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CN115441067B - Multicomponent mixed electrolyte and preparation method and application thereof - Google Patents

Multicomponent mixed electrolyte and preparation method and application thereof Download PDF

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Publication number
CN115441067B
CN115441067B CN202211124256.4A CN202211124256A CN115441067B CN 115441067 B CN115441067 B CN 115441067B CN 202211124256 A CN202211124256 A CN 202211124256A CN 115441067 B CN115441067 B CN 115441067B
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electrolyte
water
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mixed
organic
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CN115441067A (en
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方国赵
潘奕偲
刘哲轩
梁叔全
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Primary Cells (AREA)

Abstract

The invention discloses a multi-component mixed electrolyte, a preparation method and application thereof. The electrolyte comprises an aqueous solution and inorganic solid powder, wherein the inorganic solid powder is clay powder, and the clay powder controls the reactivity of a system on one hand, and provides an ion exchange channel in the solution on the other hand, so that the ion exchange rate is ensured; the electrolyte can be modified by organic liquid or organic solid, the organic liquid can break the hydrogen bond network of free water, inhibit the hydrogen evolution side reaction of water, the organic solid can strengthen the adsorptivity of the electrolyte, form a stable electrode/electrolyte interface, and reduce the generation of dendrites. The water-based ion battery prepared by the mixed-state electrolyte provided by the invention has high capacity, effectively inhibits side reactions caused by a water system, has excellent electrochemical performance, and has wide application value in the field of power batteries.

