CN115719681A - Cement-based electrochemical energy storage device and preparation method thereof - Google Patents
Cement-based electrochemical energy storage device and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electrochemistry, and particularly relates to a cement-based electrochemical energy storage device and a preparation method thereof. The preparation method of the cement-based electrochemical energy storage device comprises the following steps: (1) Pouring a uniform mixture of polyacrylic acid, potassium hydroxide solution, portland cement and carbon nanotubes into a mold; (2) Inserting two electrode plates as a positive electrode and a negative electrode respectively before the mixture is solidified; (3) And maintaining to obtain the cement-based electrochemical energy storage device. The cement-based electrochemical energy storage device provided by the invention can be applied to the field of civil engineering, and is expected to realize building electricity storage integration in future.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a cement-based electrochemical energy storage device and a preparation method thereof.
Background
China has a large number of frontier sentries, remote military bases, temporary military facilities and the like, and the areas are far away from power supply lines and difficult to stably supply power, so that the normal operation of the military facilities and equipment and the living, medical and other guarantees of officers and soldiers are seriously influenced. Portland cement is the most widely used material in the world, has high compression resistance and is a building material with wider application. If the electric energy can be stored in building materials such as cement, the energy storage problem under the special application scene can be solved. The Portland cement has certain porosity so as to facilitate free transmission of ions, and is a potential low-cost solid electrolyte material applied to electrochemical energy storage devices. Among the electrochemical energy storage devices, lithium/sodium/potassium ion batteries are mostly adopted for energy storage at present, but the electrochemical energy storage devices have the problems of easy explosion, less cycle times, high use environment requirements and the like. The super capacitor is a novel energy storage device developed in recent years and is a novel energy storage device between a traditional capacitor and a rechargeable battery. It has longer service life, faster charge and discharge rate and wider service temperature range than metal ion batteries.
Ti 3 C 2 T x MXene is a typical two-dimensional layered structure, has the characteristics of large specific surface area, good conductivity, good thermal and chemical stability, hydrophilicity, rich surface groups and the like, has good compatibility with Portland cement, and is a principleThe desired electrode material.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a cement-based electrochemical energy storage device and a preparation method thereof.
In order to achieve the above purpose, the invention provides the following technical scheme: the preparation method of the cement-based electrochemical energy storage device is characterized by comprising the following steps of: (1) Pouring a uniform mixture of polyacrylic acid, potassium hydroxide solution, portland cement and carbon nanotubes into a mold; (2) Inserting two electrode plates as a positive electrode and a negative electrode respectively before the mixture is solidified; (3) And maintaining to obtain the cement-based electrochemical energy storage device.
Preferably, in the mixture, the mass ratio of the polyacrylic acid to the portland cement is 1-8wt%; in the potassium hydroxide solution, the concentration of potassium hydroxide is 1-6mol/L; the water-cement ratio is 0.35-0.45.
Preferably, the mass ratio of the carbon nano tube to the portland cement is 0.5% -2%.
Preferably, in the step (2), the electrode sheet is prepared according to a method comprising the following steps: A. for Ti 3 C 2 T x Mixing and grinding MXene, acetylene black and PTFE solution; B. and D, coating the mixture obtained by the treatment in the step A on foamed nickel, and drying to obtain the electrode slice.
Preferably, the Ti 3 C 2 T x The mass ratio of MXene, acetylene black and PTFE is (7.0-9.5): (0.5-2.0): (0.5-2.0).
Preferably, step (2) is preceded by a step of washing and drying the nickel foam; the washing comprises the following steps: washing with hydrochloric acid, deionized water and absolute ethyl alcohol successively; the concentration of the hydrochloric acid is 2.5-3.5mol/L, and the washing time of the hydrochloric acid is less than or equal to 5min; the washing time of the deionized water is less than or equal to 10min; the washing time of the absolute ethyl alcohol is less than or equal to 5min.
