CN110085432B - Preparation method of voltage-resistant high-strength capacitor material - Google Patents
Preparation method of voltage-resistant high-strength capacitor material Download PDFInfo
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- CN110085432B CN110085432B CN201910235990.XA CN201910235990A CN110085432B CN 110085432 B CN110085432 B CN 110085432B CN 201910235990 A CN201910235990 A CN 201910235990A CN 110085432 B CN110085432 B CN 110085432B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a preparation method of a voltage-resistant high-strength capacitor material, belonging to the technical field of electronic material preparation. The invention takes bamboo chips, wood chips, iron powder and the like as raw materials to prepare reaction solid, then the reaction solid is subjected to high-temperature heat treatment and is mixed with materials such as silicon nitride, zinc nitrate and the like to prepare a prefabricated product, and finally the prefabricated product is mixed with substances such as triacetin, sodium dodecyl benzene sulfonate and the like, hot pressing and calcining to obtain the high-strength capacitor material.
Description
Technical Field
The invention relates to a preparation method of a voltage-resistant high-strength capacitor material, belonging to the technical field of electronic material preparation.
Background
With the rapid development of human society and the continuous increase of energy demand, the traditional fossil energy is rapidly reduced and the global ecological environment is increasingly worsened. There has been an urgent need to develop clean, renewable energy sources. Super capacitor as a clean energy source has received close attention from scientific research and industrial fields due to its advantages of high power density, fast charge and discharge, long cycle life, etc.
The super capacitor is a novel energy storage device with the performance between that of a physical capacitor and that of a secondary battery, has higher specific capacitance and energy density than a common capacitor, and simultaneously has higher power density than a battery. The charge is stored mainly by means of electrochemical reaction on the surface of an electrode or a double electric layer, so that the charge-discharge device has the advantages of rapid charge-discharge, long service life, good stability, wide working temperature, simple circuit, safety, reliability, environmental protection and the like, can be widely applied to a plurality of fields of automobile industry, aerospace, national defense science and technology, information technology, electronic industry and the like, and has wide application prospect.
The electrode material is used as a decisive factor for determining the performance of the super capacitor, and the electrode material determines the main performance index of the super capacitor. An ideal electrode material should have high specific capacitance, high rate performance and cycling stability. The super capacitor can be divided into a carbon electrode capacitor, a metal oxide based capacitor and a conductive polymer based capacitor according to different electrode materials; there are two types of capacitors, an electric double layer capacitor and a faraday (pseudo) capacitor, depending on the energy storage mechanism. Faraday capacitors store energy based on reversible, rapid redox reactions occurring at the electrode interface. The electric double layer capacitor stores energy based on an interfacial electric double layer capacitance formed between an electrode and an electrolyte.
Carbon materials were the first materials used as supercapacitor active materials and are currently the most used electrode materials. The activated carbon is still the preferred material for preparing the electrode material of the super capacitor due to the characteristics of large specific surface area, easy preparation, low price and the like, but the specific capacity and the energy density are relatively low. The pseudocapacitance capacitor using metal oxide or conductive polymer as electrode material not only can form a double-layer on the interface of electrolyte and electrode, but also can produce redox reaction on the surface of electrode material, so that the latter has larger specific capacitance than the former. Although both the transition metal oxide and the conductive polymer exhibit high specific capacitance and high energy density, their power densities are poor and the energy density is low at high charge-discharge rates.
Capacitor materials in the prior art often have a small dielectric constant, cannot meet the requirement of electronic circuit miniaturization, have a low withstand voltage value, are unstable in structure and high in dielectric loss, and can cause certain harm to human bodies and environment in the production, use and scrapping processes. Chinese patent publication No. CN106554201A discloses a lead-free high-voltage ceramic capacitor material, which is prepared from the following components: barium titanate, titanium dioxide, calcium carbonate, zirconium dioxide, silicon dioxide and a modification additive. The formula does not contain lead element and rare metal element, is green and environment-friendly, has low cost, greatly improves the performance of the ceramic material by adding the modified additive, greatly improves the dielectric constant and the pressure resistance value of the ceramic material, can reach smaller temperature change rate, and ensures that the working engineering performance of the capacitor is more stable, but the product adopts a solid-phase synthesis method, and the uniformity of the final product is not good, thereby influencing the performance of the product.
