CN107665987B - Battery using bromine-containing ionic liquid as positive electrode active material and assembling method thereof - Google Patents

Battery using bromine-containing ionic liquid as positive electrode active material and assembling method thereof Download PDF

Info

Publication number
CN107665987B
CN107665987B CN201610620673.6A CN201610620673A CN107665987B CN 107665987 B CN107665987 B CN 107665987B CN 201610620673 A CN201610620673 A CN 201610620673A CN 107665987 B CN107665987 B CN 107665987B
Authority
CN
China
Prior art keywords
ionic liquid
battery
bromine
positive electrode
negative electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610620673.6A
Other languages
Chinese (zh)
Other versions
CN107665987A (en
Inventor
唐怀远
王媛珍
王康彦
金源
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hengdian Group DMEGC Magnetics Co Ltd
Original Assignee
Hengdian Group DMEGC Magnetics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hengdian Group DMEGC Magnetics Co Ltd filed Critical Hengdian Group DMEGC Magnetics Co Ltd
Priority to CN201610620673.6A priority Critical patent/CN107665987B/en
Publication of CN107665987A publication Critical patent/CN107665987A/en
Application granted granted Critical
Publication of CN107665987B publication Critical patent/CN107665987B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Hybrid Cells (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a battery using bromine-containing ionic liquid as a positive active material and an assembly method thereof, wherein the battery comprises a positive electrode chamber and a negative electrode chamber which are separated by a cation exchange membrane; the electrolyte in the positive electrode chamber comprises bromine-containing ionic liquid, and the ionic liquid electrolyte is injected into the negative electrode chamber. The bromine-containing ionic liquid is obtained by reacting a bromine simple substance with an organic salt. The invention adopts the ionic liquid as the electrolyte, the bromine-containing ionic liquid as the anode active material, the aluminum or magnesium as the cathode, and the aluminum and magnesium electrodes have no passive film in the ionic liquid, thus having higher reversibility; the invention is a cheap, environment-friendly and high-energy-ratio battery system.

Description

Battery using bromine-containing ionic liquid as positive electrode active material and assembling method thereof
Technical Field
The invention relates to the field of secondary batteries, in particular to a battery and an assembly method thereof, and especially relates to a battery taking bromine-containing ionic liquid as a positive electrode active substance and an assembly method thereof.
Background
Lithium ion batteries have been considered as the most promising power batteries for electric vehicles; however, with the development of precious metals such as nickel, cobalt and lithium, the raw materials of lithium ion power batteries have greatly increased, and at present, the price of battery-grade lithium carbonate has increased by more than 4 times compared with the price of lithium carbonate in the end of 2014, which seriously restricts the popularization and application of new energy vehicles; the poor safety and the poor recovery economic benefit of the lithium ion power battery are also important factors restricting the development of the lithium ion power battery. Therefore, development and production of a secondary battery that is inexpensive, environmentally friendly, and has a high energy density have been receiving much attention.
Halogen and cheap metal aluminiumMagnesium is an element widely existing in the nature, and halogen and various metals can be respectively used as a positive electrode and a negative electrode to form a battery on the electrochemical principle; aluminum and magnesium theoretically have high capacities of 2980Ah/Kg and 2206Ah/Kg, respectively, as negative electrode materials, and have very low potentials (1.66V and 2.37V, respectively) compared to standard hydrogen electrodes, and cells based on halogen, aluminum and magnesium are very attractive. However, in a system with water, aluminum and magnesium have serious hydrogen evolution reaction as electrodes; in an organic system, aluminum and magnesium have thicker passive films, and Al3+、Mg2+The ions are slowly transferred into the electrolyte through the passivation film, so that the aluminum and magnesium electrodes show slow kinetics and inactivity, which limits their applications.
The invention adopts the ionic liquid as the electrolyte, the bromine-containing ionic liquid as the anode active material, the aluminum or magnesium as the cathode, and the aluminum and magnesium electrodes have no passive film in the ionic liquid, so the invention has higher reversibility, and is a battery system with low price, environmental protection and high energy ratio.
