Conductive paste for preparing super capacitor and preparation method thereof

文档序号：266433 发布日期：2021-11-19 浏览：24次中文

阅读说明：本技术 一种用于制备超级电容器的导电浆料及其制备方法 (Conductive paste for preparing super capacitor and preparation method thereof ) 是由潘一帆邝文辉张大康张玉露邓波周光星于 2021-05-06 设计创作，主要内容包括：本发明公开了一种用于制备超级电容器的导电浆料及其制备方法,导电浆料包括改性粉煤灰、改性碱激发剂和离子增强剂,所述改性粉煤灰由普通粉煤灰、NaOH和NaHCO-(3)制成；所述改性碱激发剂由硅铁粉和硅酸钾水溶液制成；所述离子增强剂由氯化锂和氟化钠制成。导电浆料固化后形成的地聚物孔隙率高,并含有大量的自由离子,可定向移动产生电流,并可作为具有储电性能的建筑材料。(The invention discloses a conductive paste for preparing a super capacitor and a preparation method thereof 3 Preparing; the modified alkali activator is prepared from ferrosilicon powder and a potassium silicate aqueous solution; the ion enhancer is made of lithium chloride and sodium fluoride. The geopolymer formed after the conductive paste is cured has high porosity and contains a large amount of free ions, can move in a direction to generate current, and can be used as a building material with electricity storage performance.)

1. The conductive paste for preparing the super capacitor is characterized by comprising modified fly ash, a modified alkali activator and an ion reinforcing agent,

the modified fly ash is prepared from common fly ash, NaOH and NaHCO₃Preparing;

the modified alkali activator is prepared from ferrosilicon powder and a potassium silicate aqueous solution;

the ion enhancer is made of lithium chloride and sodium fluoride.

2. The conductive paste for preparing a supercapacitor according to claim 1, wherein the preparation method of the modified fly ash comprises the following steps:

s11, preparing a modified solution, wherein the modified solution is prepared from NaOH solution and NaHCO₃Solution composition;

s12, adding the modified solution into common fly ash, uniformly stirring and standing to obtain a mixed solution;

and S13, drying and roasting the mixed solution to obtain the modified fly ash.

3. The conductive paste for preparing a supercapacitor according to claim 2, wherein NaOH solution and NaHCO₃The concentration of the solution is 0.7-1.5 mol/L, and the volume of the NaOH solution is as follows: NaHCO 2₃And (5) the volume of the solution is 1.

4. The conductive paste for producing a supercapacitor according to claim 2 or 3, wherein the mass of the modifying solution is: the mass of the common fly ash is (8-15): 1.

5. the conductive paste for preparing the supercapacitor according to claim 2, wherein in the step S13, the mixed solution is dried in an oven at 80-90 ℃, and then placed in a muffle at 550-650 ℃ for heat preservation for 1.5-2.5 h.

6. The electroconductive paste for producing a supercapacitor according to claim 1, wherein the modified alkali activator is made of 3 to 5 parts by mass of ferrosilicon powder and 28 to 32 parts by mass of an aqueous solution of potassium silicate.

7. The conductive paste for producing a supercapacitor according to claim 1 or 6, wherein the aqueous solution of potassium silicate has a modulus of 1.8 to 2.3 and a concentration of 48 to 52%.

8. The conductive paste for preparing a supercapacitor according to claim 1 or 6, wherein the silicon-iron powder has a silicon content of 90-95% and a fineness of 300-400 mesh.

9. The conductive paste for producing a supercapacitor according to claim 1, wherein the ionic enhancer is made of 1 to 3 parts by mass of lithium chloride and 1 to 3 parts by mass of sodium fluoride.

10. A method for preparing the conductive paste for preparing the supercapacitor according to any one of claims 1 to 9, comprising:

and mixing the modified fly ash, the modified alkali activator and the ionic reinforcing agent, and stirring at the rotating speed of 800-1500 r/min for 1-5 min to obtain the conductive slurry for preparing the supercapacitor.

Technical Field

The invention relates to the technical field of super capacitors, in particular to conductive paste for preparing a super capacitor and a preparation method thereof.

Background

The conductive concrete is a special concrete, and its basic principle is that the conductive material can be used for partially or completely substituting general aggregate in the concrete, and it is a special concrete with defined electric property and certain mechanical property. The conductive concrete has the sensing and conversion capability of heat and electricity, so that the conductive concrete not only can be used as a building bearing material, but also plays an important role in the aspects of electricians, electrons, electromagnetic interference shielding, static electricity prevention, electric heaters, reinforcing steel bar cathode protection, building ground heating, pavement deicing and snow melting and the like. Research on conductive concrete has received increasing attention.