Preferably, the drying temperature is 55-65 ℃, and the drying time is more than or equal to 10h.
Preferably, in the step B, the nickel foam is in a cuboid shape, the width of the nickel foam is 0.5-1.5cm, and the length of the nickel foam is 3.5-1.5cm.
Preferably, in the step (3), the curing is performed at room temperature, and the curing time is 3 to 8 days.
The invention also provides a cement-based electrochemical energy storage device, which adopts the following technical scheme: a cement-based electrochemical energy storage device is prepared by the method.
Has the advantages that:
(1) The cement-based electrochemical energy storage device has good mechanical property, and the adopted electrode plate has excellent conductivity, so that the conductivity can be increased, and the energy utilization rate of the capacitor can be greatly improved.
(2) MXene has good flexibility and corrosion resistance, and shows excellent cyclicity and high specific discharge capacity when being applied to the cement-based electrochemical energy storage device.
(3) The application of the cement-based electrochemical energy storage device in the field of civil engineering is expected to realize the integration of building electricity storage in future.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is a cyclic voltammogram provided by an embodiment of the present invention; wherein, fig. 1 (a) - (c): is a cyclic voltammetry test (CV) curve graph corresponding to the cement-based electrochemical energy storage device of examples 2-4 under different sweep rates in an electrochemical test when the content of the carbon nanotube is 0.5% (0.125 g), 1.0% (0.25 g) and 2.0% (0.5 g), respectively; 1 (d) is the sweep rate of 100mV s in electrochemical tests at different contents of carbon nanotubes -1 Comparing the corresponding Cyclic Voltammetry (CV) curves;
FIG. 2 is a graph showing charging and discharging curves provided by an embodiment of the present invention; wherein, fig. 2 (a) - (c): the content of the carbon nano tube is respectively 0.5 percent(0.125 g), 1.0% (0.25 g) and 2.0% (0.5 g), corresponding charge-discharge curves of the cement-based electrochemical energy storage devices of examples 2-4 under different current densities in electrochemical tests; 1 (d) is the current density of 0.3Ag in electrochemical test at different contents of carbon nanotube -1 Comparing the corresponding charging and discharging curves;
FIG. 3 is a graph of impedance provided by an embodiment of the present invention; wherein, fig. 3 (a) - (c): is an impedance curve diagram of the cement-based electrochemical energy storage devices of examples 2-4 in the electrochemical test when the contents of the carbon nanotubes are 0.5% (0.125 g), 1.0% (0.25 g) and 2.0% (0.5 g), respectively; 3 (d) is a comparison graph of impedance curves in electrochemical tests when the content of the carbon nano tubes is different;
FIG. 4 is a graph of compressive strength provided by an embodiment of the present invention; wherein, fig. 4 (a) is the seven day compressive strength at different carbon nanotube contents; FIG. 4 (b) is the seven day compressive strength at different KOH levels; FIG. 4 (c) is the seven day compressive strength at different PAA contents;
fig. 5 is a schematic structural diagram of a cement-based electrochemical energy storage device according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Aiming at the existing problems, the invention provides a preparation method of a cement-based electrochemical energy storage device, which comprises the following steps: (1) Pouring a uniform mixture of polyacrylic acid, potassium hydroxide solution, portland cement and carbon nanotubes into a mold; (2) Before the mixture is solidified, inserting two electrode plates as a positive electrode and a negative electrode respectively; and (3) curing to obtain the cement-based electrochemical energy storage device.
The porous cement block with the ion transmission channel is prepared by adding the carbon nano tube, the polyacrylic acid and the like into the cement powder according to a certain proportion to be used as the solid electrolyte, the prepared cement-based electrochemical energy storage device can improve the energy utilization rate of the portland cement, and the electrochemical energy storage device has the advantages of wide use temperature range (the cement-based electrochemical energy storage device can work in the temperature range of-40 ℃ to +70 ℃, and the use temperature range is wider than the commonly used temperature range of 15 ℃ to 32 ℃ in the prior art), no maintenance, long service life, low cost and the like, and can be widely applied to military/civil infrastructures such as frontier sentry posts, remote military bases, roads, bridges, tunnels and the like. The structural principle of the cement-based electrochemical energy storage device of the invention is shown in fig. 5.
