CN113860816A

CN113860816A - Chargeable, electricity-storage and discharge concrete material and preparation method thereof

Info

Publication number: CN113860816A
Application number: CN202111133323.4A
Authority: CN
Inventors: 蒋正武; 张红恩; 何倍; 宋法成
Original assignee: Tongji University
Current assignee: Tongji University
Priority date: 2021-09-27
Filing date: 2021-09-27
Publication date: 2021-12-31
Anticipated expiration: 2041-09-27
Also published as: CN113860816B

Abstract

The invention relates to a chargeable, electricity-storage and discharge concrete material and a preparation method thereof, wherein the concrete material comprises the following raw material components: the cement-based composite material comprises, by weight, 1000 parts of 600-plus-one cement, 1100 parts of 660-plus-one quartz sand, 350 parts of 210-plus-one quartz powder, 251 parts of 150-plus-one silica ash, 0-0.2% of carbon nano-material, 1.0-2.0% of steel fiber by volume, 1.0-2.0% of water reducing agent by total weight, and 1.0-10.0% of surfactant by total weight. According to the invention, the steel fiber and the carbon nano material are added, so that a capacitor is formed in the concrete, external electric energy can be stored in the capacitor when the concrete is electrified, and the stored electric energy can be automatically released after the concrete is powered off. Compared with the prior art, the concrete has high mechanical property, high toughness and high impermeability, and also has the capability of charging, storing electric energy and releasing electric energy.

Description

Chargeable, electricity-storage and discharge concrete material and preparation method thereof

Technical Field

The invention belongs to the technical field of novel energy-saving building materials, and relates to a chargeable, electricity-storage and dischargeable concrete material and a preparation method thereof.

Background

Concrete materials play an irreplaceable role in the infrastructure. With the continuous progress of the human society and the vigorous development of the technology level, especially with the proposition of the concept of the smart city, the requirements of people on the concrete material are not only limited to the ultrahigh mechanical property, the high anti-permeability performance and the high durability, and the concrete material also has the intelligent functions of structural health detection, self-perception, energy storage and the like.

Chemical batteries and fuel cells have been used for a long time to provide renewable energy sources, but the batteries can generate heavy metal toxic substances such as mercury, cadmium, lead, zinc and the like, and can discharge toxic gases to the environment. For this reason, scientists have invented various devices to utilize new clean energy sources such as solar energy, wind energy, tidal energy, etc., but expensive equipment and wide application space are required to be equipped for scientific and efficient utilization of these energy sources, and in addition, the durability of the equipment and whether the generated electric energy can be effectively stored are still problems to be solved. If the electric energy generated by the energy sources can be stored in concrete with excellent mechanical property and low engineering cost, and then the stored electric energy is reasonably utilized and converted into other energy, a new energy revolution is caused.

Scientists have preliminarily buried a capacitor device in concrete or injected an electrolyte solution into the concrete to give the concrete the ability to store electric energy, but this method not only greatly increases the cost of the concrete, but also adversely affects the mechanical properties and durability of the concrete and reduces the service life of the concrete structure.

Disclosure of Invention

The invention aims to provide a chargeable, electricity-storing and discharging concrete material and a preparation method thereof, so as to solve the problems that the mechanical property or the durability of the concrete is damaged in the prior art and the like.

The purpose of the invention can be realized by the following technical scheme:

one of the technical schemes of the invention is to provide a chargeable, electricity-storage and discharge concrete material, which comprises the following raw material components: the cement-based composite material comprises, by weight, 1000 parts of 600-plus-one cement, 1100 parts of 660-plus-one quartz sand, 350 parts of 210-plus-one quartz powder, 251 parts of 150-plus-one silica ash, 0-0.2% of carbon nano material, 1.0-2.0% of steel fiber by volume, 1.0-2.0% of water reducing agent by total weight, and 1.0-10.0% of surfactant by total weight. Here, when the amount of the carbon nanomaterial added is 0% of the total amount of the cement, it means that the carbon nanomaterial is not added at this time, and correspondingly, the surfactant is not added.

Further, the specific surface area of the cement is 398m²Per kg of Portland cement.

Further, the particle size range of the quartz sand is one or two of 0.250mm-0.595mm or 0.147mm-0.210 mm.