Disclosure of Invention
In view of this, the present invention provides a battery and an assembly method thereof, and particularly provides a battery using a bromine-containing ionic liquid as a positive active material and an assembly method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a battery comprising a positive compartment and a negative compartment separated by a cation exchange membrane; the electrolyte in the positive electrode chamber comprises bromine-containing ionic liquid, and the ionic liquid electrolyte is injected into the negative electrode chamber.
In the invention, a positive electrode and a negative electrode are separated by adopting a cation exchange membrane to form a positive electrode chamber and a negative electrode chamber, the positive electrode is inserted into the positive electrode chamber, and bromine-containing ionic liquid is injected into the positive electrode chamber to be used as a positive electrode active substance; and injecting the ionic liquid electrolyte into the negative electrode chamber, and immersing a metal Al or metal Mg sheet into the ionic liquid electrolyte to be used as a negative electrode to form a novel battery.
When the battery of the invention is discharged, the bromine of the positive electrode obtains electricityBromine is changed into bromide ions and enters the electrolyte; if the cathode adopts aluminum metal, the aluminum metal loses electrons and becomes aluminum ions, and the aluminum ions are combined with bromine ions in the electrolyte to form aluminum bromide which is dissolved in the electrolyte; similarly, if magnesium metal is used for the negative electrode, the chemical reaction is similar. In the charged state of the battery, the bromine is a liquid and can complex a large amount of Z-The anion, forming an ionic liquid, that is, the bromine-containing ionic liquid according to the present invention, at this time, the active material of the positive electrode (bromine-containing ionic liquid) migrates to the negative electrode and causes a discharge reaction with the metal of the negative electrode, and thus the migration of bromine must be prevented. The battery provided by the invention adopts a cation exchange membrane to prevent the bromine-containing ionic liquid from migrating to the negative electrode, thereby realizing the storage of electric energy.
The term "comprising" as used herein means that it may include other components in addition to the components described, which impart different characteristics to the battery. In addition, the term "comprising" as used herein may be replaced by "being" or "consisting of … …" as closed.
According to the invention, the bromine-containing ionic liquid is obtained by reacting elemental bromine (bromine) with an organic salt.
The bromine-containing ionic liquid provided by the invention is used as a novel chemical system and exists in the positive active material of the battery in the form of liquid. The bromine-containing ionic liquid is added into the positive active material, so that the prepared secondary battery has higher specific energy, rapid charge and discharge are realized, the cycle life is prolonged, and the cost of raw materials is low.
According to the invention, the organic salt has the general formula [ X ]]+Z-(ii) a Wherein, [ X ]]+Represents an organic cation, Z-Represents an anion.
The organic salt is composed of organic cations with larger volume and anions with smaller volume, and the substance has a plurality of unique properties, such as stable physicochemical properties, extremely low vapor pressure and difficult volatilization, good solubility to both organic and inorganic substances, controllable polarity and the like.
In the present invention, the organic cation may be any one of imidazolium ion, pyridinium ion, pyrrolium ion, piperidinium ion, morpholinium ion, quaternary ammonium ion or quaternary phosphonium ion or a combination of at least two thereof, for example, may be any one of imidazolium ion, pyridinium ion, pyrrolium ion, piperidinium ion, morpholinium ion, quaternary ammonium ion or quaternary phosphonium ion, and a typical but non-limiting combination is: imidazolium ions and pyridinium ions; pyridinium ions and pyrrolium ions; morpholinium ions, quaternary ammonium ions, quaternary phosphonium ions and the like.
According to the invention, the organic cation is preferably a quaternary ammonium ion, which has the following advantages over other organic cations: the quaternary ammonium salt (organic salt containing quaternary ammonium salt ions) is a common chemical, and the production process is mature, the price is low, and the quaternary ammonium salt can be purchased and used in a large scale.
In the present invention, the anion may adopt F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3SO2)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -Any one or a combination of at least two of them, for example, may be F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3S02)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -A typical but non-limiting combination of any of: f-And Cl-；Br-And I-；I-And PF6 -；Cl-、Br-And SCN-And the like.