In a preferred embodiment of the invention, the mixture has a polyacrylic acid to portland cement mass ratio of 1% to 8% (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, or 8%); the concentration of potassium hydroxide in the potassium hydroxide solution is 1 to 6mol/L (e.g., 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, or 6 mol/L); the water-to-cement ratio is 0.35-0.45 (e.g., 0.35, 0.38, 0.40, 0.42, or 0.45). If the amount of polyacrylic acid is too large, the cement is not easy to solidify, and the strength of the cement is reduced; if the amount of potassium hydroxide is too large, the strength of the cement will also be reduced. In addition, the potassium hydroxide can be replaced by magnesium sulfate with the same concentration, and the alkali aggregate reaction is easily generated by adding alkali.
In a preferred embodiment of the present invention, the mass ratio of the carbon nanotubes to the portland cement is 0.5% to 2% (e.g., 0.5%, 1%, 1.5%, or 2%).
In a preferred embodiment of the present invention, in step (2), the electrode sheet is prepared according to a method including the following steps: A. for Ti 3 C 2 T x Mixing and grinding the Mxene, the acetylene black and the PTFE solution; B. and D, coating the mixture obtained by the treatment in the step A on foamed nickel, and drying to obtain the electrode slice. The acetylene black mainly plays a role of a conductive agent, so that the conductivity of the electrode material is enhanced; PTFE is used to bond the electrode material to the nickel foam.
The invention is superiorIn an alternative embodiment, ti 3 C 2 T x MXene, acetylene black and PTFE at a mass ratio of (7.0-9.5): (0.5-2.0) (e.g., ti 3 C 2 T x MXene, acetylene black and PTFE in a mass ratio of 7.0, 7.0. Since PTFE is an insulating material, if an excessive amount is added, the electrochemical performance of the electrode material is greatly degraded.
In a preferred embodiment of the invention, ti 3 C 2 T x The mass ratio of MXene to acetylene black to PTFE was 8.
In a preferred embodiment of the invention, step (2) is preceded by a step of washing and drying the foamed nickel; the washing comprises the following steps: washing with hydrochloric acid, deionized water and absolute ethyl alcohol successively; the concentration of hydrochloric acid is 2.5-3.5mol/L (for example, 2.5mol/L, 2.8mol/L, 3.2mol/L or 3.5 mol/L), and the washing time of hydrochloric acid is less than or equal to 5min; the time of deionized water washing is less than or equal to 10min (for example, the number of deionized washing can be 3); the time of the absolute ethyl alcohol washing is less than or equal to 5min (for example, the number of the absolute ethyl alcohol washing can be 2 times).
In a preferred embodiment of the present invention, the drying temperature is 55-65 deg.C (e.g., 55 deg.C, 60 deg.C or 65 deg.C), and the drying time is 10h or more.
In a preferred embodiment of the present invention, in step B, the nickel foam has a rectangular parallelepiped shape, a width of 0.5 to 1.5cm (e.g., 0.5cm, 0.8cm, 1.0cm, 1.2cm or 1.5 cm), a length of 3.5 to 4.5cm (e.g., 3.5cm, 3.8cm, 4.0cm, 4.2cm or 4.5 cm), and a thickness of 1.5 to 2.5mm (e.g., 1.5mm, 1.8mm, 2mm, 2.2mm or 2.5 mm). Ti coated on each foamed nickel 3 C 2 T x The amount of the milled mixture (electrode material) of MXene, acetylene black and PTFE was determined according to the surface area of the nickel foam; if the electrode material is too much, the electrode material is likely to be deposited, and a "dead area" where the electrode material cannot participate in the electrochemical reaction is formed.