Further, the weight ratio of the quartz sand to the cement is 1.0-1.2: 1.

further, the specific surface area of the silica fume is 21.36m²/g。

Further, the weight ratio of the silica fume to the cement is 0.24-0.28: 1.

Further, the weight ratio of the water to the cement is 0.21-0.26.

Further, the carbon nano material is one or more of carbon nano tube, carbon nano-fiber, graphene or graphene oxide.

Further, the purity of the carbon nano material is 80-95%.

Further, the diameter of the carbon nano material is 5-30 nm.

Further, the length of the carbon nano material is 10-30 mu m.

Further, the surfactant is one or more of a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant or a compound surfactant.

Further, the steel fiber is one or more of straight steel fiber, end hook steel fiber or corrugated steel fiber.

Further, the length of the steel fiber is 5-20 mm, and the length-diameter ratio is 30-90.

The second technical scheme of the invention is to provide a preparation method of the chargeable, electricity-storage and discharge concrete material, which comprises the following steps:

(1) dispersing raw material components except quartz sand and steel fiber in water, then sequentially adding the quartz sand and the steel fiber, uniformly mixing, putting into a mold, compacting by vibration, and trowelling for molding;

(2) and (2) embedding electrodes at two ends of the concrete obtained in the step (1), compacting and leveling again, standing, and removing the mould to obtain the target product.

Further, in the step (1), when the raw material contains the carbon nanomaterial, the dispersion process of the raw material other than the quartz sand and the steel fiber is specifically as follows:

1) dispersing a carbon nano material in an aqueous solution of a surfactant to obtain a carbon nano material dispersion liquid;

2) the preparation method of the carbon nano material dispersion liquid comprises the following steps: adding a surfactant into water, uniformly stirring until the surfactant is fully dissolved, adding a carbon nano material to preliminarily prepare a carbon nano material turbid liquid, then putting the carbon nano material turbid liquid into ultrasonic dispersion equipment for dispersion for 10-20 min, then stirring for 3-8 min by using a magnetic stirrer with the rotation speed of 1800rpm, and finally dispersing for 10-20 min by using the ultrasonic dispersion equipment to prepare a carbon nano material dispersion liquid.

3) And (2) dispersing cement, silica fume, quartz powder and a water reducing agent in the carbon nano material dispersion liquid obtained in the step (1), namely completing the dispersion process of the raw materials except quartz sand and steel fiber.

Further, in the step (2), the electrode is a red copper sheet or a red copper mesh electrode.

Furthermore, the thickness of the red copper sheet or red copper net electrode is not more than 1 mm.

Further, in the step (2), before standing, a preservative film is used for wrapping the concrete, then the concrete is stood for 24 hours under standard conditions, and then the mould is removed.

Further, in the step (2), after the mould is removed, the concrete material is put into an environment with the temperature of 90 ℃ and the humidity of 100% for curing for 48 hours, and the target product is prepared.

The concrete material of the invention has the following charge, storage and discharge mechanisms: a row of spaces with different specifications are formed among raw materials, reaction products or between the raw materials and the reaction products in the concrete, and when a series of good electric conductors are distributed around the spaces, the spaces become capacitors with certain electricity storage capacity. The invention promotes the concrete to form a plurality of capacitors by doping the steel fibers and the carbon nano materials with different proportions. When the power is on, external electric energy can be stored in a capacitor inside the concrete, meanwhile, free cations and anions inside the concrete can be directionally distributed under the action of current, and a positive electrode and a negative electrode are respectively formed on the end face of the concrete; after the power is cut off, the electric energy stored in the concrete can be released automatically, and the duration time is up to more than 10h at most.

The water reducing agent used in the invention can optimize the working performance of the concrete material and facilitate pouring and forming, and can improve the void structure in the concrete material and the uniform distribution of the steel fibers in the concrete material. The agent such as a surfactant plays a role of activating the carbon nanomaterial. The carbon nano material has very small particle size and large specific surface area, is extremely easy to gather in the concrete to form a weak area, not only weakens the performance of the concrete material, but also wastes the carbon nano material, and the purpose of activating the carbon nano material can be achieved by using reagents such as a surfactant and the like, so that the carbon nano material can be uniformly distributed in the concrete material and does not gather. The concrete material is put into an environment with the temperature of 90 ℃ and the humidity of 100% for curing for 48 hours, so that the process of the cement hydration reaction can be accelerated, and the utilization rate of the cement can be improved.