Therefore, it is an urgent need to solve the above-mentioned problems by those skilled in the art to provide a capacitor material and a method for preparing the same, which does not contain toxic substances, does not pollute the environment, and has a high dielectric constant and a high withstand voltage.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the defects of low dielectric constant, limited application range, insufficient withstand voltage value and unstable structure of the existing capacitor material, the preparation method of the withstand voltage high-strength capacitor material is provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
the specific preparation steps of the high-strength capacitor material are as follows:
(1) putting the heat treatment product into a planetary ball mill, grinding and mixing for 40-50 min under the conditions that the ball material ratio is 10:1 and the rotating speed is 300-350 r/min to obtain a grinding mixture, and putting the grinding mixture, silicon nitride, strontium carbonate, zinc nitrate and bismuth titanate into a blender to be uniformly mixed to obtain a prefabricated product;
(2) uniformly mixing the prefabricated product, triacetin, sodium dodecyl benzene sulfonate and vinyl trimethoxy silane, putting the mixture into a hot press, pressing the mixture at a constant temperature of 140-150 ℃ and a pressing pressure of 0.8-1.0 MPa for 30-40 min, putting the pressed mixture into a sintering furnace, and sintering the pressed mixture for 50-60 min under an argon atmosphere and at a temperature of 1100-1200 ℃ to obtain the high-strength capacitor material;
the specific preparation steps of the heat-treated product are as follows:
(1) putting the acid emulsion and aluminum chloride crystal powder into a beaker, putting the beaker into an ultrasonic oscillator, oscillating for 1-2 hours under the condition that the frequency is 32-36 kHz, dropwise adding a potassium hydroxide solution with the mass fraction of 5-8% into the beaker after oscillation to adjust the pH value to be neutral to prepare a prefabricated solution, adding iron powder into the beaker, and mixing and stirring for 1-2 hours by using a stirrer at the rotating speed of 300-350 r/min to obtain mixed slurry;
(2) putting the mixed slurry into a suction filter, removing filtrate by suction filtration, washing with distilled water for 3-5 times to obtain reaction solid, putting the reaction solid into a tubular furnace, continuously introducing nitrogen into the tubular furnace, raising the temperature in the tubular furnace to 105-115 ℃, preheating for 60-80 min, raising the temperature in the tubular furnace to 500-550 ℃ after preheating, and calcining at high temperature for 50-60 min to obtain a heat treatment product;
the specific preparation steps of the acidic emulsion are as follows:
(1) putting bamboo chips and sawdust into an oven, drying for 2-3 hours at the temperature of 70-80 ℃, grinding into powder after drying, sieving with a 50-mesh sieve to obtain a dry mixed material, putting the dry mixed material and water into a reaction kettle, sealing the reaction kettle, raising the temperature in the reaction kettle to 120-130 ℃, standing at a constant temperature for 100-120 min to obtain reaction slurry;
(2) dropwise adding 6-10% by mass of sodium hydroxide solution into a reaction kettle to adjust the pH value to 10-11, mixing and stirring for 50-60 min at a rotating speed of 600-700 r/min by using a stirrer, increasing the pressure in the reaction kettle to 0.8-1.2 MPa, increasing the temperature to 90-100 ℃, standing for 2-3 h at a constant temperature and a constant pressure, dropwise adding 20-25% by mass of sulfuric acid solution after standing to adjust the pH value to 4-5, and thus obtaining the acid emulsion.
Preferably, the grinding mixture comprises 8-10 parts by weight of silicon nitride, 0.5-0.7 part by weight of strontium carbonate, 1.1-1.3 parts by weight of zinc nitrate and 0.3-0.5 part by weight of bismuth titanate.
Preferably, the weight parts of the preformed product are 10-12 parts, the glycerol triacetate is 1.2-1.4 parts, the sodium dodecyl benzene sulfonate is 0.3-0.6 part, and the vinyl trimethoxy silane is 2-3 parts.
The mass ratio of the acidic emulsion to the aluminum chloride crystal powder in the specific preparation step (1) of the heat-treated product is 15: 1.
The mass of the iron powder added into the beaker in the specific preparation step (1) of the heat-treated product is 5-9% of the mass of the pre-prepared solution.
The mass ratio of the bamboo chips to the wood chips in the specific preparation step (1) of the acidic emulsion is 5: 1.
In the specific preparation step (1) of the acidic emulsion, the bamboo chips are preferably one or more of moso bamboo, arhat bamboo and square bamboo in any proportion, and the wood chips are preferably one or more of pine, poplar and peach wood in any proportion.