In a preferred embodiment of the present invention, in step (3), the curing is performed at room temperature, and the curing time is 3 to 8 days (e.g., 3 days, 4 days, 5 days, 6 days, 7 days, or 8 days). The curing time affects the strength of the cement-based electrochemical energy storage device. The long-time curing can cause shrinkage to cause damage to the cement-based electrochemical energy storage device; if the curing time is too short, sufficient hydration of the solid electrolyte cannot be achieved, and damage to the cement-based electrochemical energy storage device may also result.
The invention also provides a cement-based electrochemical energy storage device, and the cement-based electrochemical energy storage device provided by the embodiment of the invention is prepared by adopting the method.
The cement-based electrochemical energy storage device of the present invention, its preparation method and details are described in the following by specific examples.
Ti used in the following examples 3 C 2 T x Mxene is prepared according to the following method: 1g of titanium aluminum carbide (Ti) 3 AlC 2 ) Added to 20mL HF solution while stirring continuously at room temperature for more than 10min to avoid overheating due to the exothermic reaction. Stirring was continued in the oil bath at 60 ℃ for 48h, and then the mixture was washed several times with deionized water by centrifugation until a pH of 6 to 7 was reached. Washing the collected precipitate with ethanol for 2 times, and drying in a vacuum drying oven at 60 deg.C for 12 hr to obtain Ti 3 C 2 T x MXene。
The rest raw materials can be purchased from the market.
Example 1
The electrode plate of the embodiment is prepared by adopting a method comprising the following steps:
(1) Firstly, cutting the foamed nickel into cuboids (the thickness is 1.5-2.5 mm) with the width of 1cm and the length of 4cm, then respectively washing for 5min by using 3mol/L hydrochloric acid, washing for 3 times by using deionized water within 10min, and washing for 2 times by using absolute ethyl alcohol within 5min.
(2) And drying the washed foam nickel in a vacuum drying oven at 60 ℃ for more than 10h, taking out and weighing, and recording the mass of each foam nickel according to a weighing standard.
(3) Weighing Ti 3 C 2 T x Placing 8mg of Mxene and 1mg of acetylene black into a mortar, dripping a PTFE solution (diluted according to the proportion of 1; each foamed nickel is coated withTi of smear 3 C 2 T x The mass of the mixture after grinding of MXene, acetylene black and PTFE solution was 10mg.
(4) Will contain Ti after the treatment 3 C 2 T x MXene and acetylene black foamed nickel are dried in vacuum at 60 ℃ for 10h, and then taken out and weighed to obtain the electrode slice of the embodiment.
Example 2
The cement-based electrochemical energy storage device of the embodiment is prepared by the following steps:
(1) Stirring 25g of portland cement, 1.5g of polyacrylic acid (6 wt%), 10mL of KOH solution (prepared by dissolving 13.464g of KOH in 40mL of deionized water) with the concentration of 6mol/L and 0.125g of carbon nano tubes for 15-20min to obtain a uniform mixture;
(2) Pouring the uniform mixture obtained by the treatment in the step (1) into a mold of 2cm multiplied by 2cm, and inserting two electrode plates prepared in the example 1 before the mixture is completely solidified, wherein the electrode plates are respectively used as a positive electrode and a negative electrode;
(3) And curing for 7 days at room temperature to obtain the cement-based electrochemical energy storage device of the embodiment.
Example 3
The cement-based electrochemical energy storage device of the embodiment is prepared by the following steps:
(1) Stirring 25g of portland cement, 1.5g of polyacrylic acid (6 wt%), 10mL of a KOH solution (prepared by dissolving 13.464g of KOH in 40mL of deionized water) with the concentration of 6mol/L and 0.25g of carbon nanotubes for 15-20min to obtain a uniform mixture;
(2) Pouring the uniform mixture obtained by the treatment in the step (1) into a mold of 2cm multiplied by 2cm, and inserting two electrode plates prepared in the example 1 before the mixture is completely solidified, wherein the electrode plates are respectively used as a positive electrode and a negative electrode;
(3) And curing for 7 days at room temperature to obtain the cement-based electrochemical energy storage device of the embodiment.