Description

Multicomponent mixed electrolyte and preparation method and application thereof
Technical Field
The invention relates to a mixed electrolyte, in particular to a multi-component mixed electrolyte, a preparation method and application thereof, and belongs to the technical field of battery electrolytes.
Background
The water-based ion battery adopts water as a solvent, has the advantages of safety, green, environmental protection and low cost, but the solvent of water also has a huge problem. For the negative electrode, there are serious corrosion problems, oxidation problems, dendrite growth problems, and the like; for the positive electrode, the dissolution problem of the material (e.g., vanadium dissolution, manganese dissolution, etc.) is particularly serious; the water solvent itself has serious problems of hydrogen evolution and oxygen evolution due to water decomposition, and may have serious side reactions with the positive and negative electrodes due to high water activity.
In order to ensure that the activity of the electrolyte in the water-based battery stays in a reasonable range, chinese patent (CN 110994046A) discloses a mixed-state electrolyte of the water-based battery, which consists of liquid substances and solid substances, and by improving the solid content of the mixed-state electrolyte, the occurrence of side reactions such as corrosion, oxidation and the like of a metal negative electrode is inhibited, the dissolution condition of a positive electrode can be obviously reduced, and dendrite generation is effectively inhibited; however, the solid content in the mixed electrolyte is too high, and the selected solid substance is inert powder, so that the side reaction of the anode and the cathode is reduced, the migration rate of metal ions is seriously influenced, and the battery capacity is reduced.
Therefore, the existing problems of the water-based battery have seriously hindered the further industrial application and development of the water-based ion battery, and how to stabilize and improve the water system environment, so that the side reactions of the anode and the cathode can be reduced, and the battery capacity can be improved, and the technical problem to be solved is urgent.
Disclosure of Invention
Aiming at the problems existing in the prior art, the first object of the invention is to provide a multi-component mixed electrolyte, which comprises an aqueous solution and inorganic solid powder, wherein the inorganic solid powder is clay powder, the clay powder controls the reactivity of a water system on one hand, and an ion exchange channel in the solution is provided on the other hand, so that the ion exchange rate is ensured; meanwhile, based on the synergistic effect of the aqueous solution and the inorganic solid powder, the electrolyte effectively solves the problems of corrosion, dissolution, passivation and the like of the electrode material in the water system.
The second object of the present invention is to provide a method for preparing a multicomponent mixed electrolyte, wherein the method comprises the steps of fully mixing inorganic solid powder with an aqueous solution. The method is simple and convenient, has no waste water and waste gas, can carry out intermittent or continuous production according to production requirements, and effectively reduces production cost.
The invention provides an application of a multi-component mixed electrolyte, wherein clay solids in the mixed electrolyte can be tightly adsorbed with an electrode, a stable electrode/electrolyte interface is formed on the surface of an electrode material, free exchange of ions can be ensured, dendrite formation can be effectively inhibited, and a negative electrode is protected.
In order to achieve the technical aim, the invention provides a multi-component mixed state electrolyte, which comprises an aqueous solution and inorganic solid powder; the aqueous solution is a soluble metal salt solution; the inorganic solid powder is clay powder; the mass ratio of the aqueous solution to the inorganic solid powder is 1-3: 1.
The inorganic solid powder in the mixed electrolyte has extremely strong chemical stability, can control the reactivity of a water system, and has a microcosmic layered structure which is favorable for the transmission of ions and provides an effective channel for the efficient transmission of ions. Further, the aqueous solution in the mixed-state electrolyte provides metal ions on the one hand and water molecules on the other hand, which are beneficial to efficient ion transport.
In the mixed electrolyte provided by the invention, the addition of the aqueous solution and the inorganic solid powder is strictly carried out according to the set proportion, and if the proportion of the aqueous solution is too low, the ion migration rate in the electrolyte is low, the reaction efficiency is low, and the capacity of a battery is further influenced; if the ratio is too large, the water activity is too high, side reactions such as hydrogen evolution oxygen absorption corrosion and the like are greatly increased, and the instability of the battery is increased.
As a preferred scheme, the anions contained in the soluble metal salt solution are at least one of sulfate ions, trifluoromethyl sulfonate ions and bistrifluoromethane sulfonyl imide ions, and the contained metal cations are at least one of zinc ions, lithium ions and sodium ions.
As a preferred embodiment, the molar concentration of the metal cations in the soluble metal salt solution is 1 to 3mol/L. The concentration of metal ions is too low, the number of ions used for transportation in the electrolyte cannot meet the demand, and the battery capacity is low. With the increase of the concentration of the metal ions, the capacity is correspondingly increased, but after the concentration exceeds a proper concentration, the electrochemical performance such as the capacity is not increased, and the viscosity is increased due to the increase of the concentration, so that the problem of increasing the ion transport resistance is also solved. Thus, too high a metal ion concentration results in insignificant cost consumption.
As a preferred embodiment, the clay powder is at least one of montmorillonite, palygorskite, bentonite and kaolin. Montmorillonite can be ion-exchanged with metal cations, and palygorskite has the same ion conductivity as the aqueous electrolyte and higher migration number of zinc ions than the aqueous electrolyte. The kaolin lattice shift and good adsorption of zinc ions can reduce the solvation sheath which is stronger and more compact with water. The bentonite can promote the surfaces of the anode and the cathode to form a protective layer at the same time, so that the dissolution of manganese is inhibited, and the metal zinc anode which is well preserved and has no dendrite is obtained.
As a preferred embodiment, the clay powder is any two of montmorillonite, palygorskite, bentonite and kaolin.
As a preferable scheme, the clay powder is formed by combining any two of montmorillonite, palygorskite, bentonite and kaolin according to a mass ratio of 1:1-1.5. Further preferably, the clay powder is composed of kaolin and montmorillonite, and the mass ratio of the kaolin to the montmorillonite is 1:1. in the water system solution, the kaolin and the montmorillonite have strong synergistic effect, so that the ion exchange property of the clay powder is stimulated, ions between clay powder layers can be easily exchanged by Zn 2+, and the migration capacity and the transport capacity of Zn 2+ are greatly improved.
As a preferred embodiment, the multi-component mixed state electrolyte further comprises an organic liquid or an organic solid.
