CN115466095B - Solid energy storage material applied to targeted flow battery and preparation method thereof - Google Patents

Solid energy storage material applied to targeted flow battery and preparation method thereof Download PDF

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CN115466095B
CN115466095B CN202211102575.5A CN202211102575A CN115466095B CN 115466095 B CN115466095 B CN 115466095B CN 202211102575 A CN202211102575 A CN 202211102575A CN 115466095 B CN115466095 B CN 115466095B
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storage material
solid
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solid energy
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CN115466095A (en
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吴晓宏
卢松涛
郭宝
李杨
秦伟
洪杨
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Harbin Institute of Technology
Chongqing Research Institute of Harbin Institute of Technology
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Chongqing Research Institute of Harbin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/04—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by dissolving-out added substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/40—Porous or lightweight materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a solid energy storage material applied to a targeted flow battery and a preparation method thereof, and belongs to the technical field of redox targeted reaction flow battery electrochemical energy storage. The invention solves the problem of poor infiltration capacity of the prepared particles caused by the hydrophobicity of the existing solid energy storage material. According to the invention, the hydrophilic material is doped into the energy storage material and the chiseled substance, the silica sol is used as an adhesive after grinding, the mixture is kneaded into a dough shape, then the mixture is granulated, the granules are soaked and pore-formed after drying, and the solid energy storage granules with a certain pore diameter are obtained after drying, and can be fully soaked in the electrolyte, so that the air on the surfaces of the granules is discharged, the contact area between the solution and the solid energy storage granules is improved, and ions (electrons) are more easily embedded/extracted (transferred), so that the utilization rate of the solid material is improved from 40% to more than 75%.