Example 4
The cement-based electrochemical energy storage device of the embodiment is prepared by the following steps:
(1) 25g of portland cement, 1.5g of polyacrylic acid (6 wt%), 10mL of a KOH solution (prepared by dissolving 13.464g of KOH in 40mL of deionized water) with the concentration of 6mol/L and 0.5g of carbon nanotubes are stirred for 15-20min to obtain a uniform mixture;
(2) Pouring the uniform mixture obtained by the treatment in the step (1) into a mold of 2cm multiplied by 2cm, and inserting two electrode plates prepared in the example 1 before the mixture is completely solidified, wherein the electrode plates are respectively used as a positive electrode and a negative electrode;
(3) And curing for 7 days at room temperature to obtain the cement-based electrochemical energy storage device of the embodiment.
Comparative example 1
The preparation of the cement-based solid electrolyte of this comparative example included the following steps:
(1) Stirring 25g of portland cement and 10mL of water for 15-20min to obtain a uniform mixture;
(2) Pouring the homogeneous mixture into a mold of 2cm × 2cm × 2 cm;
(3) Curing was carried out at room temperature for 7 days to obtain a solid electrolyte of this comparative example (comparative example 1).
In addition, in the solid electrolyte preparation process of comparative example 1 (in step (1) of comparative example 1), carbon nanotubes in an amount of 0.5%, 1.0%, 1.5%, and 2.0% by mass of portland cement were added, respectively, to test the influence of the carbon nanotubes on the mechanical properties of the cement-based solid electrolyte;
in the preparation process of the solid electrolyte of comparative example 1 (in step (1) of comparative example 1), 2mL, 4mL, 6mL, 8mL and 10mL of 6mol/L KOH solution were added, respectively, to test the effect of potassium hydroxide on the mechanical properties of the cement-based solid electrolyte;
in the preparation process of the solid electrolyte of comparative example 1 (in step (1) of comparative example 1), polyacrylic acids were added in amounts of 2%, 4%, 6% and 8% by mass of portland cement, respectively, to test the effect of polyacrylic acids on the mechanical properties of the cement-based solid electrolyte.
Examples of the experiments
1. Cyclic voltammetry tests were performed on the cement-based electrochemical energy storage devices of examples 2-4, respectively:
the test results are shown in fig. 1.
Wherein: fig. 1 (a), (b), (c) are graphs of Cyclic Voltammetry (CV) corresponding to the cement-based electrochemical energy storage devices of examples 2, 3 and 4 at different sweep rates, respectively; the voltage window was 0-3v, indicating that the solid-state electrolytes of the cement-based electrochemical energy storage devices of examples 2-4 can reach a very high voltage range, according to the formula for calculating energy density:
E＝0.5CV 2 (1)
where E is the energy density, C is the specific capacitance per unit, and V is the voltage window.
Such a high voltage window results in the energy storage device possessing a high energy density.
As can be seen from fig. 1 (a) - (c), as the scanning speed increases, the area of the whole voltammogram is gradually increased and has better symmetry, which indicates that the cement-based electrochemical energy storage device of the present invention has good reversibility. The electrochemical reactions that occur during charging and discharging can be summarized as follows:
Ti 3 C 2 O x (OH) y F z +δOH - ←→Ti 3 C 2 (OOH) x+y F z +H 2 O+δe - (3)
FIG. 1 (d) shows the cement-based electrochemical energy storage devices of examples 2-4 (carbon nanotubes used at 0.5%, 1%, and 2%, respectively) at 100mVs -1 Comparing the CV curves at the same rate, it can be seen from fig. 1 (d) that when the amount of the carbon nanotubes is 2%, the total area of the CV curves is the largest, and the cement-based electrochemical energy storage device of example 4 has a larger specific capacitance than those of examples 2 and 3.