The mass ratio of the dry mixed material to water in the specific preparation step (1) of the acidic emulsion is 1: 5.
The beneficial technical effects of the invention are as follows:
(1) the invention firstly dries bamboo chips and wood chips, mixes the dried bamboo chips and water at high temperature and boils the dried bamboo chips and the wood chips to prepare reaction slurry, then adds alkali liquor into the reaction slurry for high-temperature reaction, adjusts the pH value to acidity after the reaction, adds aluminum chloride powder, then adjusts the pH value to neutrality, adds iron powder for mixing reaction, filters the reaction to obtain reaction solid, then carries out high-temperature treatment on the reaction solid to obtain a heat treatment product, then mixes the heat treatment product with materials such as silicon nitride, zinc nitrate and the like to prepare a prefabricated product, finally mixes the prefabricated product with substances such as triacetin, sodium dodecyl benzene sulfonate and the like, puts the mixture into a hot press for hot pressing, puts into a sintering furnace after the hot pressing for high-temperature calcination to obtain the high-strength capacitor material, the invention carries out high-temperature hydrolysis and alkali liquor high-temperature treatment on the bamboo chips and the wood chips, extracts organic components such as bamboo, through high-temperature hydrolysis, functional groups such as hydroxyl, carboxyl and the like are generated on the surface of the bamboo fiber, so that a cross-linked structure with higher density and high bonding degree is formed, the mechanical strength of the microstructure of the capacitor material is improved, the voltage-resisting performance of the capacitor is enhanced, other components in the capacitor material can be protected by the cross-linked structure, the cross-linked structure is carbonized after high-temperature calcination, the fiber structure is condensed under the high-temperature condition, the density of the fiber structure is improved, the density of the microstructure is enhanced, lignin is carbonized, carbon particles are formed to fill each pore component in the capacitor material, covalent bond adsorption is formed between the carbon particles and other surrounding components, the structural strength of the capacitor material is enhanced, and the chemical stability and the voltage-resisting performance of the;
(2) according to the invention, aluminum ions are introduced into the structures of bamboo fibers and lignin, and are adsorbed on the surfaces of the bamboo fibers and the lignin by utilizing the effects of complexation, ionic bond adsorption and the like, then iron is added for replacement reaction, so that the aluminum ions react to generate aluminum simple substance particles, the aluminum simple substance particles are filled in the cross-linked structure of the bamboo fibers, and the aluminum simple substance particles are calcined at high temperature to generate aluminum oxide, covalent bonds can be formed among the aluminum oxides, intermolecular forces are adsorbed to form an aluminum oxide film layer to coat the carbon fibers, so that the chemical stability of the capacitor material is improved, meanwhile, the conductivity of the aluminum oxide is poor, the dielectric constant of the capacitor material can be improved, and the capacitor material has a wide.
Detailed Description
Putting bamboo chips and sawdust into an oven according to a mass ratio of 5:1, drying for 2-3 hours at a temperature of 70-80 ℃, grinding into powder after drying, sieving with a 50-mesh sieve to obtain a dried mixed material, putting the dried mixed material and water into a reaction kettle according to a mass ratio of 1:5, sealing the reaction kettle, raising the temperature in the reaction kettle to 120-130 ℃, and standing at a constant temperature for 100-120 min to obtain reaction slurry; dropwise adding 6-10% by mass of sodium hydroxide solution into the reaction kettle to adjust the pH value to 10-11, mixing and stirring for 50-60 min at a rotating speed of 600-700 r/min by using a stirrer, increasing the pressure in the reaction kettle to 0.8-1.2 MPa, increasing the temperature to 90-100 ℃, standing for 2-3 h at a constant temperature and a constant pressure, dropwise adding 20-25% by mass of sulfuric acid solution after standing to adjust the pH value to 4-5, and preparing an acid emulsion; putting the acid emulsion and aluminum chloride crystal powder into a beaker according to a mass ratio of 15:1, placing the beaker into an ultrasonic oscillator, oscillating for 1-2 hours under the condition of frequency of 32-36 kHz, dropwise adding a potassium hydroxide solution with the mass fraction