Conventional electrically conductive concrete is made using electrically conductive additives, such as Carbon Fibers (CFs), steel fibers, graphene, etc., which are themselves good conductors of electricity, to induce electrical conductivity in the cement-based material. The conductive additives are interconnected in the cement-based material to form a good conductor path for electrical conduction. The current technology only develops the conductivity of the building material, but does not develop the electricity storage performance of the building material.

Disclosure of Invention

The invention aims to provide conductive paste for preparing a super capacitor, which has high porosity of geopolymer formed after curing, contains a large amount of free ions and can directionally move to generate current.

The invention also aims to provide the conductive paste for preparing the super capacitor, and the cured conductive paste can form geopolymer with low resistivity and can be used as a building material with electricity storage performance.

The technical problem to be solved by the invention is to provide a preparation method of conductive paste for preparing a super capacitor, which is simple in process, high in porosity of geopolymer formed after the conductive paste is solidified, contains a large amount of free ions, and can directionally move to generate current.

In order to solve the technical problem, the invention provides a conductive paste for preparing a super capacitor, which comprises modified fly ash, a modified alkali activator and an ion reinforcing agent,

the modified fly ash is prepared from common fly ash, NaOH and NaHCO₃Preparing;

the modified alkali activator is prepared from ferrosilicon powder and a potassium silicate aqueous solution;

the ion enhancer is made of lithium chloride and sodium fluoride.

As an improvement of the scheme, the preparation method of the modified fly ash comprises the following steps:

s11, preparing a modified solution, wherein the modified solution is prepared from NaOH solution and NaHCO₃Solution composition;

s12, adding the modified solution into common fly ash, uniformly stirring and standing to obtain a mixed solution;

and S13, drying and roasting the mixed solution to obtain the modified fly ash.

As an improvement of the above scheme, NaOH solution and NaHCO₃The concentration of the solution is 0.7-1.5 mol/L, and the volume of the NaOH solution is as follows: NaHCO 2₃And (5) the volume of the solution is 1.

As an improvement of the above scheme, the quality of the modified solution: the mass of the common fly ash is (8-15): 1.

in the improvement of the scheme, in step S13, the mixed solution is placed in an oven at 80-90 ℃ for drying, and then placed in a muffle at 550-650 ℃ for heat preservation for 1.5-2.5 h.

As an improvement of the scheme, the modified alkali activator is prepared from 3-5 parts of ferrosilicon powder and 28-32 parts of potassium silicate aqueous solution by mass.

As an improvement of the scheme, the modulus of the potassium silicate aqueous solution is 1.8-2.3, and the concentration is 48-52%.

As an improvement of the scheme, the silicon content of the ferrosilicon powder is 90-95%, and the fineness is 300-400 meshes.

As an improvement of the scheme, the ion reinforcing agent is prepared from 1-3 parts by mass of lithium chloride and 1-3 parts by mass of sodium fluoride.

Correspondingly, the invention also provides a preparation method of the conductive paste for preparing the supercapacitor, which comprises the following steps:

The implementation of the invention has the following beneficial effects:

the invention is prepared from NaOH solution and NaHCO₃The modified solution composed of the solution can destroy partial glass state structure and protective film on the surface of the fly ash, so that the structure of the modified fly ash becomes looser and more porous than the structure of the common fly ash, a through pipeline is formed, and the directional movement of charged ions is facilitated.

According to the invention, lithium chloride and sodium fluoride are doped into the geopolymer, and the released lithium ions and fluorine ions can directionally move through silicon-aluminum oxide (-Si-O-Al-O-) tetrahedrons formed in the hardened geopolymer due to the small volume of the geopolymer, so that the conductivity of the geopolymer is enhanced.

According to the invention, the ferrosilicon powder is added into the potassium silicate aqueous solution, so that hydroxide ions can be removed and a large amount of heat can be released, thereby enhancing the polymerization of the potassium silicate aqueous solution and the modified fly ash, simultaneously precipitating hydrogen, forming a large amount of micro bubbles in the hardened alkali-excited geopolymer matrix, and gathering the ionic aqueous solution in the bubbles, so as to be beneficial to the directional movement of charged particles.

Compared with the common fly ash, the porosity of the modified fly ash is improved by 50 percent; compared with geopolymer prepared from common fly ash, the geopolymer prepared from the modified fly ash and the modified alkali activator has the porosity increased by 20%.

The geopolymer formed by the conductive paste of the invention contains interconnected micropores, wherein a pore water solution (potassium silicate solution remained after the excitation modified fly ash) is present in the micropores, and the pore water solution contains a preset amount of freely movable ions. Wherein the resistivity of the conductive paste after 28 days of curing is less than or equal to 0.2 omega-m, and the conductive paste has the electricity storage performance which is not possessed by the conventional polymer. The energy density of the super capacitor formed by the geopolymer is calculated to be 16-20 W.h/kg, and the LED lamp bulb with the rated voltage of 1.8-2.1V can be lightened for more than 5 hours after being charged for 1 minute by a 30V direct current power supply.