Illustratively, the organic salt in the present invention may be: 1-butyl-3-methylimidazolium hexafluorophosphate ([ C)4-min]PF4) 1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride, 2-chloro-1, 3-dimethylimidazolium hexafluorophosphate, 1-N-butyl-3-methylimidazolium hexafluorophosphate, 1-methyl-3-propylimidazolium iodide, cetylpyridinium chloride, pyridinium tribromide, N-allyl-2-alkylpyridinium chloride, 1-butyl-1-methylpiperidinium bromide, chlorodipiperidinium hexafluorophosphate, cetyltrimethylammonium chloride, tetramethylammonium chloride, ethyltriphenylphosphonium bromide, hexadecyltributylphosphonium bromide, and the like.
Illustratively, the bromine-containing ionic liquid in the present invention may be any one of tetraethyl poly ammonium halide, tetrabutyl poly ammonium halide, 1-ethyl-3-methyl-polyhaloimidazole, phenyltrimethyl poly ammonium halide, benzyltriethyl poly ammonium halide, benzyltrimethyl poly ammonium halide, dodecyltrimethyl poly ammonium halide or a combination of at least two thereof.
According to the invention, the positive electrode is inserted into the positive electrode chamber of the battery, and the positive electrode is preferably a carbon electrode.
The carbon material used in the carbon electrode in the present invention is any one or a combination of at least two of carbon nanotube, carbon quantum dot, graphite, expanded graphite, graphene, carbon black, or nano carbon powder, for example, any one of carbon nanotube, carbon quantum dot, graphite, expanded graphite, graphene, carbon black, or nano carbon powder, and a typical but non-limiting combination is: carbon nanotubes and carbon quantum dots; carbon quantum dots and graphite; expanded graphite and graphene; graphite and carbon black; carbon quantum dots, graphite, and carbon black; graphite, carbon black and nano carbon powder, expanded graphite and carbon black, carbon nano tube and graphene and carbon black and the like.
According to the present invention, the negative electrode is inserted into the negative electrode chamber, and the negative electrode is made of any one of magnesium and aluminum, thereby forming an aluminum secondary battery or a magnesium secondary battery.
According to the present invention, the membrane used for separating the positive electrode compartment and the negative electrode compartment is a cation exchange membrane, and the "cation exchange membrane" in the present invention means a membrane that allows cations, not anions, to pass therethrough. Cation exchange membranes are known to those skilled in the art, and such membranes are selected based on the environment of use and operating conditions. Exemplary cation exchange membranes are: any one of a Nafion membrane, a Selemion membrane, and a Daramic membrane can be used as a battery separator.
The reason why the cation exchange membrane is used in the present invention is that: when the battery discharges, the bromine at the positive electrode obtains electrons, and the bromine is changed into bromide ions to enter the electrolyte; if the cathode adopts aluminum metal, the aluminum metal loses electrons and becomes aluminum ions, and the aluminum ions are combined with bromine ions in the electrolyte to form aluminum bromide which is dissolved in the electrolyte; similarly, if magnesium metal is used for the negative electrode, the chemical reaction is similar; in the charged state of the battery, the bromine is a liquid and can complex a large amount of Z-And (2) anions form ionic liquid, namely the bromine-containing ionic liquid, at this time, an active material (the bromine-containing ionic liquid) of the positive electrode can migrate to the negative electrode and generate a discharge reaction with metal of the negative electrode, so that the battery provided by the invention adopts a cation exchange membrane to prevent the bromine-containing ionic liquid from migrating to the negative electrode, and thus, the electric energy storage is realized.
According to the invention, the ionic liquid electrolyte in the negative electrode chamber is prepared by anhydrous aluminum halide and the general formula [ X]+Z-The chemical reaction of the organic salt of (1) can be expressed by the following equation:
AlT3+[X]+Z-→[X]+[AlT3Z]-
wherein the anhydrous aluminum halide has a general formula of AlT3Wherein T represents any one or a combination of at least two of F, Cl, Br or I, which may be, for example, any one of F, Cl, Br or I, with a typical but non-limiting combination being: f and Cl, Cl and Br, Br and I, F, Cl and Br.