As a preferred embodiment, the organic liquid is at least one of methanol, ethylene glycol, glycerol, ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate. Hydroxyl carried by alcohols can effectively inhibit the activity of water through hydrogen bonding; the hydrophobic carbonic ester can reduce the quantity of coordinated water, break the hydrogen bond network of free water, further inhibit the hydrogen evolution side reaction caused by water, and effectively solve the problem of unstable battery cathode.
As a preferred scheme, the mass ratio of the organic liquid to the soluble metal salt solution is 1:19 to 49.
As a preferred scheme, the mass ratio of the organic solid to the clay powder is 1:1 to 10. Further preferably, the organic solid is polyvinylidene fluoride, and the weight ratio of polyvinylidene fluoride to clay powder is 1:10.
As a preferred embodiment, the organic solid is polyvinylidene fluoride. The polyvinylidene fluoride has the characteristics of low internal resistance, high uniformity, good mechanical property, good chemical and electrochemical stability and the like. The addition of polyvinylidene fluoride to form quasi-solid electrolyte based on water electrolyte reduces free water molecules, and has high (thickness/void ratio) uniformity, thus providing pore size suitable for zinc ion movement. The low heat conductivity improves the high temperature resistance of the battery and avoids the short circuit of the battery caused by high temperature.
The invention also provides a preparation method of the multicomponent mixed state electrolyte, which comprises the steps of mixing raw materials including clay powder, adding the raw materials into a soluble metal salt solution, and stirring and performing ultrasonic dispersion.
Further, the invention also provides a detailed preparation method of the multi-component mixed state electrolyte, which comprises the following steps: mixing any two different clay powders uniformly, adding the mixture into a soluble metal salt solution in a stirring state, continuously stirring for 4-8 hours at a rotating speed of 500r/min, and performing ultrasonic dispersion for 1 hour at normal temperature after stirring is finished to obtain the clay powder; or uniformly mixing the organic liquid and the soluble metal solution, adding any clay powder under stirring, continuously stirring for 4-8 hours at the rotating speed of 500r/min, and performing ultrasonic dispersion for 1 hour at normal temperature after stirring is finished to obtain the composite material; or mixing organic solid and any clay powder uniformly, adding the mixture into the soluble metal salt solution in a stirring state, continuously stirring for 4-8 h at the rotating speed of 500r/min, and performing ultrasonic dispersion for 1h at normal temperature after stirring.
The invention also provides application of the multi-component mixed state electrolyte to preparation of a water-based ion battery. The water-based ion battery comprises the following components: positive electrode shell, positive electrode plate, mixed electrolyte, diaphragm, electrolyte, zinc negative electrode and negative electrode shell; and assembling the components to obtain the zinc ion water system battery.
The multi-state electrolyte provided by the invention utilizes the characteristics of each phase, so that the electrolyte not only has the advantage of high conductivity of the aqueous electrolyte, but also overcomes the problems of corrosion, dissolution, passivation and the like of electrode materials caused by a water system. The clay material adopted by the invention controls the reactivity of the water system on one hand, and provides an ion exchange channel in the solution on the other hand, thereby ensuring the ion exchange rate; furthermore, the invention has strong expansibility, and the three-phase or multi-phase electrolyte is formed by adding organic liquid or organic solid, wherein the hydroxyl of the organic liquid can effectively inhibit the activity of water in the electrolyte through hydrogen bonding, while the hydrophobic ester can effectively reduce the quantity of coordinated water, break the hydrogen bonding network of free water, and further inhibit the hydrogen evolution side reaction caused by water; the introduction of the organic solid greatly improves the mechanical property of the electrolyte, improves the adsorptivity and stability of the electrolyte, can form a stable electrode/electrolyte interface, reduces the generation of dendrites and prolongs the service life of the battery.
Compared with the prior art, the invention has the following beneficial technical effects:
1) The mixed electrolyte provided by the invention consists of an aqueous solution and inorganic solid powder, wherein the inorganic solid powder is clay powder, so that on one hand, the reactivity of a water system is controlled, and on the other hand, an ion exchange channel in the solution is provided, and the ion exchange rate is ensured; meanwhile, based on the synergistic effect of the aqueous solution and the inorganic solid powder, the electrolyte effectively solves the problems of corrosion, dissolution, passivation and the like of the electrode material in the water system.
2) In the technical scheme provided by the invention, organic liquid is also introduced into the mixed electrolyte, wherein alcohols can inhibit the activity of water in the electrolyte through the hydrogen bond action of hydroxyl and water molecules, and hydrophobic esters can effectively reduce the quantity of coordinated water, break the hydrogen bond network of free water and further inhibit hydrogen evolution side reaction caused by water.
3) In the mixed electrolyte provided by the invention, the organic solid is also introduced into the mixed electrolyte, so that the mechanical property of the electrolyte is greatly improved, the adsorptivity and stability of the electrolyte are improved, a stable electrode/electrolyte interface can be formed, the generation of dendrites is reduced, and the service life of the battery is prolonged.
Drawings
FIG. 1 is a graph of the long cycle performance of a comparative example 1 mixed state electrolyte assembled Zn/MnO 2 cell at a current density of 1A g -1;
Fig. 2 is a Zn/MnO 2 cell assembled with the mixed electrolyte of example 1, and the mass ratio of conventional aqueous electrolyte to ethylene glycol of comparative example 1 is 49: 1a graph comparing cycle performance at a current density of 1A g -1;
FIG. 3 is a graph comparing the cycling performance of the comparative example 2 mixed state electrolyte assembled Zn/MnO 2 cell with the example 2 mixed state electrolyte assembled Zn/MnO 2 cell at a current density of 0.3A g -1;
FIG. 4 is a graph comparing the cycling performance of the comparative example 3 mixed state electrolyte assembled Zn/MnO 2 cell with the example 3 mixed state electrolyte assembled Zn/MnO 2 cell at a current density of 0.3A g -1;
FIG. 5 is a graph showing the reversible performance test of the Zn/Zn cell with the mixed state electrolyte of example 2 at a current density of 1A cm -2.
Detailed Description
The invention will now be further illustrated by reference to the accompanying drawings and examples, wherein the starting materials are obtained commercially, and wherein the preparation process according to the invention is conventional in the art unless otherwise specified, and wherein the following examples are intended to illustrate the invention and are not intended to limit the invention further.
Example 1
1) Preparing 2g of kaolin solid powder and 1g of ethylene glycol;