Detailed Description

The invention provides conductive paste for preparing a super capacitor, which comprises modified fly ash, a modified alkali activator and an ion reinforcing agent.

The modified fly ash is prepared from common fly ash, NaOH and NaHCO₃And (4) preparing.

The preparation method of the modified fly ash comprises the following steps:

s11, preparing a modified solution, wherein the modified solution is prepared from NaOH solution and NaHCO₃Solution composition;

s12, adding the modified solution into common fly ash, uniformly stirring and standing to obtain a mixed solution;

and S13, drying and roasting the mixed solution to obtain the modified fly ash.

The common fly ash contains a large amount of micro glass beads, the component is silicon dioxide, the structure is compact, and NaOH solution and NaHCO in the modified solution of the invention₃The solution can corrode silicon dioxide, so that a large number of cavities are generated by corrosion of micro glass beads in the common fly ash, and the transmission of conductive particles can be accelerated.

Specifically, the invention is composed of NaOH solution and NaHCO₃The modified solution composed of the solution can destroy partial glass state structure and protective film on the surface of the fly ash, so that the structure of the modified fly ash becomes looser and more porous than the structure of the common fly ash, a through pipeline is formed, and the directional movement of charged ions is facilitated.

Wherein, NaOH solution and NaHCO₃The concentration of the solution is 0.7-1.5 mol/L, and the volume of the NaOH solution is as follows: NaHCO 2₃And (5) the volume of the solution is 1. If NaOH solution and NaHCO₃If the concentration of the solution is less than 0.7mol/L, the concentration is too low, the corrosion capability of the modified solution is weakened, the modification effect is reduced, and the porosity of the modified fly ash is reduced; if NaOH solution and NaHCO₃If the concentration of the solution is more than 1.5mol/L, the concentration is too high, the corrosion effect is too strong, and the corrosion is also causedThe modification effect is influenced, so that the porosity of the modified fly ash cannot be effectively improved. If the volume of the NaOH solution: NaHCO 2₃If the volume of the solution is more than 5:1, the content of the NaOH solution is excessive, and if the volume of the NaOH solution is: NaHCO 2₃If the volume of the solution is less than 2:1, the content of the NaOH solution is too small, which affects the corrosion capability of the modified solution, reduces the modification effect and reduces the porosity of the modified fly ash.

Preferably, NaOH solution and NaHCO₃The concentration of the solution is 0.9-1.3 mol/L, and the volume of the NaOH solution is as follows: NaHCO 2₃The volume of the solution is (2.5-4) and 1.

More preferably, NaOH solution and NaHCO₃The concentration of the solution is 1mol/L, the volume of the NaOH solution is as follows: NaHCO 2₃The volume of the solution was 3: 1.

Wherein the mass of the modified solution is as follows: the mass of the common fly ash is (8-15): 1. if the quality of the modified solution: the mass of the common fly ash is more than 15: 1, the use amount of the modification solution is excessive, and the modification solution is excessively wasted; if the quality of the modified solution: the mass of the common fly ash is less than 10: 1, the dosage of the modified solution is too small, and the common fly ash cannot be completely modified.

Preferably, the mass of the ordinary fly ash: mass of modified solution 1: (9-13).

More preferably, the mass of the common fly ash is as follows: mass of modified solution 1: 10.

specifically, in step S13, the mixed solution is placed in an oven at 80-90 ℃ for drying, and then placed in a muffle at 550-650 ℃ for heat preservation for 1.5-2.5 h. Wherein the temperature of the muffle furnace is raised to 550-650 ℃ within 1.5-2.5 h.

Specifically, the common fly ash is first-grade fly ash.

The modified alkali activator is prepared from ferrosilicon powder and a potassium silicate aqueous solution.

Preferably, the modified alkali activator is prepared from 3-5 parts by mass of ferrosilicon powder and 28-32 parts by mass of potassium silicate aqueous solution.

The preparation method of the modified alkali activator comprises the following steps: adding 3-5 parts of ferrosilicon powder into 28-32 parts of potassium silicate aqueous solution, and uniformly stirring to obtain the modified alkali activator.

The principle of the modified alkali activator is as follows: the ferrosilicon powder and water can react to generate a large amount of hydrogen, and after the modified alkali activator and the modified fly ash are mixed, the hydrogen forms a large amount of micro bubbles in the slurry, and the micro bubbles can contain the conductive liquid, so that the transmission resistance of conductive ions is reduced, and the conductivity of the slurry is improved.

Specifically, the ferrosilicon powder is added into the potassium silicate aqueous solution, so that hydroxide ions can be removed and a large amount of heat can be released, thereby enhancing the polymerization of the potassium silicate aqueous solution and the modified fly ash, simultaneously precipitating hydrogen, forming a large amount of micro bubbles in the hardened alkali-activated geopolymer matrix, and gathering the ionic aqueous solution in the bubbles, which is beneficial to the directional movement of charged particles.