Description

Solid energy storage material applied to targeted flow battery and preparation method thereof
Technical Field
The invention relates to a solid energy storage material applied to a targeted flow battery and a preparation method thereof, and belongs to the technical field of redox targeted reaction flow battery electrochemical energy storage.
Background
The renewable energy power generation has large grid connection difficulty due to the characteristics of discontinuity, instability and uncontrollable, so that the large-scale energy storage technology becomes an important means for effectively reducing the wind and light rejection rate, the problems of the intermittent property and the fluctuation of the renewable energy power generation can be effectively solved, and the renewable energy power generation system can be used for peak clipping and valley filling of a power grid and improving the electric energy quality. The flow battery is very suitable for large-scale energy storage system application due to expansibility, safety and flexible modular design, and is particularly suitable for power grid and micro-grid energy storage application.
The current developed and mature flow battery is an all-vanadium flow battery, and the energy of the flow battery is not stored in the battery but in the electrolyte separated from the battery, unlike other traditional batteries such as a lithium ion battery, so that the energy density of the flow battery is mainly limited by the concentration of soluble redox substances in the electrolyte, and the problems of high vanadium cost, high maintenance cost caused by strong acidity of solution and cost improvement caused by high requirement of the battery on temperature are still solved although the active concentration of the all-vanadium flow battery is improved through research in recent years. For other low cost aqueous flow batteries, the solubility of the electrolyte still needs to be further improved.
The redox targeted flow battery is a novel flow battery recently proposed, and the energy storage substance is added into the liquid storage tank to enable the active substance in the solution to be subjected to electronic or ion exchange with the solid material, so that energy is stored in the solid material, and the problem that the capacity of the flow battery is limited by the solubility of the active substance can be effectively solved. However, the existing solid materials are generally prepared by mixing energy storage substances, carbon black and polyvinylidene fluoride through organic solvents, and granulating or filament-forming the solid materials through a granulator or an electrostatic spinning technology so as to improve the specific surface area. Although the specific surface area of the solid energy storage particles obtained by the process is improved, the prepared particles have poor infiltration capacity due to the hydrophobicity of the material, bubbles exist in the surfaces of the particles in the solution, the particles cannot fully contact the solution, and electrons or ions in the solution cannot be embedded/extracted, so that the utilization rate of the solid material is only 50% or even lower of the theoretical capacity. And the phenomenon has larger influence on the thicker electrolyte, the larger the concentration of the solution is, the larger the surface tension of the liquid is, and the wettability of particles is further reduced.
Disclosure of Invention
The invention provides a solid energy storage material applied to a redox targeted flow battery and a preparation method thereof, aiming at solving the problem of poor infiltration capacity of prepared particles caused by hydrophobicity of the existing solid energy storage material.
The technical scheme of the invention is as follows:
one of the purposes of the invention is to provide a preparation method of a solid energy storage material, which comprises the following steps:
s1, preparing silica sol;
s2, mixing and grinding the pore-forming agent, the hydrophilic material and the energy storage material, uniformly mixing to obtain mixed powder, dropwise adding the silica sol into the mixed powder, stirring while dropwise adding, and kneading to be in a dough shape after dropwise adding is completed;
s3, granulating the dough-like solid in a granulator to prepare cylindrical particles, drying, grinding to enable the particle size of the particles to reach 30-60 meshes, soaking the particles in water, changing water every 8 hours, soaking for 24 hours, and drying to obtain the solid energy storage material particles.
Further limited, the operation process of S1 is to mix dilute hydrochloric acid and tetraethyl silicate and then magnetically stir the mixture to obtain silica sol.
Further defined, the mass ratio of the dilute hydrochloric acid to the tetraethyl silicate is (1-4): 6-9.
Further defined, the concentration of the dilute hydrochloric acid is 0.005-0.02mol/L.
Further defined, the magnetic stirring time is 2-6 hours.
Further defined, the pore-forming agent in S2 is one or a combination of two soluble lithium, sodium or potassium salts.
Further defined, the hydrophilic material is hydrophilic nanosilica or/and hydrophilic carbon black.
Further defined, the energy storage material Lu Shilan, prussian blue analogues, liFePO 4 、LiTiPO 4 Polyimide or Ni (OH) 2 。
Further defined, the mass ratio of pore-forming agent, hydrophilic material and energy storage material in S2 is (6-9): (0.5-3): (0-3).
Further defined, the diameter of the cylindrical particles in S3 is 0.5-2mm and the length is 1-4mm.
Further defined, the drying conditions in S3 are 70 ℃ for 24 hours.
The second object of the invention is to provide a solid energy storage material prepared by the method, which is used for redox targeted flow batteries.
Further defined, the solid energy storage material is disposed within a positive electrolyte reservoir of the redox targeted flow battery.
According to the invention, hydrophilic materials are mixed into energy storage materials and pore-forming substances, silica sol is used as an adhesive after grinding, the mixture is kneaded into dough, and then the dough is granulated, dried, soaked and pore-formed, and dried to obtain solid energy storage particles with a certain pore diameter. Compared with the prior art, the application has the following beneficial effects:
(1) By doping hydrophilic silicon dioxide, the hydrophilicity of the material is improved, so that the solid energy storage particles can be fully soaked in the electrolyte, air on the surfaces of the particles is discharged, the contact area of the solution and the solid energy storage particles is improved, ions (electrons) are more easily embedded/extracted (transferred), and the utilization rate of the solid material is improved from 40% to more than 75%.
(2) The solid energy storage material provided by the invention has a stable structure, and the situation that most solid substances flow into the battery and the pipeline of the flow battery is blocked due to the fact that object particles are scattered by water flow is avoided.
(3) The solid energy storage material provided by the invention has the advantages of low cost of raw materials, simple preparation process, suitability for large-scale production, great reduction of production cost and improvement of production efficiency.
Drawings
FIG. 1 is a schematic diagram of a targeted flow battery;
FIG. 2 is a physical diagram of the solid energy storage material particles prepared in example 1;
FIG. 3 is SEM pictures (at different magnifications) of particles of solid energy storage material prepared according to example 1;
FIG. 4 is a photograph of the solid energy storage material particles prepared in example 1 immersed in a solution;
FIG. 5 is a photograph of the solid energy storage material of comparative example 1 immersed in a solution;
fig. 6 is a charge-discharge capacity-voltage graph of a battery prepared using the solid energy storage materials provided in example 1 and comparative example 1;
fig. 7 is a cycle life schematic of batteries prepared using the solid energy storage materials provided in example 1 and comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The following examples relate to the manufacturer, model number of the raw materials:
