method thereof |
| CN108300153A (en) * | 2017-10-13 | 2018-07-20 | 深圳市峰泳科技有限公司 | High energy storage density dielectric substance and preparation method thereof |
| CN111171514A (en) * | 2018-11-09 | 2020-05-19 | 深圳先进技术研究院 | Low dielectric composite material, preparation method and application thereof, and method for reducing dielectric constant of polymer |
Non-Patent Citations (2)
| Title |
|---|
| 康永: ""聚苯乙烯/CaCu3Ti4O12复合材料制备研究"", 《陶瓷》, no. 07, pages 26 - 29 * |
| 廖杨科: ""钛酸铜钙纳米线制备及其复合材料介电性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 08, pages 020 - 94 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114854140B (en) | 2024-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Azam et al. | Recent advances of silicon, carbon composites and tin oxide as new anode materials for lithium-ion battery: A comprehensive review | |
| Hu et al. | Ti 2 Nb 2x O 4+ 5x anode materials for lithium-ion batteries: a comprehensive review | |
| CN101712784B (en) | Core-shell structured packing/polymer-based composite material and preparation method thereof | |
| Li et al. | Progress of layered double hydroxide-based materials for supercapacitors | |
| Feng et al. | Highly dispersive Ba0. 6 Sr0. 4 TiO3 nanoparticles modified P (VDF‐HFP)/PMMA composite films with improved energy storage density and efficiency | |
| CN108329027B (en) | Fine-grain energy storage medium ceramic material with double-layer core-shell structure and preparation method thereof | |
| WO2003044881A1 (en) | Positive electrode active material for lithium secondary cell and lithium secondary cell | |
| CN103975100A (en) | Metal and ceramic nanofibers | |
| Chen et al. | Core-shell TiO2@ HfO2 nanowire arrays with designable shell thicknesses for improved permittivity and energy density in polymer nanocomposites | |
| CN110885473B (en) | Nano-particles, composite film, and preparation method and application thereof | |
| CN112185703B (en) | Dielectric energy storage material with two-dimensional composite sandwich structure and preparation method and application thereof | |
| Bhattacharya et al. | Delafossite type CuCo0. 5Ti0. 5O2 composite structure: a futuristic ceramics for supercapacitor and EMI shielding application | |
| JP2015043389A (en) | Manufacturing of ceramic capacitor containing micro metallic particles | |
| CN113024974B (en) | One-dimensional TiO2Polyvinylidene fluoride composite film doped with nanowire hybrid structure and preparation method thereof | |
| Dhere | Electrode materials for supercapacitors synthesized by sol–gel process | |
| Dhandapani et al. | Progress in Spinel‐Structured Cobaltite‐Based Positive Electrode Materials for Supercapacitors | |
| CN114854140B (en) | Preparation method of copper calcium titanate nanowire/polystyrene composite material | |
| CN102653621A (en) | Composite material with high dielectric constant and preparation method for composite material | |
| CN103755958A (en) | Preparation method of polyimide/copper calcium titanate coated silver nanoparticle composite material | |
| CN109119251B (en) | Porous MnCo2O4．5Preparation method of electrode material | |
| CN104505146B (en) | Dielectric composite material with nano core-shell and inner crystal structures, and preparation method of dielectric composite material | |
| CN109003815A (en) | Giant dielectric matter and rechargeable storage device based on it | |
| Moharana et al. | Synthesis and properties of percolative metal oxide-polymer composites | |
| Augustin et al. | Combustion synthesis of ABO~ 3 and AB~ 2O~ 4 compounds-An overview | |
| CN112846209A (en) | Preparation method of rod-shaped cobalt powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20220805 Assignee: SHANGHAI RUIJU ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Assignor: Shanghai Polytechnic University Contract record no.: X2024980014462 Denomination of invention: Preparation method of copper calcium titanate nanowire/polystyrene composite material Granted publication date: 20240301 License type: Common License Record date: 20240910 |
|
| EE01 | Entry into force of recordation of patent licensing contract |