of 5-8% into the beaker after oscillation to adjust the pH value to be neutral to prepare a prefabricated solution, adding iron powder with the mass fraction of 5-9% of the prefabricated solution into the beaker, and mixing and stirring for 1-2 hours at the rotating speed of 300-350 r/min by using a stirrer to obtain mixed slurry; putting the mixed slurry into a suction filter, removing filtrate by suction filtration, cleaning for 3-5 times by using distilled water to obtain reaction solid, putting the reaction solid into a tubular furnace, continuously introducing nitrogen into the tubular furnace, raising the temperature in the tubular furnace to 105-115 ℃, preheating for 60-80 min, raising the temperature in the tubular furnace to 500-550 ℃ after preheating, and calcining for 50-60 min at high temperature to obtain a heat treatment product; putting the heat treatment product into a planetary ball mill, grinding and mixing for 40-50 min under the conditions that the ball material ratio is 10:1 and the rotating speed is 300-350 r/min to obtain a grinding mixture, and putting 8-10 parts by weight of the grinding mixture, 0.5-0.7 part by weight of silicon nitride, 1.1-1.3 parts by weight of strontium carbonate, 1.0-1.4 parts by weight of zinc nitrate and 0.3-0.5 part by weight of bismuth titanate into a blender to be uniformly mixed to obtain a prefabricated product; according to the weight parts, 10-12 parts of the prefabricated product, 1.2-1.4 parts of triacetin, 0.3-0.6 part of sodium dodecyl benzene sulfonate and 2-3 parts of vinyl trimethoxy silane are uniformly mixed and then put into a hot press, the mixture is pressed for 30-40 min at a constant temperature under the conditions that the temperature is 140-150 ℃ and the pressing pressure is 0.8-1.0 MPa, and the pressed mixture is put into a sintering furnace and sintered for 50-60 min under the argon atmosphere and the temperature is 1100-1200 ℃ to obtain the high-strength capacitor material.
Example 1
Bamboo chip: mao bamboo
Wood chip: pine wood
Preparation of reaction slurry:
putting the moso bamboo chips and the pine wood chips into an oven according to the mass ratio of 5:1, drying for 2 hours at the temperature of 70 ℃, grinding into powder after drying, sieving with a 50-mesh sieve to obtain a dried mixed material, putting the dried mixed material and water into a reaction kettle according to the mass ratio of 1:5, sealing the reaction kettle, raising the temperature in the reaction kettle to 120 ℃, and standing at a constant temperature for 100 minutes to obtain reaction slurry.
Preparation of acidic emulsion:
and dropwise adding a sodium hydroxide solution with the mass fraction of 6% into the reaction kettle to adjust the pH value to 10, mixing and stirring for 50min at the rotating speed of 600r/min by using a stirrer, increasing the pressure in the reaction kettle to 0.8MPa, increasing the temperature to 90 ℃, standing for 2h at constant temperature and constant pressure, dropwise adding a sulfuric acid solution with the mass fraction of 20% after standing to adjust the pH value to 4, and thus obtaining the acid emulsion.
Preparation of mixed slurry:
putting the acid emulsion and aluminum chloride crystal powder into a beaker according to the mass ratio of 15:1, placing the beaker into an ultrasonic oscillator, oscillating for 1h under the condition of 32kHz frequency, dropwise adding 5% by mass of potassium hydroxide solution into the beaker after oscillation to adjust the pH value to be neutral to prepare a prefabricated solution, adding 5% by mass of iron powder into the beaker, and mixing and stirring for 1h at the rotating speed of 300r/min by using a stirrer to obtain mixed slurry.
Preparation of heat-treated product:
putting the mixed slurry into a suction filter, removing filtrate by suction filtration, washing for 3 times by using distilled water to obtain reaction solid, putting the reaction solid into a tubular furnace, continuously introducing nitrogen into the tubular furnace, raising the temperature in the tubular furnace to 105 ℃, preheating for 60min, raising the temperature in the tubular furnace to 500 ℃ after preheating, and calcining for 50min at high temperature to obtain a heat treatment product.
Preparation of a preformed product:
putting the heat treatment product into a planetary ball mill, grinding and mixing for 40min under the conditions that the ball-material ratio is 10:1 and the rotating speed is 300r/min to obtain a grinding mixture, and putting 8 parts of the grinding mixture, 0.5 part of silicon nitride, 1.1 part of strontium carbonate, 1.0 part of zinc nitrate and 0.3 part of bismuth titanate into a blender to be uniformly mixed according to parts by weight to obtain a prefabricated product.