2. The corresponding charge-discharge curves of the cement-based electrochemical energy storage devices of examples 2-4 at different current densities were tested:
the test results are shown in fig. 2:
fig. 2 (a), (b), and (c) are corresponding charge-discharge curves of the cement-based electrochemical energy storage devices of examples 2-4 at different current densities, respectively, and show that MXene in the electrode sheet shows faradaic induced capacitance characteristics in the solid dielectric.
In equation (4): c s I, m, Δ V, and Δ t are mass specific capacitances (F g), respectively -1 ) Applied current (mA), active material mass (mg), voltage window (V) and discharge time(s). Fig. 2 (a), (b), and (c) show that the electrodes in the cement-based electrochemical energy storage devices of examples 2-4 have good reversibility, high energy storage rate, and good charge and discharge characteristics.
FIG. 2 (d) shows the current density of 0.3Ag in electrochemical tests at different contents of carbon nanotubes (0.5%, 1%, and 2% for the carbon nanotubes in examples 2-4, respectively) -1 The corresponding charging and discharging curve chart is shown. The mass specific capacitances of the cement-based electrochemical energy storage devices of examples 2 to 4 calculated by the formula (4) are respectively: 27F g -1 、23.78F g -1 、37.5F g -1 . Fig. 2 (d) shows that the electrode has good reversibility, high energy storage rate and good charge and discharge characteristics.
3. The impedance curves of the cement-based electrochemical energy storage devices of examples 2-4 corresponding to different current densities were tested:
fig. 3 (a), (b), and (c) are graphs of ac impedance curves (EIS curves) of the internal resistances of the cement-based electrochemical energy storage devices of examples 2-4, respectively, and it can be found from the EIS curves that the cement-based electrochemical energy storage devices of examples 2-4 have a greater slope in the low frequency range, indicating that the ion diffusion is faster; there is a smaller radius of curvature in the high frequency range, indicating less resistance to charge transfer.
Fig. 3 (d) is a graph of impedance plots in electrochemical tests at different contents of carbon nanotubes (in examples 2 to 4, the amounts of carbon nanotubes are 0.5%, 1%, and 2%, respectively), and analysis shows that the slope of the EIS curve is larger with the increase of CNTs, indicating that the diffusion resistance is lower and the ion transport rate is higher in the solid electrolyte of the cement-based electrochemical energy storage device.
4. Mechanical Property test
The mechanical properties of the solid electrolyte of comparative example 1 (omitting the step of adding electrode sheets) and the solid electrolyte added with carbon nanotubes, KOH or polyacrylic acid with different contents were tested:
fig. 4 (a) shows the compressive strength of the solid electrolyte under different doping amounts of the carbon nanotubes, and it is obtained through analysis that the compressive strength of the solid electrolyte increases with the increase of the doping amount of the CNTs (carbon nanotubes), mainly because the doping of the CNTs can not only effectively prevent the generation of microcracks inside the mortar, but also serve as nucleation cores for the hydration reaction of the cement, so as to accelerate the hydration process of the cement, and at the same time, have the effect of filling the voids inside the matrix, and can greatly improve the compressive strength of the cement-based material.
Fig. 4 (b) is a graph showing the compressive strength of the solid electrolyte at different KOH incorporation levels, and it was analyzed that the compressive strength of the solid electrolyte decreased as the KOH incorporation level increased, mainly because KOH inhibited the hydration process and generated the alkali-aggregate reaction.
Fig. 4 (c) is the compressive strength of the solid-state electrolyte under different PAA (polyacrylic acid) incorporation amounts, and it is analyzed that the compressive strength of the solid-state electrolyte decreases with the increase of the PAA incorporation amount, mainly because the PAA incorporation forms a cross-linked network structure inside the cement to maintain the solid-state electrolyte in a certain structural strength range.