2) Zinc sulfate is dissolved in deionized water to prepare a liquid electrolyte with zinc sulfate concentration of 2mol L -1;
3) The mass ratio of the glycol to the liquid electrolyte is 1:49 into a mixed liquid electrolyte;
4) Mixing kaolin and a mixed liquid electrolyte according to the mass ratio of 2:4, uniformly mixing, stirring for 6 hours at normal temperature and carrying out ultrasonic treatment for 1 hour to obtain the mixed electrolyte.
Example 2
1) Preparing 1g of kaolin solid powder and 1g of montmorillonite solid powder;
2) Zinc sulfate is dissolved in deionized water to prepare liquid electrolyte with zinc sulfate concentration of 2mol L -1;
3) The solid powder and the liquid electrolyte are mixed according to the mass ratio of 2:4, uniformly mixing, stirring for 6 hours at normal temperature and carrying out ultrasonic treatment for 1 hour to obtain the mixed electrolyte.
Example 3
1) Preparing 1g of kaolin and 1g of polyvinylidene fluoride;
2) Zinc sulfate is dissolved in deionized water to prepare liquid electrolyte with zinc sulfate concentration of 2mol L -1;
3) Mixing 1g of kaolin powder and 1g of polyvinylidene fluoride;
4) The solid powder and the liquid electrolyte are mixed according to the mass ratio of 2:4, uniformly mixing, stirring for 6 hours at normal temperature and carrying out ultrasonic treatment for 1 hour to obtain the mixed electrolyte.
Example 4
1) Preparing 2g of kaolin solid powder and 1g of ethylene glycol;
2) Zinc sulfate is dissolved in deionized water to prepare liquid electrolyte with zinc sulfate concentration of 2mol L -1;
3) The mass ratio of the glycol to the liquid electrolyte is 1:9, uniformly mixing to obtain a mixed liquid electrolyte;
4) Mixing kaolin and a mixed liquid electrolyte according to the mass ratio of 2:4, uniformly mixing, stirring for 6 hours at normal temperature and carrying out ultrasonic treatment for 1 hour to obtain the mixed electrolyte.
Example 5
1) Preparing 2g of kaolin solid powder and 1g of ethylene glycol;
2) Zinc sulfate is dissolved in deionized water to prepare liquid electrolyte with zinc sulfate concentration of 2mol L -1;
3) The mass ratio of the glycol to the liquid electrolyte is 1:19, uniformly mixing to obtain a mixed liquid electrolyte;
4) Mixing kaolin and a mixed liquid electrolyte according to the mass ratio of 2:4, uniformly mixing, stirring for 6 hours at normal temperature and carrying out ultrasonic treatment for 1 hour to obtain the mixed electrolyte.
Example 6
1) Preparing 0.5g of kaolin solid powder and 1.5g of montmorillonite solid powder;
2) Zinc sulfate is dissolved in deionized water to prepare a liquid electrolyte with zinc sulfate concentration of 2mol L -1;
3) The solid powder and the liquid electrolyte are mixed according to the mass ratio of 2:4, uniformly mixing, stirring for 6 hours at normal temperature and carrying out ultrasonic treatment for 1 hour to obtain the mixed electrolyte.
Example 7
1) Preparing 1.5g of kaolin solid powder and 0.5g of montmorillonite solid powder;
2) Zinc sulfate and manganese sulfate are respectively dissolved in deionized water to prepare liquid electrolyte with zinc sulfate concentration of 2mol L -1;
3) The solid powder and the liquid electrolyte are mixed according to the mass ratio of 2:4, uniformly mixing, stirring for 6 hours at normal temperature and carrying out ultrasonic treatment for 1 hour to obtain the mixed electrolyte.
Comparative example 1
1) Preparing 2g of ethylene glycol;
2) Zinc sulfate is dissolved in deionized water to prepare a liquid electrolyte with zinc sulfate concentration of 2mol L -1;
3) Respectively mixing ethylene glycol and liquid electrolyte according to the mass ratio of 1: 19. 1:49 are mixed uniformly.
Comparative example 2
1) Preparing 1g of kaolin;
2) Zinc sulfate is dissolved in deionized water to prepare liquid electrolyte with zinc sulfate concentration of 2mol L -1;
3) Respectively mixing kaolin and liquid electrolyte according to the mass ratio of 1:2 (g) are uniformly mixed.
Comparative example 3
1) Preparing 1g of polyvinylidene fluoride powder;
2) Zinc sulfate is dissolved in deionized water to prepare a liquid electrolyte with zinc sulfate concentration of 2mol L -1;
3) Respectively mixing polyvinylidene fluoride powder and liquid electrolyte according to the mass ratio of 1:2 (g) are uniformly mixed.
Comparative example 1a modified ion battery electrolyte was obtained by blending a conventional aqueous electrolyte with an organic liquid, a Zn/MnO 2 battery assembled with the electrolyte was able to stably circulate over 200 cycles at a current density of 1A g -1, the capacity was kept at 100mAh g -1, and as can be seen from fig. 1, the mass ratio of aqueous electrolyte to ethylene glycol in comparative example 1 was 49:1, the circulation effect is better. Example 1 also provided a mixed electrolyte with kaolin added thereto, and a Zn/MnO 2 cell assembled using the mixed electrolyte provided in example 1 had a capacity of about 150mAh g -1 at a current density of 1A g -1, which was 50% higher than comparative example 1 at the same current density; the mixed state electrolyte is modified by clay powder, so that the water content is correspondingly reduced, the problem of strong corrosion and oxidation of the cathode can be solved, dendrite formation can be effectively inhibited by a mixed state interface, the cathode can be effectively protected, and the capacity of the battery is greatly improved.
The Zn/MnO 2 cell prepared using the mixed electrolyte provided in example 2 was stable to cycle at a current density of 0.3A g -1 and the cell capacity was stable at 350mAh g -1, whereas the Zn/MnO 2 cell prepared using the electrolyte provided in comparative example 2 had a cell capacity of only 250mAh g -1 at a current density of 0.3Ag -1. The method is characterized in that due to the synergistic effect among kaolin, montmorillonite and zinc ion solution, the ion exchange property of clay powder is stimulated, ions among clay powder layers can be easily exchanged out by Zn 2+, and the migration capacity and the transport capacity of Zn 2+ are greatly improved, so that the battery capacity is greatly improved.
The Zn/MnO 2 cell prepared using the mixed state electrolyte provided in example 3 was stable to cycle at a current density of 0.3A g -1 and the cell capacity was stable to 200mAh g -1, whereas the Zn/MnO 2 cell prepared using the electrolyte provided in comparative example 3 had a cell capacity of only 150mAh g -1 at a current density of 0.3A g -1. The solid material formed by the clay powder and the organic solid phase forms a stable interface layer at the anode-cathode interface of the battery, so that side reactions and byproducts in the electrochemical reaction are reduced, and the electrode reaction has extremely strong reversibility, thereby greatly improving the battery capacity.
The mixed-state electrolyte provided by the embodiment of the invention not only can be used for preparing an asymmetric water-based ion battery, but also can be used for preparing the symmetric water-based ion battery. The Zn/Zn battery assembled by adopting the mixed-state electrolyte provided in example 2 shows excellent reversibility under the current of 1Acm -2, and the test result is shown in figure 5, because in the mixed-state electrolyte, the layered structure pores of kaolin and montmorillonite are uniformly distributed, the mixed-state electrolyte has good migration and transportation capability on Zn 2+ in a neutral environment, dendrites are not easy to form at the anode of the battery, and the corrosion resistance of the electrode is greatly improved, so that the cycle life of the rechargeable zinc ion water system battery is prolonged.