hydrophilic nanosilica is purchased for the microphone reagent functional network, CAS number: 7631-86-9;
the hydrophilic carbon black is a water-soluble carbon black product of a Taobao-Xiangzhu colorful flagship store;
the common carbon black is a common carbon black product of a colorful flagship store.
Example 1:
the specific process for preparing the solid energy storage material particles in the embodiment is carried out according to the following steps:
step 1, preparing silica sol:
preparing a 30g mixed solution of tetraethyl silicate and dilute hydrochloric acid with the mass concentration of 0.01mol/L according to the mass ratio of 7:3, and magnetically stirring for 4 hours to obtain silica sol;
step 2, preparing a dough solid:
putting 8g of Prussian blue, 1g of hydrophilic nano silicon dioxide, 1g of hydrophilic carbon black and 1g of KCl into a mortar, grinding and mixing uniformly to obtain mixed powder, dropwise adding the silica sol prepared in the step 1 into the mixed powder, stirring while dropwise adding 10g of silica sol, and kneading to be in a dough state after the dropwise adding is completed to obtain a dough solid;
step 3, preparing solid energy storage material particles:
granulating the dough-like solid obtained in the step 2 in a granulator, wherein the aperture of the granulator is 1mm, obtaining cylindrical particles with the length of 1-4mm, drying at 70 ℃ for 24 hours, crushing the particles after drying to reach the particle size of 30-60 meshes, soaking in water for 24 hours, changing deionized water every 8 hours to enable the pore-forming agent in the particles to be fully dissolved in the water to obtain holes, increasing the surface area of the energy storage particles, and drying to obtain the solid energy storage material particles shown in fig. 2, wherein the solid energy storage material particles prepared in the embodiment are uniform as can be seen from fig. 2.
The obtained solid energy storage material particles are subjected to structure and performance characterization, and the test structure is as follows:
(1) The obtained solid energy storage material particles are subjected to microscopic morphology characterization, SEM pictures are shown in figure 3, and as can be seen from figure 3, the surfaces of the solid energy storage material particles obtained by the method provided by the invention are provided with micro holes, so that the solid energy storage material particles prepared by the method provided by the invention have a certain aperture.
(2) The wettability test is performed on the obtained solid energy storage material particles, a photograph of the solid energy storage material particles immersed in the KCl solution is shown in fig. 4, and as can be seen from fig. 4, the solid energy storage material particles prepared in the embodiment have good hydrophilicity, and no bubbles exist on the surfaces of the particles immersed in the KCl solution.
Comparative example 1:
the comparative example is different from example 1 in that the mixed powder consists of Prussian blue, common carbon black and KCl, and the remaining materials and the procedure are the same as example 1.
The preparation process comprises the following steps:
step 1, preparing silica sol:
preparing a 30g mixed solution of tetraethyl silicate and dilute hydrochloric acid with the mass concentration of 0.01mol/L according to the mass ratio of 7:3, and magnetically stirring for 4 hours to obtain silica sol;
step 2, preparing a dough solid:
grinding 8g of Prussian blue, 2g of common carbon black and 1g of KCl in a mortar, uniformly mixing to obtain mixed powder, dropwise adding the silica sol prepared in the step 1 into the mixed powder, stirring while dropwise adding 10g of the silica sol, and kneading to be in a dough state after the dropwise adding is completed to obtain a dough-like solid;
step 3, preparing solid energy storage material particles:
granulating the dough-like solid obtained in the step 2 in a granulator, wherein the aperture of the granulator is 1mm, obtaining cylindrical particles with the length of 1-4mm, drying at 70 ℃ for 24 hours, crushing the particles after drying to enable the particle size to reach 30-60 meshes, soaking the particles in water for 24 hours, changing deionized water every 8 hours, enabling the pore-forming agent in the particles to be fully dissolved in the water to obtain holes, increasing the surface area of the energy storage particles, and drying to obtain the solid energy storage material particles.
The wettability test is performed on the obtained solid energy storage material particles, a photo of the solid energy storage material particles immersed in the KCl solution is shown in fig. 5, and as can be seen from fig. 5, bubbles exist on the surface of the solid energy storage material, wherein small bubbles exist in the surface concave position of the energy storage material, so that the contact area between the solution and the energy storage material is reduced, the ion and electron transmission speed is reduced or even the transmission is impossible, and the utilization rate of the energy storage material is low. As can be seen from comparing fig. 4 and fig. 5, the solid energy storage material particles prepared in example 1 have better hydrophilic properties.
Effect example:
the solid energy storage material particles obtained in example 1 and comparative example 1 were applied to a targeted redox flow battery, respectively, as shown in fig. 1, the flow battery was a symmetric battery composed of a positive electrode energy storage tank and a negative electrode energy storage tank, and 15ml of electrolyte in the positive electrode energy storage tank was composed of 1mol/LKCl and 0.4mol/LK 3 [Fe(CN) 6 ]Composition of electrolyte in the negative electrode energy storage tank is 60ml composed of 1mol/LKCl and 0.3mol/LK 4 [Fe(CN) 6 ]The composition of the battery is that the internal electrode of the battery is graphite felt, the ion exchange membrane is H-shaped Nafion117 ion exchange membrane, and the graphite felt or filter cloth with the aperture larger than 60 meshes is used for fixing the side of the positive electrode energy storage tank flowing into the battery at a liquid inlet to prevent solid energy storage particles from flowing into the battery along with liquid, 1.6g of the solid energy storage material particles obtained in the example 1 and the comparative example 1 are respectively added into the positive electrode of the flow battery for storageIn the energy tank, 1 cycle of activation is carried out, then constant-current charge and discharge is carried out on the flow battery, and the charge and discharge steps are as follows:
the shelf life is 1 minute;
constant current discharge, voltage set to-0.5V, current set to 0.27A;
the shelf life is 1 minute;
constant current charging, the voltage is set to 0.5V, and the current is set to 0.27A;
the shelf life is 1 minute;
cycling for 200 times;
and (5) ending.
As shown in fig. 6, in example 1, hydrophilic silica is doped to improve hydrophilicity of the material, so that the solid energy storage particles can be fully soaked in the electrolyte, air on the surfaces of the particles is discharged, contact area between the solution and the solid energy storage particles is improved, and ions (electrons) are more easily embedded/extracted (transferred), so that utilization rate of the solid material is improved from 40% to more than 75%.
Fig. 7 is a cycle life schematic of a battery prepared by using the solid energy storage material provided in example 1, and as can be seen from fig. 7, the solid energy storage material prepared in example 1 has a stable particle structure, and the capacity of the battery has no significant attenuation in 200 cycles.
While the invention has been described in terms of preferred embodiments, it is not intended to be limited thereto, but rather to enable any person skilled in the art to make various changes and modifications without departing from the spirit and scope of the present invention, which is therefore to be limited only by the appended claims.

