CN-122025993-A - High-service-life cement-based battery and preparation method thereof

CN122025993ACN 122025993 ACN122025993 ACN 122025993ACN-122025993-A

Abstract

The invention discloses a cement-based battery with long service life and a preparation method thereof, wherein the cement-based battery comprises a cement matrix, an electrolyte, a positive electrode, an insulator diaphragm, a negative electrode, a positive current collector and a negative current collector, wherein the insulator diaphragm is embedded in the cement matrix to divide the cement matrix into two independent areas, one area is internally provided with the positive electrode, the other area is internally provided with the negative electrode, the positive current collector is tightly attached to the positive electrode, the negative current collector is tightly attached to the negative electrode, the positive current collector and the negative current collector are both extended to the outer end of the cement matrix and led out, and the electrolyte is filled in an inner hole of the cement matrix and a gap between the positive electrode and the negative electrode and the insulator diaphragm. According to the cement-based battery provided by the invention, the nano silicon dioxide, the lanthanum cobaltate, the manganese dioxide and the composite conductive carbon material are added into the conductive concrete, so that the cement-based battery has the electrochemical performance and the mechanical performance, and meanwhile, the service life is long, and the cement-based battery has extremely high industrial application value.

Inventors

FENG SHOUZHONG
MAO WEIXING
Tong Xianggui
WANG LIMEI
LIU LIXIANG
DAI BIN
ZHENG SHUANGSHUANG
LIU XIANLING
XIE CHENGDONG

Assignees

安徽中益新材料科技股份有限公司

Dates

Publication Date: 20260512
Application Date: 20260209

Claims (10)

1. A high-service-life cement-based battery is characterized by comprising a cement matrix, an electrolyte, a positive electrode, an insulator diaphragm, a negative electrode, a positive current collector and a negative current collector, wherein the insulator diaphragm is embedded in the cement matrix and divides the cement matrix into two independent areas, wherein the positive electrode is arranged in one area, and the negative electrode is arranged in the other area; The cement matrix is obtained by pouring and curing conductive concrete slurry, and the conductive concrete slurry has the following composition and proportion: 100 parts by mass of cement; 60-80 parts by mass of particle filler; 30-40 parts of deionized water; 1.0 to 1.5 parts by mass of nano silicon dioxide; 2-3 parts by mass of lanthanum cobaltite; 2-4 parts by mass of manganese dioxide; 3-5 parts by mass of composite conductive carbon material; 0.5-1 parts by mass of nonionic dispersant; 0.5-1 parts by mass of sulfonate dispersant; 0.5-1 parts by mass of a hydrating agent; 0.5-1 parts by mass of lithium nitrate; 0.5-1 parts by mass of corrosion inhibitor; 0.5-1 parts by mass of interface modification material; 0.01 to 0.05 part by mass of air entraining agent; 3-5 parts by mass of porous material; The composite conductive carbon material is prepared by sequentially carrying out silanization modification and water reducer modification at the tail end of an amino group on redox graphene to obtain modified redox graphene mGO, then taking graphite as a core, coating mGO on the surface of the graphite to obtain graphite@ mGO with a core-shell structure, and finally compositing graphite@ mGO with carbon fibers.
2. The high life cement-based battery as claimed in claim 1, wherein the particulate filler is selected from one or more of quartz sand, river sand, aeolian sand, copper mine tailings, iron mine tailings, manganese mine tailings, tungsten mine tailings, zinc mine tailings, red mud; The nonionic dispersing agent is selected from one or more of PVP, poloxamer and Tween 80; The hydrating agent is one or more selected from lithium carbonate, barium nitrate, calcium nitrate, sodium sulfate and calcium formate; the air entraining agent is one or more selected from rosin thermopolymer, sodium dodecyl benzene sulfonate, tea saponin and fatty alcohol polyoxyethylene ether; The interface modification material is one or more selected from KH550, KH560, KH570 and TiN/CrN; the corrosion inhibitor is one or more selected from sodium phosphate, sodium silicate, benzimidazole and hexadecylamine; the porous material is one or more selected from zeolite, montmorillonite and diatomite.
3. The high life cement-based battery of claim 1, wherein the preparation of the composite conductive carbon material comprises the steps of: 1) Dispersing 190-210 parts by mass of rGO of redox graphene in an ethanol aqueous solution to obtain rGO slurry with 5% of solid content, adding the rGO slurry into a reaction kettle, dispersing at high speed, adjusting pH to be 5.3-5.7 by hydrochloric acid, heating to 58-62 ℃, dropwise adding 28-32 parts by mass of GPTMS, carrying out heat preservation reaction for 1-3 hours after the dropwise adding is finished, cooling to below 40 ℃, carrying out solid-liquid separation, and washing the separated solid with ethanol for 1-3 times to obtain a silanized graphene oxide GO-EP wet filter cake; 2) Redispersing the GO-EP wet filter cake in water, regulating the solid content to 15%, adding NaOH aqueous solution to adjust the pH value to be 8.3-8.7, adding water reducer with an amino terminal with a dry basis of 230-250 parts by mass, stirring and reacting for 3-5 hours at 78-82 ℃, cooling to below 50 ℃ after the reaction is finished, carrying out solid-liquid separation, washing and drying the separated solid to obtain modified redox graphene mGO; 3) Uniformly mixing 49-51 parts by mass of mGO, 0.4-0.6 part by mass of sodium hexametaphosphate and 440-460 parts by mass of deionized water to obtain mGO coating liquid; adding 490-510 parts by mass of graphite into a fluidized bed, fluidizing for 20-40 minutes by adopting 78-82 ℃ hot air, uniformly preheating materials, then spraying and coating the mGO coating liquid, and drying, cooling and screening after coating is finished to obtain graphite@ mGO with a core-shell structure; 4) Uniformly mixing 9-11 parts by mass of hydrophobic silica, 1.8-2.2 parts by mass of antistatic agent and 19-21 parts by mass of ethanol to form uniform slurry, spraying the obtained slurry onto 49-51 parts by mass of graphite@ mGO, and drying to remove ethanol to obtain SiO 2 master batch; Adding 790-810 parts by mass of graphite @ mGO into a mixer, adding the SiO 2 master batch, uniformly mixing, adding 178-182 parts by mass of carbon fiber, mixing for 45-60 minutes, sieving the obtained mixture, and homogenizing to obtain the composite conductive carbon material.
4. The method of claim 3, wherein the antistatic agent is dioctadecyl dimethyl ammonium chloride.
5. The method for preparing the high-life cement-based battery as claimed in claim 1, wherein the preparation of the lanthanum cobaltite comprises the following steps: dissolving lanthanum nitrate hexahydrate and cobalt nitrate hexahydrate in water to obtain a metal ion solution; stirring and mixing citric acid, glycol and water uniformly to obtain a complexing agent solution; slowly dripping a metal ion solution into a complexing agent solution, continuously stirring and heating to 80 ℃, preserving heat and evaporating water until deep blue transparent viscous sol is formed, and continuously stirring to form wet gel; Re-dispersing wet gel with deionized water to form homogeneous solution, transferring to inside lining of reaction kettle, setting the reaction kettle inside microwave synthesizer, hydrothermal reaction at 175-185 deg.c for 50-70 min, and natural cooling to room temperature; centrifugally separating the microwave hydrothermal product, washing and drying the separated solid to obtain precursor powder; and (3) placing the precursor powder into a crucible, placing the crucible into a muffle furnace, calcining for 2-3 hours at 550-600 ℃ in an air atmosphere, cooling to room temperature along with the furnace, and grinding to obtain the lanthanum cobaltite nano powder.