In addition, in the present invention, if the particle size of the silica sand is too large, the porosity of the concrete material is affected, and the strength of the cast concrete material is significantly reduced. If the particle size is too small, the working performance and the cement consumption of the concrete material are affected, and the forming quality of the concrete material is further affected.

Compared with the prior art, the invention has the following advantages:

(1) the invention organically combines the conductive phase material with the concrete, so that the concrete not only has high mechanical property, high toughness and high impermeability, but also has the unique capabilities of charging, storing electric energy and releasing electric energy.

(2) The invention improves the proportion of the silica fume, and can effectively improve the dispersing ability of the carbon nano material in the concrete.

(3) The invention firstly mixes the cement, the silica fume, the quartz powder and the carbon nano material together and stirs the mixture to a flowing state, then adds the quartz sand and stirs the mixture to a homogeneous state, and then adds the steel fiber, thereby further improving the dispersing ability of the carbon nano material in the concrete.

(4) The chargeable, electric storage and discharge ultrahigh-performance concrete material prepared by the invention can reach the following technical standards:

1) mechanical properties: the compressive strength of 28 days is more than or equal to 152MPa, and the breaking strength is more than or equal to 34 MPa;

2) the unit electric energy storage capacity of 28d under the condition of charging for 1h by a 20V power supply is 13V/m³～16.3V/m³The maximum autonomous discharge time is more than 10 hours;

3) impermeability: the impermeability grade is more than or equal to P6 (impermeability grade is determined according to the specification T0568-2005 impermeability test method of cement concrete).

Drawings

FIG. 1 is a graph showing the discharge tendency of a concrete material prepared in example 1 of the present invention;

FIG. 2 is a graph showing the discharge tendency of the concrete material prepared in example 2 of the present invention;

FIG. 3 shows the discharge tendency of the concrete material prepared in example 3 of the present invention.

Detailed Description

The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.

In the following examples, the silica fume had a specific surface area of 21.36m²(ii)/g; the purity of the carbon nano material is 80-95%, the diameter is 5-30 nm, and the length is 10-30 mu m; the length of the steel fiber is 5-20 mm, and the length-diameter ratio is 30-90.

Meanwhile, the raw materials in the embodiment are all commercial products, and the cement is 52.5 early strength cement in small open-field fields in the south of the Yangtze river; the silica fume is pure white 970U micro silica fume from Shanghai day; the quartz sand is prosperous in Shanghai; the quartz powder is prosperous; the steel fiber is copper-plated steel fiber produced by Jiangxi Daihe Metal Limited company; the water reducing agent is; the carbon nano tube is TNIMH1 produced by Chengdu organic chemistry GmbH of Chinese academy of sciences; the surfactant is TNWDIS nonionic surfactant produced by Chengdu organic chemistry GmbH of Chinese academy of sciences.

The remaining raw materials or processing steps used are, unless otherwise specified, conventional commercial products or conventional techniques.

Example 1:

a preparation method of a chargeable, electricity-storage and discharge concrete material comprises the following steps:

(1) raw materials were weighed as in table 1: in this example, the steel fiber is a copper-plated straight fiber having a length of 13mm and an aspect ratio of 65.

Table 1 example 1 raw material mixing ratio

(2) Adding cement, silica fume, quartz powder and a water reducing agent, uniformly mixing, adding water, stirring to a flowing state, adding quartz sand with two particle sizes of 0.147mm-0.210mm and 0.250mm-0.595mm according to a ratio of 1:1, stirring to a homogeneous state, adding steel fibers, stirring until the steel fibers are uniformly dispersed, putting into a mold, compacting by vibration, and trowelling for forming;

(3) after compaction and trowelling molding, red copper sheet electrodes with the thickness of 1mm are immediately embedded into the two ends of the concrete, and compaction and trowelling are performed again to ensure that the electrodes are well connected with the concrete;

(4) and (3) wrapping the molded test piece by using a preservative film, standing for 24 hours under standard conditions, removing the mold, and then putting the concrete material into an environment with the temperature of 90 ℃ and the humidity of 100% for curing for 48 hours to obtain the chargeable, electricity-storage and dischargeable concrete material.