Illustratively, the anhydrous aluminum halide isAlBr3、AlCl3、AlI3、AlF3、AlClBr2、AlCl2Br、AlClI2、AlICl2、AlIBr2、AlI2Br、AlFBr2、AlF2Br、AlFCl2、AlF2Cl、AlFI2Or AlF2Any one or a combination of at least two of I, for example, AlBr3、AlCl3、AlI3、AlF3、AlClBr2、AlCl2Br、AlClI2、AlICl2、AlIBr2、AlI2Br、AlFBr2、AlF2Br、AlFCl2、AlF2Cl、AlFI2Or AlF2Any one of, typically but not limited to, combinations of I: AlBr3And AlCl3，AlI3And AlF3，AlFBr2、AlF2Br and AlFCl2，AlICl2And AlIBr2，AlI2Br and AlFBr2，AlF2Cl、AlFI2And AlF2I。
According to the invention, the organic salt which is reacted with the anhydrous aluminum halide has the general formula [ X]+Z-Wherein [ X ]]+Represents an organic cation, Z-Represents an anion.
In the present invention, the organic cation is any one or a combination of at least two of imidazolium ion, pyridinium ion, pyrrolium ion, piperidinium ion, morpholinium ion, quaternary ammonium salt ion, and quaternary phosphonium salt ion, and is preferably a quaternary ammonium salt ion.
In the present invention, the anion is F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3SO2)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -Any one or a combination of at least two of them.
The electrochemical principle of the invention is based on the oxidation-reduction reaction of bromine and aluminum or magnesium, wherein the chemical equation of the oxidation-reduction reaction of bromine and aluminum is as follows:
3Br2+2Al+2[X]+[AlT3Z]-＝2[X]+[Al2Br3T3Z]-
during discharging, the bromine at the positive electrode obtains electrons, and the bromine is changed into bromide ions to enter the electrolyte; the aluminum metal of the cathode loses electrons and becomes aluminum ions, and the aluminum ions are combined with bromine ions in the electrolyte to form aluminum bromide which is dissolved in the electrolyte. In the charged state of the battery, the bromine is a liquid at normal temperature and can complex a large amount of Z-The anion, forming an ionic liquid, that is, the bromine-containing ionic liquid according to the present invention, at this time, the active material of the positive electrode (bromine-containing ionic liquid) migrates to the negative electrode and causes a discharge reaction with aluminum of the negative electrode, and thus the migration of bromine must be prevented. Therefore, the battery designed by the invention needs to adopt a cation exchange membrane to prevent the bromine-containing ionic liquid from migrating to the negative electrode, which is the most basic condition for realizing the storage of electric energy, therefore, the diaphragm adopted by the invention is a cation exchange membrane, and the cation exchange membrane can be a commercial proton exchange membrane and mainly comprises a Nafion membrane, a Selemion membrane and a Daramic membrane.
In a second aspect, the present invention also provides a method of assembling a battery according to the first aspect, comprising the steps of:
(1) placing the anode, the bromine-containing ionic liquid and the ionic liquid electrolyte in a glove box filled with argon;
(2) laminating and assembling by using a cation exchange membrane and a sealing ring;
(3) and inserting the positive electrode into the positive electrode chamber, injecting bromine-containing ionic liquid into the positive electrode chamber, injecting ionic liquid electrolyte into the negative electrode chamber, immersing the metal negative electrode into the ionic liquid electrolyte, and then sealing, cleaning and forming to obtain the battery.
The present invention is not particularly limited to the method for assembling a battery, and the battery may be assembled by the following method in addition to the above-described method for assembling:
first, a positive electrode active material layer containing a bromine-containing ionic liquid as a positive electrode active material is formed on one surface of a positive electrode current collector by using a coating method or the like to form a positive electrode, and subsequently, a negative electrode active material layer containing a negative electrode active material is formed on one surface of a negative electrode current collector by using a coating method or the like to form a negative electrode; subsequently, the positive electrode is accommodated in the exterior can and the negative electrode is accommodated in the exterior cap, and finally, the exterior can and the exterior cap are swaged using the cation exchange membrane impregnated with the ionic liquid electrolyte and the gasket, whereby the assembly of the secondary battery is completed.
The battery of the present invention may be formed in any shape such as a cylindrical shape, a coin shape, a rectangular shape, and others, and the basic configuration of the battery is not dependent on the shape but the same, and the design may be changed according to the purpose.