6. The high life cement-based battery as claimed in claim 5, wherein the total concentration of metal ions in the metal ion solution during the preparation of lanthanum cobaltite is 0.1-0.3 mol/L, n (citric acid): n (total metal ions) = (1-2): 1.
7. The high life cement-based battery as claimed in claim 1, wherein the electrolyte has the following composition and proportion: 10-15 parts by mass of potassium hydroxide; 5-10 parts by mass of potassium silicate; 0.5-2 parts by mass of lithium nitrate; 52-58 parts of deionized water; 3.5-5 parts by mass of sodium carboxymethylcellulose; 1.5 to 2.5 parts by mass of polyvinyl alcohol; 7-10 parts by mass of glycerol; 3-5 parts by mass of polyethylene glycol; 0.3-0.8 part by mass of silane coupling agent; boric acid 0.4-0.8 mass parts.
8. The high life cement-based battery of claim 7, wherein the preparation of the electrolyte comprises the steps of: Adding a proportioning amount of polyvinyl alcohol into 60% proportioning amount of deionized water, stirring at 85-90 ℃ until the polyvinyl alcohol is completely dissolved, then cooling to 70-75 ℃, adding a proportioning amount of sodium carboxymethyl cellulose, stirring until the sodium carboxymethyl cellulose is completely dissolved, then cooling to below 40 ℃, sequentially adding a proportioning amount of glycerin, polyethylene glycol and a silane coupling agent, and uniformly stirring to obtain a main polymer solution; Dissolving a proportioning amount of potassium hydroxide in 40% proportioning amount of deionized water to obtain a potassium hydroxide solution; adding potassium hydroxide solution into main polymer solution, stirring and mixing uniformly, adding the potassium silicate and the lithium nitrate in the proportion, stirring and dissolving to obtain gel solution, slowly adding the boric acid in the proportion into the gel solution, and stirring and mixing uniformly to obtain gel electrolyte.
9. The cement-based battery with long service life of claim 1, wherein the positive electrode and the negative electrode are both made of carbon fiber cloth, the positive current collector and the negative current collector are both made of aluminum strips, the insulator diaphragm is made of polyethylene film or polypropylene film, and the thickness of the insulator diaphragm is 0.1-0.3mm.
10. A method of preparing a high life cement-based battery as claimed in any one of claims 1 to 9, comprising the steps of: a) Preparation of conductive concrete slurry: the component materials with the proportion are stirred and mixed uniformly, so that the uniform mixing of all the component materials is ensured, the particle agglomeration phenomenon is avoided, and the conductive concrete slurry is obtained; b) Pouring, forming and maintaining: Pouring conductive concrete slurry into a preset die, and respectively pouring a positive electrode cement matrix lower unit and a negative electrode cement matrix lower unit; then, paving positive electrode materials and negative electrode materials on the top surfaces of the positive electrode cement matrix lower unit and the negative electrode cement matrix lower unit respectively, wherein the sizes of the positive electrode materials and the negative electrode materials are slightly smaller than those of the die, fixing one sides of the positive electrode materials and the negative electrode materials with positive current collector materials and negative current collector materials respectively, and welding wires on the positive current collector materials and the negative current collector materials respectively and leading out the outside of the die; Continuously pouring conductive concrete slurry into a mold, respectively pouring an anode cement matrix upper unit and a cathode cement matrix upper unit at the tops of an anode cement matrix lower unit and a cathode cement matrix lower unit, wherein the anode cement matrix lower unit, the cathode cement matrix lower unit, the anode cement matrix upper unit and the cathode cement matrix upper unit form a cement matrix together; c) Soaking in potassium hydroxide solution: Respectively soaking the anode cement matrix-electrode-current collector combination and the cathode cement matrix-electrode-current collector combination which are subjected to maintenance in a 20-30wt% potassium hydroxide aqueous solution for 2-3 days at room temperature, taking out after the soaking is finished, and airing; d) Coating and penetrating electrolyte, namely uniformly coating gel electrolyte on the surfaces of a positive electrode cement matrix and a negative electrode cement matrix in the combined body, and then placing the coated combined body in a constant temperature and constant humidity environment for standing for 24-48 hours to fully penetrate and solidify the electrolyte; e) And forming the battery, namely inserting an insulator diaphragm between the positive and negative electrode cement matrixes when electrolyte gel coated on the surfaces of the positive and negative electrode cement matrixes is solidified to a touch dry state, and pressing the insulator diaphragm and the combined body into a whole to obtain the cement-based battery.