The discharge trend of the chargeable, stored and discharged concrete material prepared according to example 1 after charging for 1h at a voltage of 20V is shown in fig. 1, and the maximum autonomous discharge time of the concrete material is as long as 10h or more. The 28-day performance test shows that the compressive strength of the concrete material is 152MPa, the breaking strength is 34.57MPa, and the maximum electric energy storage capacity is 13V/m³Maximum current areal density of 3.54x 10^-2A/m²And the anti-permeability grade is more than or equal to P6.

Example 2:

(1) weighing the raw materials according to table 2: in this example, the carbon nanomaterial is a (carbon nanotube), the surfactant is a nonionic surfactant, and the steel fiber is a copper-plated straight fiber having a length of 13mm and an aspect ratio of 65.

Table 2 example 2 raw material mixing ratio

(2) Adding a surfactant into water, uniformly stirring until the surfactant is fully dissolved, adding a carbon nano material to preliminarily prepare a carbon nano material suspension, then putting the carbon nano material suspension into ultrasonic dispersion equipment for dispersion for 15min, then stirring for 5min by using a magnetic stirrer with the rotation speed of 1800rpm, and finally dispersing for 15min by using the ultrasonic dispersion equipment to prepare a carbon nano material dispersion liquid for later use;

(3) firstly adding cement, silica fume, quartz powder and a water reducing agent, uniformly mixing, then adding the prepared carbon nano material dispersion liquid, stirring to a flowing state, then adding quartz sand with the particle size of 0.250-0.595 mm, stirring to a homogeneous state, then adding steel fibers, stirring until the steel fibers are uniformly dispersed, putting into a die, compacting, and trowelling for forming;

(4) after compaction and trowelling molding, red copper mesh electrodes with the thickness of 1mm are immediately embedded into the two ends of the concrete, and compaction and trowelling are performed again to ensure that the electrodes are well connected with the concrete;

(5) and (3) wrapping the molded test piece by using a preservative film, standing for 24 hours under standard conditions, removing the mold, and then putting the concrete material into an environment with the temperature of 90 ℃ and the humidity of 100% for curing for 48 hours to obtain the chargeable, electricity-storage and dischargeable concrete material.

The discharge trend of the chargeable, stored and discharged concrete material prepared according to example 2 after charging for 1h at a voltage of 20V is shown in fig. 2, and the maximum autonomous discharge time of the concrete material is as long as 10h or more. The performance test for 28 days shows that the compressive strength of the concrete material is 172MPa, the breaking strength is 37MPa, and the maximum electric energy storage capacity is 14.9V/m³Maximum current areal density of 4.49x 10^-2A/m²And the anti-permeability grade is more than or equal to P6.

Example 3:

(1) raw materials were weighed as in table 3: in this embodiment, the carbon nanomaterial is a carbon nanotube, the surfactant is a nonionic surfactant, and the steel fiber is a copper-plated straight fiber having a length of 18mm and a length-diameter ratio of 90.

Table 3 example 3 raw material mixing ratio

(3) firstly adding cement, silica fume, quartz powder and a water reducing agent, uniformly mixing, then adding the prepared carbon nano material dispersion liquid, stirring to a flowing state, then adding quartz sand with the particle size of 0.147mm-0.210mm, stirring to a homogeneous state, then adding steel fibers, stirring until the steel fibers are uniformly dispersed, putting into a die, compacting by vibration, and trowelling for forming;

(4) after compaction and trowelling molding, red copper sheet electrodes with the thickness of 1mm are immediately embedded into the two ends of the concrete, and compaction and trowelling are performed again to ensure that the electrodes are well connected with the concrete;

The discharge trend of the chargeable, stored and discharged concrete material prepared according to example 3 after charging for 1h at a voltage of 20V is shown in fig. 3, and the maximum autonomous discharge time of the concrete material is as long as 10h or more. The performance test for 28 days shows that the compressive strength of the concrete material is 160MPa, the breaking strength is 35.4MPa, and the maximum electric energy storage capacity is 16.3V/m³Maximum current areal density of 7.51x 10^-2A/m²And the anti-permeability grade is more than or equal to P6.