Claims (7)

1. A multi-component mixed electrolyte characterized by: comprises an aqueous solution and inorganic solid powder; the aqueous solution is a soluble metal salt solution; the inorganic solid powder is clay powder; the mass ratio of the aqueous solution to the inorganic solid powder is 1-3: 1, a step of;
The clay powder consists of kaolin and montmorillonite, wherein the mass ratio of the kaolin to the montmorillonite is 1:1.
2. The multi-component mixed electrolyte according to claim 1, wherein: the anions contained in the soluble metal salt solution are at least one of sulfate ions, trifluoromethyl sulfonate ions and bistrifluoromethane sulfonyl imide ions, and the contained metal cations are at least one of zinc ions, lithium ions and sodium ions.
3. A multi-component mixed state electrolyte according to claim 1 or 2, characterized in that: the molar concentration of metal cations in the soluble metal salt solution is 1-3 mol/L.
4. The multi-component mixed electrolyte of claim 1, wherein: also included are organic liquids or organic solids; the organic liquid is at least one of methanol, glycol, glycerol, ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate; the organic solid is polyvinylidene fluoride.
5. The multi-component mixed electrolyte of claim 4, wherein: the mass ratio of the organic liquid to the soluble metal salt solution is 1: 19-49; the mass ratio of the organic solid to the clay powder is 1: 1-10.
6. The method for preparing the multi-component mixed electrolyte according to any one of claims 1 to 5, which is characterized in that: mixing the raw materials including clay powder, adding into soluble metal salt solution, stirring, and ultrasonic dispersing.
7. Use of a multi-component mixed electrolyte according to any one of claims 1 to 5, characterized in that: is used for preparing the water-based ion battery.
CN202211124256.4A 2022-09-15 2022-09-15 Multicomponent mixed electrolyte and preparation method and application thereof Active CN115441067B (en)