Wherein the modulus of the potassium silicate aqueous solution is 1.8-2.3, and the concentration is 48-52%; the silicon content of the ferrosilicon powder is 90-95%, and the fineness of the ferrosilicon powder is 300-400 meshes. If the silicon content in the ferrosilicon powder is less than 90%, the purity is insufficient, and the number of micro-bubbles is influenced; wherein, the finer the ferrosilicon powder is, the more sufficient the reaction with water glass is, the better the conductivity of the formed slurry is, but if too fine, the oxidation after processing is fast, and the slurry is easy to lose efficacy and difficult to store.

More preferably, the modulus of the potassium silicate aqueous solution is 2.0, and the concentration is 48-52%; the silicon content of the ferrosilicon powder is 90-95%, and the fineness of the ferrosilicon powder is 300-400 meshes.

The modified alkali activator of the invention needs to be prepared at any time, and loses efficacy after being placed for about 10 min.

The ion enhancer is made of lithium chloride and sodium fluoride. Preferably, the ion enhancer is prepared from 1-3 parts by mass of lithium chloride and 1-3 parts by mass of sodium fluoride.

The preparation method of the ionic reinforcing agent comprises the following steps: and uniformly mixing 1-3 parts of lithium chloride and 1-3 parts of sodium fluoride to obtain the ionic reinforcing agent. Wherein, the lithium chloride and the sodium fluoride are common chemical pure reagents.

Specifically, the conductive slurry comprises 56-64 parts of modified fly ash, 28-32 parts of potassium silicate aqueous solution, 3-5 parts of ferrosilicon powder, 1-3 parts of lithium chloride and 1-3 parts of sodium fluoride.

Correspondingly, the invention also provides a preparation method of the conductive paste for preparing the supercapacitor, which comprises the following steps:

The invention will be further illustrated by the following specific examples

Example 1

S1, adding 56 parts of common fly ash into 560 parts of modified solution, stirring at normal temperature for 2 hours, standing for 30 minutes, drying in an oven at 80 ℃, placing in a muffle furnace at 600 ℃, and preserving heat for 2 hours to obtain modified fly ash;

wherein the modification solution consists of 1mol/L NaOH solution and 1mol/L NaHCO solution₃Solution composition, volume of NaOH solution: NaHCO 2₃Body of solutionProduct is 3: 1;

s2, uniformly mixing 2 parts of lithium chloride and 2 parts of sodium fluoride to obtain an ion reinforcing agent:

s3, adding 3 parts of silicon iron powder containing 90% of silicon and having fineness of 300 meshes into 28 parts of potassium silicate aqueous solution with modulus of 2.0 and concentration of 48%, and uniformly stirring to obtain a modified alkali activator;

s4, adding the newly prepared modified alkali activator into the uniformly mixed ionic reinforcing agent and the modified fly ash within 10min, and stirring for 2min at the rotating speed of 1000r/min to obtain the conductive slurry for preparing the super capacitor.

After the conductive paste of example 1 was cured for 28 days, the resistivity of the formed geopolymer was 0.1. + -. 0.02. omega. m.

Example 2

S1, adding 64 parts of common fly ash into 640 parts of modified solution, stirring at normal temperature for 2 hours, standing for 30 minutes, drying in a 90 ℃ oven, and then placing in a 600 ℃ muffle furnace for heat preservation for 2 hours to obtain modified fly ash;

wherein the modification solution consists of 1mol/L NaOH solution and 1mol/L NaHCO solution₃Solution composition, volume of NaOH solution: NaHCO 2₃The volume of the solution was 3: 1;

s2, uniformly mixing 3 parts of lithium chloride and 3 parts of sodium fluoride to obtain an ion reinforcing agent:

s3, adding 5 parts of silicon iron powder containing 95% of silicon and having fineness of 400 meshes into 30 parts of potassium silicate aqueous solution with modulus of 2.0 and concentration of 52%, and uniformly stirring to obtain a modified alkali activator;

After the conductive paste of example 2 was cured for 28 days, the resistivity of the formed geopolymer was 0.08. + -. 0.02. omega. m.

Comparative example 1

64 parts of common fly ash is added into 32 parts of 52 percent potassium silicate aqueous solution, and the mixture is stirred for 2min at the rotating speed of 1000r/min, so as to obtain common slurry.

After the slurry of example 3 was cured for 28 days, the resistivity of the geopolymer formed was 52.5. omega. m.

Because the common fly ash contains carbon powder particles, geopolymer formed by the common fly ash has weak electrical conductivity but does not have electricity storage performance.

While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

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Conductive paste for preparing super capacitor and preparation method thereof

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