Comparative example 1:

the preparation method of the concrete material of the embodiment comprises the following steps:

(1) the raw materials were weighed as in table 4:

table 4 raw material mixing ratio of comparative example 1

(2) Adding cement, silica fume, quartz powder and a water reducing agent, uniformly mixing, adding water, stirring to a flowing state, adding quartz sand with two particle sizes of 0.147mm-0.210mm and 0.250mm-0.595mm according to a ratio of 1:1, stirring to a homogeneous state, putting into a mold, compacting, and trowelling for molding;

(4) and (3) wrapping the formed test piece by using a preservative film, standing for 24 hours under standard conditions, removing the mold, and then putting the concrete material into an environment with the temperature of 90 ℃ and the humidity of 100% for curing for 48 hours to obtain the concrete material of the comparative example.

The concrete material prepared according to the comparative example 1 has the compression strength of 70MPa, the breaking strength of 6MPa and the electric energy storage capacity of 0V/m when the impermeability grade is not less than P4 according to the performance test of 28 days³Maximum current areal density of 0A/m²I.e., exhibiting no charge, charge storage and discharge properties.

Example 4

Compared with example 2, most of the surfactant is the same, except that the proportion of the surfactant is changed to 0.75kg.m^-3。

Example 5

Compared with example 2, most of the components are the same, except that the proportion of the surfactant is changed to 7.5kg^-3。

Example 6

Compared with the example 2, most of the water reducing agents are the same, except that in the example, the proportion of the water reducing agent is changed to 7.4kg.m^-3。

Example 7

Compared with the example 2, most of the materials are the same, except that in the example, the mixture ratio of the quartz sand is changed to 740kg^-3。

Example 8

Compared with example 2, most of the samples were the same except that in this example, the mixture ratio of quartz sand was changed to 888kg.m^-3。

Example 9

Compared with the example 2, the most parts are the same, except that in the example, the mixture ratio of the silica fume is changed to 177.6kg^-3。

Example 10

Compared with the embodiment 2, the most parts are the same, except that in the embodiment, the ratio of the silica fume is changed to 207.2kg^-3。

Example 11

Compared with the embodiment 2, most of the materials are the same, except that in the embodiment, the proportion of the quartz powder is changed to 370kg^-3。

The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims

1. The chargeable, electricity-storage and discharge concrete material is characterized by comprising the following raw material components: the cement-based composite material comprises, by weight, 1000 parts of 600-plus-one cement, 1100 parts of 660-plus-one quartz sand, 350 parts of 210-plus-one quartz powder, 251 parts of 150-plus-one silica ash, 0-0.2% of carbon nano material, 1.0-2.0% of steel fiber by volume, 1.0-2.0% of water reducing agent by total weight, and 1.0-10.0% of surfactant by weight.

2. The concrete material of claim 1, wherein the cement has a specific surface area of 398m²Per kg of Portland cement.

3. The concrete material capable of being charged, stored and discharged according to claim 1, wherein the quartz sand has a particle size in a range of one or both of 0.250mm to 0.595mm or 0.147 to 0.210 mm.

4. The concrete material capable of being charged, stored and discharged according to claim 1, wherein the silica fume has a specific surface area of 21.36m²/g。

5. The chargeable, electric-storage and electric-discharge concrete material according to claim 1, wherein the weight ratio of the quartz sand to the cement is 1.0-1.2: 1;

the weight ratio of the silica fume to the cement is 0.24-0.28: 1;

the weight ratio of water to cement is 0.24-0.28: 1.

6. the concrete material capable of being charged, stored and discharged according to claim 1, wherein the carbon nano-material is one or more of carbon nano-tube, carbon nano-fiber, graphene or graphene oxide.

7. The concrete material capable of being charged, stored and discharged according to claim 1, wherein the carbon nanomaterial has a purity of 80-95%, a diameter of 5-30 nm, and a length of 10-30 μm.

8. The chargeable, electricity-storage and electric-discharge concrete material as claimed in claim 1, wherein the surfactant is one or more of cationic surfactant, anionic surfactant, nonionic surfactant, amphoteric surfactant or compound surfactant.

9. The concrete material capable of being charged, stored and discharged according to claim 1, wherein the steel fibers are one or more of straight steel fibers, end hook steel fibers or corrugated steel fibers;

the length of the steel fiber is 5-20 mm, and the length-diameter ratio is 30-90.

10. A method of preparing a concrete material for charging, storing and discharging according to any one of claims 1 to 9, comprising the steps of: