CN-122025435-A - Cement-based supercapacitor based on copper ions and preparation method thereof

CN122025435ACN 122025435 ACN122025435 ACN 122025435ACN-122025435-A

Abstract

The invention relates to the technical field of civil engineering materials and energy storage, in particular to a cement-based supercapacitor based on copper ions and a preparation method thereof. The cement-based supercapacitor comprises electrode layers and cement-based functional layers arranged between the electrode layers, wherein the raw materials of the cement-based functional layers comprise cement, carbon black, anionic polyacrylamide, copper sulfate, water and a water reducer. By introducing a synergistic mechanism of copper ions and anionic polyacrylamide, the carbon black doping amount, the water-gel ratio and the proportion of functional components are optimized, the structural integrity of a cement matrix is maintained while the continuity of a conductive network is ensured, the synergistic improvement of electrochemical performance and mechanical performance is realized, the specific capacitance of the prepared cement-based supercapacitor can be more than or equal to 80F/g, the energy density is more than or equal to 5Wh/kg, the capacity retention rate is still more than or equal to 80% after more than or equal to 10000 charge and discharge cycles, the compressive strength can be stably more than or equal to 30MPa, and the volume resistivity is less than or equal to 10 3 Ω & cm.

Inventors

LIU QIAOLING
CAO ZHENYU
WANG ZHEN
Zhou Zaibo
CHEN JIALE
JIANG RONGYAN
CHEN TING
ZHANG WENHAI

Assignees

山东建筑大学

Dates

Publication Date: 20260512
Application Date: 20260415

Claims (10)

1. The cement-based supercapacitor based on copper ions is characterized by comprising electrode layers and cement-based functional layers arranged between the electrode layers, wherein the raw materials of the cement-based functional layers comprise cement, carbon black, anionic polyacrylamide, copper sulfate, water and a water reducing agent, the water-cement ratio of the cement-based functional layers is 0.45-0.55, the mixing amount of the carbon black is 1-3% of the cement mass, the mixing amount of the anionic polyacrylamide is 0.1-0.5% of the cement mass, the mixing amount of the copper sulfate is 0.1-2% of the cement mass, and the mixing amount of the water reducing agent is 0.05-0.3% of the cement mass.
2. The cement-based supercapacitor of claim 1, wherein the electrode layer is a composite electrode of a foamed nickel-loaded activated carbon slurry coating, and wherein the raw materials of the activated carbon slurry coating include activated carbon, conductive carbon black, polyvinylidene fluoride, and N-methylpyrrolidone solvent.
3. The cement-based supercapacitor of claim 1, wherein the mass ratio of the activated carbon, the conductive carbon black and the polyvinylidene fluoride is 7-9:0.5-1.5:0.5-1.5.
4. The cement-based supercapacitor of claim 2, wherein the activated carbon slurry coating has a thickness of 100-200 μιη.
5. The cement-based supercapacitor of claim 2, wherein the raw material of the cement-based functional layer further comprises nanocellulose, and the doping amount of the nanocellulose is 0.05% -0.3% of the mass of cement.
6. A method of manufacturing a cement-based supercapacitor according to any one of claims 1 to 4, comprising the steps of: (1) Cutting foam nickel, ultrasonically cleaning with ethanol and deionized water, and drying; mixing active carbon, conductive carbon black, polyvinylidene fluoride and N-methyl pyrrolidone to prepare active carbon slurry, coating the active carbon slurry on the surface of foam nickel, and vacuum drying to prepare the foam nickel-loaded active carbon composite electrode; (2) The preparation of cement-based slurry comprises the steps of weighing various raw materials according to a proportion, mixing cement and carbon black, stirring to obtain a dry material, uniformly mixing anionic polyacrylamide, water and a water reducing agent, pouring the mixture into the dry material, and wet-stirring the mixture to obtain a wet material; (3) And (3) molding and curing, namely pouring the cement-based slurry into a mold, inserting the composite electrode, vibrating and molding, standing at room temperature, demolding, and transferring into a standard curing box for curing to obtain the cement-based supercapacitor.
7. The method of claim 6, wherein the dry mixing time in step (2) is 1 to 4 minutes and the wet mixing time is 2 to 6 minutes.
8. The method according to claim 6, wherein the concentration of the copper sulfate solution in the step (2) is 0.1 to 0.5mol/L.
9. The method of manufacturing according to claim 6, wherein in the step (3), a vibration table with a frequency of 50Hz is used for vibration molding, natural vibration is performed for 2 to 5 minutes after the air bubbles are discharged, the insertion position of the composite electrode is fixed by a separator, the standing time is 18 to 36 hours, and the curing time is 3 to 28 days.
10. A method of making a cement-based supercapacitor of claim 5, comprising the steps of: (1) Cutting foam nickel, ultrasonically cleaning with ethanol and deionized water, and drying; mixing active carbon, conductive carbon black, polyvinylidene fluoride and N-methyl pyrrolidone to prepare active carbon slurry, coating the active carbon slurry on the surface of foam nickel, and vacuum drying to prepare the foam nickel-loaded active carbon composite electrode; (2) The preparation of cement-based slurry comprises the steps of weighing various raw materials according to a proportion, mixing cement and carbon black, stirring to obtain dry materials, adding nanocellulose into water in advance, and carrying out high-speed shearing or ultrasonic dispersion treatment to obtain nanocellulose dispersion liquid; (3) And (3) molding and curing, namely pouring the cement-based slurry into a mold, inserting the composite electrode, vibrating and molding, standing at room temperature, demolding, and transferring into a standard curing box for curing to obtain the cement-based supercapacitor.

Description

Cement-based supercapacitor based on copper ions and preparation method thereof Technical Field The invention relates to the technical field of civil engineering materials and energy storage, in particular to a cement-based supercapacitor based on copper ions and a preparation method thereof. Background Along with the large-scale application of intermittent renewable energy sources such as wind energy, solar energy and the like, the problem of mismatch of energy supply and demand in time is increasingly outstanding, and higher requirements are put forward on efficient and large-scale energy storage technology. Although the traditional lithium ion battery has higher energy density, the traditional lithium ion battery is difficult to meet the energy storage requirement of low cost, environmental friendliness and integration with infrastructure due to factors such as raw material resources, cost, environmental influence, independent occupied space and the like. The super capacitor has the advantages of high power density, high charge and discharge speed, long cycle life and the like, and is an important supplement for energy storage of renewable energy sources. However, the existing super capacitor mostly adopts organic electrolyte and a complex layered structure, has high preparation cost and complex structure, and is not beneficial to the integrated application of engineering scenes such as building structures and the like. The cement-based material has the characteristics of wide sources, low cost and good durability as the building material with the largest global consumption, and is considered to have the potential of building the structural energy storage device in recent years. By introducing conductive fillers such as carbon black, the cement-based composite material can form a porous structure after solidification, and a channel is provided for electrolyte infiltration and ion transmission, so that a material foundation is provided for the development of the cement-based supercapacitor. Supercapacitor structures constructed based on cement-based materials have been reported. For example, chinese patent CN117976422a discloses a cement-based carbon black supercapacitor, in which both the electrolyte and the electrode are made of cement-based carbon black materials, and the separator is a polypropylene modified separator, but the final capacitor has limited charge storage capacity and low overall energy density. Chinese patent CN119495513B discloses a cement-based zinc ion hybrid capacitor and a method for preparing the same, wherein the composite air entraining is introduced into a cement-based energy storage device, so that the ion conductivity of the electrolyte of the cement-based structure is improved, the electricity storage performance is remarkably improved, the compactness of the cement matrix and the continuity of the bearing skeleton are inevitably weakened by excessively high porosity, and the compressive strength is difficult to meet the bearing requirement of the structural member of the reagent engineering. Disclosure of Invention Aiming at the technical problems that the electrochemical performance and the mechanical performance of a cement-based supercapacitor are difficult to cooperate, the preparation process is complex and the application is limited in the prior art, the invention provides a copper ion-based cement-based supercapacitor and a preparation method thereof. The specific technical scheme is as follows: according to the first aspect, the invention provides a copper ion-based cement-based super capacitor, which comprises electrode layers and cement-based functional layers arranged between the electrode layers, wherein raw materials of the cement-based functional layers comprise cement, carbon black, anionic polyacrylamide, copper sulfate, water and a water reducing agent, the water-cement ratio of the cement-based functional layers is 0.45-0.55, the mixing amount of the carbon black is 1-3% of the cement mass, the mixing amount of the anionic polyacrylamide is 0.1-0.5% of the cement mass, the mixing amount of the copper sulfate is 0.1-2% of the cement mass, and the mixing amount of the water reducing agent is 0.05-0.3% of the cement mass. The cement-based super capacitor has the structure bearing function and the energy storage function, realizes the structure-energy storage integrated design, reduces the setting of an independent diaphragm or an independent energy storage unit, and improves the space utilization rate. In the raw materials of the cement-based functional layer, carbon black is used for constructing a continuous electronic conductive network, copper sulfate provides copper ions to improve the ionic conductivity of a pore solution and reduce interface charge transfer impedance, anionic polyacrylamide is used for improving the stability of copper ions and the dispersibility of the carbon black, enhancing the ion migration efficiency, and a water reducer improves