Preparing a high-strength capacitor material:
according to the weight portion, 10 portions of the prefabricated product, 1.2 portions of triacetin, 0.3 portion of sodium dodecyl benzene sulfonate and 2 portions of vinyl trimethoxy silane are uniformly mixed and then put into a hot press, the mixture is pressed for 30min at a constant temperature under the conditions that the temperature is 140 ℃ and the pressing pressure is 0.8MPa, the pressed mixture is put into a sintering furnace, and the pressed mixture is sintered for 50min under the argon atmosphere and the temperature is 1100 ℃, so that the high-strength capacitor material with the pressure resistance is obtained.
Example 2
Bamboo chip: arhat bamboo
Wood chip: poplar wood
Preparation of reaction slurry:
putting the momordica grosvenori bamboo chips and the poplar wood chips into an oven according to the mass ratio of 5:1, drying for 2 hours at the temperature of 75 ℃, grinding into powder after drying, sieving with a 50-mesh sieve to obtain a dried mixed material, putting the dried mixed material and water into a reaction kettle according to the mass ratio of 1:5, sealing the reaction kettle, raising the temperature in the reaction kettle to 125 ℃, and standing at the constant temperature for 110 minutes to obtain reaction slurry.
Preparation of acidic emulsion:
and dropwise adding 8% by mass of sodium hydroxide solution into the reaction kettle to adjust the pH value to 10, mixing and stirring the mixture for 55min at a rotating speed of 650r/min by using a stirrer, increasing the pressure in the reaction kettle to 1.0MPa, increasing the temperature to 95 ℃, standing the mixture for 2h at a constant temperature and a constant pressure, dropwise adding 23% by mass of sulfuric acid solution after standing the mixture to adjust the pH value to 4, and thus obtaining the acid emulsion.
Preparation of mixed slurry:
putting the acid emulsion and aluminum chloride crystal powder into a beaker according to the mass ratio of 15:1, placing the beaker into an ultrasonic oscillator, oscillating for 1h under the condition of the frequency of 34kHz, dropwise adding 7% by mass of potassium hydroxide solution into the beaker after oscillation to adjust the pH value to be neutral to prepare a prefabricated solution, adding 6% by mass of iron powder of the prefabricated solution into the beaker, and mixing and stirring for 1h at the rotating speed of 325r/min by using a stirrer to obtain mixed slurry.
Preparation of heat-treated product:
putting the mixed slurry into a suction filter, removing filtrate by suction filtration, washing for 4 times by using distilled water to obtain reaction solid, putting the reaction solid into a tubular furnace, continuously introducing nitrogen into the tubular furnace, raising the temperature in the tubular furnace to 110 ℃, preheating for 70min, raising the temperature in the tubular furnace to 525 ℃ after preheating, and calcining for 55min at high temperature to obtain a heat treatment product.
Preparation of a preformed product:
putting the heat treatment product into a planetary ball mill, grinding and mixing for 45min under the conditions that the ball-material ratio is 10:1 and the rotating speed is 325r/min to obtain a grinding mixture, and putting 9 parts of the grinding mixture, 0.6 part of silicon nitride, 1.2 parts of strontium carbonate, 1.2 parts of zinc nitrate and 0.4 part of bismuth titanate into a blender to be uniformly mixed according to parts by weight to obtain a prefabricated product.
Preparing a high-strength capacitor material:
according to the weight portion, 11 portions of the prefabricated product, 1.3 portions of triacetin, 0.4 portion of sodium dodecyl benzene sulfonate and 2 portions of vinyl trimethoxy silane are uniformly mixed and then put into a hot press, the mixture is pressed for 35min at the constant temperature of 1405 ℃ and the pressing pressure of 0.9MPa, the pressed mixture is put into a sintering furnace, and the pressed mixture is sintered for 55min under the argon atmosphere and the temperature of 1150 ℃, so that the high-strength capacitor material with high pressure resistance is obtained.
Example 3
Bamboo chip: square bamboo
Wood chip: peach wood
Preparation of reaction slurry:
putting the square bamboo chips and the peach wood chips into an oven according to the mass ratio of 5:1, drying for 3 hours at the temperature of 80 ℃, grinding into powder after drying, sieving with a 50-mesh sieve to obtain a dried mixed material, putting the dried mixed material and water into a reaction kettle according to the mass ratio of 1:5, sealing the reaction kettle, raising the temperature in the reaction kettle to 130 ℃, and standing at the constant temperature for 120min to obtain reaction slurry.