Description

High-service-life cement-based battery and preparation method thereof Technical Field The invention relates to a high-service-life cement-based battery and a preparation method thereof, and belongs to the technical field of cement-based batteries. Background Under the guidance of the 'double carbon' target, power stations and power generation equipment of clean energy sources such as solar energy, wind energy, water energy and the like are well established and put into use. However, solar energy, wind energy, water energy and the like have different defects under the influence of seasons, climates, geographical positions and other factors, and the power generation capacity is excessive and overload operation is easy to occur to a power grid system, so that the effective storage of energy becomes one of key problems of efficient utilization of clean energy. Chemical energy storage batteries are one of the most commonly used energy storage devices in the world, which generally employ conventional electrochemical energy storage principles, relying on chemical reactions of electrodes with electrolytes to achieve energy storage and release. Cement-based batteries are used as an emerging electrochemical energy storage battery, and cement-based materials (such as concrete) are combined with conductive additives and electrode materials to provide an energy storage function. With the development of low-carbon buildings and smart cities, cement-based batteries are one of the key technologies of "energy storage buildings". Although the existing cement-based battery can realize building fusion, the service life is short, the energy storage requirement of a building structure for long-term service is difficult to meet, and the commercialization popularization of the cement-based battery is restricted, so that the development of a preparation method of the cement-based battery capable of improving the service life and considering the building structure fusion property and the mechanical property is necessary, and the technical problem to be solved by the person in the field is urgent. Disclosure of Invention The present invention has been made in view of the above problems occurring in the prior art, and an object of the present invention is to provide a long-life cement-based battery and a method for manufacturing the same. In order to achieve the above purpose, the present invention adopts the following technical scheme: the high-service-life cement-based battery comprises a cement matrix, an electrolyte, a positive electrode, an insulator diaphragm, a negative electrode, a positive current collector and a negative current collector, wherein the insulator diaphragm is embedded in the cement matrix to divide the cement matrix into two independent areas, wherein the positive electrode is arranged in one area, and the negative electrode is arranged in the other area; The cement matrix is obtained by pouring and curing conductive concrete slurry, and the conductive concrete slurry has the following composition and proportion: 100 parts by mass of cement; 60-80 parts by mass of particle filler; 30-40 parts of deionized water; 1.0 to 1.5 parts by mass of nano silicon dioxide; 2-3 parts by mass of lanthanum cobaltite; 2-4 parts by mass of manganese dioxide; 3-5 parts by mass of composite conductive carbon material; 0.5-1 parts by mass of nonionic dispersant; 0.5-1 parts by mass of sulfonate dispersant; 0.5-1 parts by mass of a hydrating agent; 0.5-1 parts by mass of lithium nitrate; 0.5-1 parts by mass of corrosion inhibitor; 0.5-1 parts by mass of interface modification material; 0.01 to 0.05 part by mass of air entraining agent; 3-5 parts by mass of porous material; The composite conductive carbon material is prepared by sequentially carrying out silanization modification and water reducer modification at the tail end of an amino group on redox graphene to obtain modified redox graphene mGO, then taking graphite as a core, coating mGO on the surface of the graphite to obtain graphite@ mGO with a core-shell structure, and finally compositing graphite@ mGO with carbon fibers. One or more of quartz sand, river sand, aeolian sand, copper mine tailings, iron mine tailings, manganese mine tailings, tungsten mine tailings, zinc mine tailings and red mud are selected from the group consisting of the following materials; The nonionic dispersing agent is selected from one or more of PVP, poloxamer and Tween 80; The hydrating agent is one or more selected from lithium carbonate, barium nitrate, calcium nitrate, sodium sulfate and calcium formate; the air entraining agent is one or more selected from rosin thermopolymer, sodium dodecyl benzene sulfonate, tea saponin and fatty alcohol polyoxyethylene ether; The interface modification material is one or more selected from KH550, KH560, KH570 and TiN/CrN; the corrosion inhibitor is one or more selected from sodium phosphate, sodium silicate, benzimidazole and hexadecylamine; the porous ma