Wherein, in FIGS. 4 (a), (b) and (c), when the blending amount of CNT, KOH and PAA is 0, the compressive strength of the solid electrolyte corresponding to comparative example 1 is obtained
Research results show that increasing the doping amount of CNT (carbon nano tube) is helpful for improving the electrochemical performance and compressive strength of the Portland cement-based composite electrolyte; increasing the amount of PAA and KOH incorporation increases the electrochemical performance of the solid composite electrolyte while inevitably decreasing the compressive strength of the electrolyte. When the doping amounts of CNT, PAA and KOH are respectively 2 percent6% and 10mL (example 4), the electrochemical performance and compressive strength can be ideally balanced, the compressive strength is as high as 39.2MPa (the compressive strength is basically equivalent to that of a test block made of pure portland cement, the carbon nanotube in the invention also plays a role in resisting the damage of KOH and PAA to the compressive strength of the cement-based solid electrolyte), and the mass specific capacitance reaches 37.5F g -1 . The performances show that the super capacitor with the structure has wide application prospect in the field of building energy storage.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the cement-based electrochemical energy storage device is characterized by comprising the following steps of:
(1) Pouring a uniform mixture of polyacrylic acid, potassium hydroxide solution, portland cement and carbon nanotubes into a mold;
(2) Inserting two electrode plates as a positive electrode and a negative electrode respectively before the mixture is solidified;
(3) And maintaining to obtain the cement-based electrochemical energy storage device.
2. The method of manufacturing a cement-based electrochemical energy storage device according to claim 1, wherein the mass ratio of the polyacrylic acid to the portland cement in the mixture is 1-8wt%;
in the potassium hydroxide solution, the concentration of potassium hydroxide is 1-6mol/L;
the water-cement ratio is 0.35-0.45.
3. The method for preparing a cement-based electrochemical energy storage device according to claim 1, wherein the mass ratio of the carbon nanotubes to the portland cement is 0.5% -2%.
4. The method for preparing the cement-based electrochemical energy storage device as claimed in any one of claims 1 to 3, wherein in the step (2), the electrode sheet is prepared according to a method comprising the following steps:
A. for Ti 3 C 2 T x Mixing and grinding MXene, acetylene black and PTFE solution;
B. and D, coating the mixture obtained by the treatment in the step A on foamed nickel, and drying to obtain the electrode slice.
5. The method of manufacturing a cement-based electrochemical energy storage device according to claim 4, characterized in that the Ti 3 C 2 T x The mass ratio of MXene, acetylene black and PTFE is (7.0-9.5): (0.5-2.0): (0.5-2.0).
6. The method for preparing a cement-based electrochemical energy storage device according to claim 4, wherein step (2) is preceded by a step of washing and drying the foamed nickel;
the washing comprises the following steps: washing with hydrochloric acid, deionized water and absolute ethyl alcohol successively;
the concentration of the hydrochloric acid is 2.5-3.5mol/L, and the washing time of the hydrochloric acid is less than or equal to 5min;
the washing time of the deionized water is less than or equal to 10min;
the washing time of the absolute ethyl alcohol is less than or equal to 5min.
7. The preparation method of the cement-based electrochemical energy storage device as claimed in claim 6, wherein the drying temperature is 55-65 ℃ and the drying time is not less than 10h.
8. The method for preparing a cement-based electrochemical energy storage device according to claim 4, wherein in the step B, the foamed nickel is in a rectangular parallelepiped shape, the width of the foamed nickel is 0.5-1.5cm, and the length of the foamed nickel is 3.5-1.5cm.
9. The method for preparing a cement-based electrochemical energy storage device according to claim 1, wherein in the step (3), the curing is performed at room temperature for 3-8 days.
10. A cement-based electrochemical energy storage device, characterized in that it is produced by a method according to any of claims 1-9.
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