Preparation of acidic emulsion:
and dropwise adding a sodium hydroxide solution with the mass fraction of 10% into the reaction kettle to adjust the pH value to 11, mixing and stirring for 60min at the rotating speed of 700r/min by using a stirrer, increasing the pressure in the reaction kettle to 1.2MPa, increasing the temperature to 100 ℃, standing for 3h at constant temperature and constant pressure, dropwise adding a sulfuric acid solution with the mass fraction of 25% after standing to adjust the pH value to 5, and thus obtaining the acid emulsion.
Preparation of mixed slurry:
putting the acid emulsion and aluminum chloride crystal powder into a beaker according to the mass ratio of 15:1, placing the beaker into an ultrasonic oscillator, oscillating for 2 hours under the condition that the frequency is 36kHz, dropwise adding a potassium hydroxide solution with the mass fraction of 8% into the beaker after oscillation to adjust the pH value to be neutral to prepare a prefabricated solution, adding iron powder with the mass fraction of 9% of the prefabricated solution into the beaker, and mixing and stirring for 2 hours at the rotating speed of 350r/min by using a stirrer to obtain mixed slurry.
Preparation of heat-treated product:
putting the mixed slurry into a suction filter, removing filtrate by suction filtration, washing for 5 times by using distilled water to obtain reaction solid, putting the reaction solid into a tubular furnace, continuously introducing nitrogen into the tubular furnace, raising the temperature in the tubular furnace to 115 ℃, preheating for 80min, raising the temperature in the tubular furnace to 550 ℃ after preheating, and calcining for 60min at high temperature to obtain a heat treatment product.
Preparation of a preformed product:
and putting the heat treatment product into a planetary ball mill, grinding and mixing for 50min under the conditions that the ball-material ratio is 10:1 and the rotating speed is 350r/min to obtain a grinding mixture, and putting 10 parts of the grinding mixture, 0.7 part of silicon nitride, 1.3 parts of strontium carbonate, 1.4 parts of zinc nitrate and 0.5 part of bismuth titanate into a blender to be uniformly mixed according to parts by weight to obtain a prefabricated product.
Preparing a high-strength capacitor material:
according to the weight portion, 12 portions of the prefabricated product, 1.4 portions of triacetin, 0.6 portion of sodium dodecyl benzene sulfonate and 3 portions of vinyl trimethoxy silane are uniformly mixed and then put into a hot press, the mixture is pressed for 40min at a constant temperature under the conditions that the temperature is 150 ℃ and the pressing pressure is 1.0MPa, the pressed mixture is put into a sintering furnace, and the pressed mixture is sintered for 60min under the argon atmosphere and the temperature is 1200 ℃ to obtain the high-strength capacitor material.
Comparative example 1: essentially the same procedure was followed as in example 1, except that no acidic emulsion was added.
Comparative example 2: the preparation was essentially the same as in example 2, except that no heat-treated product was added.
Comparative example 3: capacitor materials produced by a company in the city are announced.
The voltage-resistant high-strength capacitor material prepared by the invention and the capacitor material in the comparative example are detected, and the detection results are shown in table 1:
dielectric loss test
The voltage-resistant high-strength capacitor material prepared by the invention and the capacitor material in the comparative example are tested by a dielectric loss tester in the range of 1 +/-0.1 kHz of frequency and 1 +/-0.1V of alternating current effective value.
TABLE 1 measurement results of Properties
The data in table 1 show that the voltage-resistant high-strength capacitor material prepared by the invention has the characteristics of high dielectric constant, high voltage-resistant value, small dielectric loss, stable structure and the like, shows good circulation stability, prolongs the service life by 2-3 times compared with the common capacitor material, has a simple preparation method, is easy to operate in a preparation process flow, is suitable for large-scale production, and has extremely wide market prospect and application value.