Claims (8)

1. The preparation method of the solid energy storage material is characterized by comprising the following steps of:
s1, preparing silica sol;
s2, mixing a hydrophilic material into an energy storage material and a pore-forming agent, grinding to obtain mixed powder, dropwise adding silica sol serving as an adhesive into the mixed powder, stirring while dropwise adding, and kneading into a dough shape after dropwise adding is completed;
the pore-forming agent is one or two of soluble lithium, sodium or potassium salts, the hydrophilic material is hydrophilic nano silicon dioxide or/and hydrophilic carbon black, and the energy storage material is Prussian blue or LiFePO 4 、LiTiPO 4 Polyimide or Ni (OH) 2 ；
The mass ratio of pore-forming agent, hydrophilic material and energy storage material is (6-9): (0.5-3): (0-3), wherein the energy storage material is other than 0;
s3, granulating the dough-like solid in a granulator to prepare cylindrical particles, drying and grinding the cylindrical particles to enable the particle size of the particles to reach 30-60 meshes, then soaking the cylindrical particles in water, changing water every 8 hours, soaking the cylindrical particles for 24 hours, and drying the cylindrical particles to obtain the solid energy storage material particles.
2. The preparation method according to claim 1, wherein S1 is a silica sol obtained by mixing dilute hydrochloric acid and tetraethyl silicate and magnetically stirring.
3. The preparation method according to claim 2, wherein the mass ratio of the dilute hydrochloric acid to the tetraethyl silicate is (1-4): (6-9), and the concentration of the dilute hydrochloric acid is 0.005-0.02mol/L.
4. The method of claim 2, wherein the magnetic stirring time is 2-6 hours.
5. The preparation method according to claim 1, wherein the mass ratio of the silica sol to the mixed powder in S2 is (1-3): (3-1).
6. The method according to claim 1, wherein the diameter of the cylindrical particles in S3 is 0.5-2mm and the length is 1-4mm.
7. A solid energy storage material made by the method of claim 1.
8. A solid energy storage material prepared by the method of claim 1 for use in a redox flow battery.
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JP2010086935A (en) * 2008-09-03 2010-04-15 Sharp Corp Redox flow battery
DE102010004942A1 (en) * 2010-01-18 2011-07-21 Garzem, Michael, 53881 Electrochemical energy storage i.e. redox-flow-cell, for storing electrical power in chemical components in liquid form, has container comprising guard, which comprises hydrophobic liquid with low density than that of electrolytes
KR101752889B1 (en) * 2015-09-25 2017-06-30 롯데케미칼 주식회사 Porous membrane of zinc-bromine redox flow battery, preparation method for porous membrane of zinc-bromine redox flow battery, and zinc-bromine redox flow battery
CN108539203B (en) * 2017-03-03 2021-04-02 湖南省银峰新能源有限公司 Super-hydrophilic material modified electrode material for energy storage flow battery
CN110120485B (en) * 2018-02-06 2021-06-18 比亚迪股份有限公司 Polymer diaphragm and preparation method and application thereof, and lithium ion battery and preparation method thereof
CN114342133A (en) * 2019-04-01 2022-04-12 新加坡国立大学 Redox flow battery
US11837767B2 (en) * 2020-12-23 2023-12-05 Uop Llc Electrolyte compositions for redox flow batteries

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