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Publication number Priority date Publication date Assignee Title
CN1331847A (en) * 1998-12-22 2002-01-16 株式会社华仁电池 Solid electrolytes using aborbing agent and methods for preparing them
CN109980302A (en) * 2019-04-29 2019-07-05 中南大学 A kind of water system Zinc ion battery colloidal electrolyte and its preparation method and application
CN110994046A (en) * 2019-12-04 2020-04-10 中南大学 Mixed electrolyte of water-based ion battery
CN112927949A (en) * 2019-12-06 2021-06-08 中国科学院大连化学物理研究所 Water system mixed electrolyte and application thereof in zinc ion mixed super capacitor

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Publication number Priority date Publication date Assignee Title
JP2002260737A (en) * 2001-03-01 2002-09-13 Denso Corp Gel electrolyte battery and manufacturing method
CN100456552C (en) * 2005-01-28 2009-01-28 株式会社Lg化学 Paste electrolyte and rechargeable lithium battery containing the same
KR100927246B1 (en) * 2006-09-11 2009-11-16 주식회사 엘지화학 Electrode mixture containing clay mineral and electrochemical cell using the same
CN113130984A (en) * 2019-12-31 2021-07-16 深圳新宙邦科技股份有限公司 Solid electrolyte and solid lithium ion battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1331847A (en) * 1998-12-22 2002-01-16 株式会社华仁电池 Solid electrolytes using aborbing agent and methods for preparing them
CN109980302A (en) * 2019-04-29 2019-07-05 中南大学 A kind of water system Zinc ion battery colloidal electrolyte and its preparation method and application
CN110994046A (en) * 2019-12-04 2020-04-10 中南大学 Mixed electrolyte of water-based ion battery
CN112927949A (en) * 2019-12-06 2021-06-08 中国科学院大连化学物理研究所 Water system mixed electrolyte and application thereof in zinc ion mixed super capacitor

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