Claims (8)
1. A preparation method of a voltage-resistant high-strength capacitor material is characterized by comprising the following specific preparation steps:
(1) putting the heat treatment product into a planetary ball mill, grinding and mixing for 40-50 min under the conditions that the ball material ratio is 10:1 and the rotating speed is 300-350 r/min to obtain a grinding mixture, and putting the grinding mixture, silicon nitride, strontium carbonate, zinc nitrate and bismuth titanate into a blender to be uniformly mixed to obtain a prefabricated product;
(2) uniformly mixing the prefabricated product, triacetin, sodium dodecyl benzene sulfonate and vinyl trimethoxy silane, putting the mixture into a hot press, pressing the mixture at a constant temperature of 140-150 ℃ and a pressing pressure of 0.8-1.0 MPa for 30-40 min, putting the pressed mixture into a sintering furnace, and sintering the pressed mixture for 50-60 min under an argon atmosphere and at a temperature of 1100-1200 ℃ to obtain the high-strength capacitor material;
the specific preparation steps of the heat treatment product are as follows:
(1) putting the acid emulsion and aluminum chloride crystal powder into a beaker, putting the beaker into an ultrasonic oscillator, oscillating for 1-2 hours under the condition that the frequency is 32-36 kHz, dropwise adding a potassium hydroxide solution with the mass fraction of 5-8% into the beaker after oscillation to adjust the pH value to be neutral to prepare a prefabricated solution, adding iron powder into the beaker, and mixing and stirring for 1-2 hours by using a stirrer at the rotating speed of 300-350 r/min to obtain mixed slurry;
(2) putting the mixed slurry into a suction filter, removing filtrate by suction filtration, washing with distilled water for 3-5 times to obtain reaction solid, putting the reaction solid into a tubular furnace, continuously introducing nitrogen into the tubular furnace, raising the temperature in the tubular furnace to 105-115 ℃, preheating for 60-80 min, raising the temperature in the tubular furnace to 500-550 ℃ after preheating, and calcining at high temperature for 50-60 min to obtain a heat treatment product;
the specific preparation steps of the acidic emulsion are as follows:
(1) putting bamboo chips and sawdust into an oven, drying for 2-3 hours at the temperature of 70-80 ℃, grinding into powder after drying, sieving with a 50-mesh sieve to obtain a dry mixed material, putting the dry mixed material and water into a reaction kettle, sealing the reaction kettle, raising the temperature in the reaction kettle to 120-130 ℃, standing at a constant temperature for 100-120 min to obtain reaction slurry;
(2) dropwise adding 6-10% by mass of sodium hydroxide solution into a reaction kettle to adjust the pH value to 10-11, mixing and stirring for 50-60 min at a rotating speed of 600-700 r/min by using a stirrer, increasing the pressure in the reaction kettle to 0.8-1.2 MPa, increasing the temperature to 90-100 ℃, standing for 2-3 h at a constant temperature and a constant pressure, dropwise adding 20-25% by mass of sulfuric acid solution after standing to adjust the pH value to 4-5, and thus obtaining the acid emulsion.
2. The method for preparing a voltage-resistant high-strength capacitor material according to claim 1, wherein the method comprises the following steps: the grinding mixture comprises, by weight, 8-10 parts of silicon nitride, 0.5-0.7 part of strontium carbonate, 1.1-1.3 parts of zinc nitrate, and 0.3-0.5 part of bismuth titanate.
3. The method for preparing a voltage-resistant high-strength capacitor material according to claim 1, wherein the method comprises the following steps: the weight parts of the prefabricated product are 10-12 parts, 1.2-1.4 parts of glycerol triacetate, 0.3-0.6 part of sodium dodecyl benzene sulfonate and 2-3 parts of vinyl trimethoxy silane.
4. The method for preparing a voltage-resistant high-strength capacitor material according to claim 1, wherein the method comprises the following steps: the mass ratio of the acidic emulsion to the aluminum chloride crystal powder in the specific preparation step (1) of the heat-treated product was 15: 1.
5. The method for preparing a voltage-resistant high-strength capacitor material according to claim 1, wherein the method comprises the following steps: the mass of the iron powder added into the beaker in the specific preparation step (1) of the heat-treated product is 5-9% of the mass of the pre-prepared solution.
6. The method for preparing a voltage-resistant high-strength capacitor material according to claim 1, wherein the method comprises the following steps: the mass ratio of the bamboo chips to the wood chips in the specific preparation step (1) of the acidic emulsion is 5: 1.
7. The method for preparing a voltage-resistant high-strength capacitor material according to claim 1, wherein the method comprises the following steps: the specific preparation step (1) of the acidic emulsion comprises the step of mixing one or more of moso bamboo, arhat bamboo and square bamboo in any proportion, and the wood chips are one or more of pine, poplar and peach wood in any proportion.
8. The method for preparing a voltage-resistant high-strength capacitor material according to claim 1, wherein the method comprises the following steps: the mass ratio of the dry mixed material to water in the specific preparation step (1) of the acidic emulsion is 1: 5.
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