The battery of the present invention is, for example, a cylindrical type, and is obtained by coating a negative electrode active material on a negative electrode current collector to form a negative electrode, coating a positive electrode active material on a positive electrode current collector to form a positive electrode, winding a cation exchange membrane between the negative electrode and the positive electrode, housing the wound body in a battery case, injecting an ionic liquid containing bromine into a battery positive electrode chamber, injecting an ionic liquid electrolyte into a battery negative electrode chamber, and sealing the battery in a state in which an insulating plate is interposed therebetween.
When a coin-type battery is used, a disk-shaped negative electrode, a cation exchange membrane, a disk-shaped positive electrode, and a stainless steel plate are stacked and housed in a coin-type battery case, and an ionic liquid containing bromine is injected into a battery positive electrode chamber, and an ionic liquid electrolyte is injected into a battery negative electrode chamber and sealed.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention adopts ionic liquid as electrolyte, bromine-containing ionic liquid as anode active material, aluminum or magnesium as cathode, and aluminum and magnesium electrodes have no passive film in the ionic liquid, thus having higher reversibility.
Drawings
Fig. 1 is a schematic view of the structure of a battery of the present invention.
In the figure: 1-ionic liquid containing bromine, 2-carbon electrode, 3-cation exchange membrane, 4-metal cathode, and 5-ionic liquid electrolyte.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The composition and assembly of the cells of the invention were achieved on a laboratory scale using the following general methods:
the battery comprises the following components:
as shown in fig. 1, the battery of the present invention comprises a positive electrode compartment and a negative electrode compartment separated by a cation exchange membrane 3; the electrolyte in the positive electrode chamber comprises ionic liquid 1 containing bromine, and the electrolyte in the negative electrode chamber comprises ionic liquid electrolyte 5; the positive electrode chamber is inserted with a carbon electrode 2 as a positive electrode, and the negative electrode chamber is inserted with a metal negative electrode 4. The positive and negative electrodes are separated by the cation exchange membrane, and the bromine-containing ionic liquid 1 is injected into the positive electrode chamber to be used as a positive electrode active substance; and the ionic liquid electrolyte 5 is injected into the negative electrode chamber, and the metal negative electrode comprising an Al or Mg sheet is immersed into the ionic liquid electrolyte to serve as a negative electrode, so that the battery is formed.
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A battery comprising a positive compartment and a negative compartment separated by a Nafion membrane; the electrolyte in the positive electrode chamber comprises tetraethylammonium tribromide, and the ionic liquid electrolyte is injected into the negative electrode chamber; the positive electrode chamber is inserted with a carbon nano tube positive electrode, and the negative electrode chamber is immersed with an aluminum negative electrode.
Wherein the ionic liquid electrolyte is prepared by mixing anhydrous aluminum chloride and 1-ethyl-3 methyl-imidazole chloride salt according to the molar ratio of 2:1 for reaction.
The battery assembling method specifically comprises the following steps:
(1) placing a carbon nano tube anode, tetraethylammonium tribromide and an ionic liquid electrolyte in a glove box filled with argon;
(2) laminating and assembling by using a Nafion film and a sealing ring;
(3) inserting the positive electrode of the carbon nano tube into the positive electrode chamber, and injecting tetraethyl ammonium tribromide into the positive electrode chamber of the battery; and injecting the ionic liquid electrolyte into a battery negative electrode chamber, immersing the aluminum negative electrode into the ionic liquid electrolyte, and then sealing, forming and cleaning to obtain the battery.
Example 2
Compared with example 1, Selemion membrane was used instead of Nafion membrane, and the rest was the same as example 1.
Example 3
Compared with example 1, Daramic membrane was used instead of Nafion membrane, and the rest was the same as example 1.
Example 4
Graphite was used as a positive electrode as compared with example 1, and the other steps were the same as in example 1.
Example 5
A battery comprising a positive chamber and a negative chamber separated by a Selemion membrane; electrolyte in the positive electrode chamber comprises 1-ethyl-3-methylimidazolium dibromoiodide salt, and ionic liquid electrolyte is injected into the negative electrode chamber; the positive electrode chamber is inserted with a carbon nano tube positive electrode, and the negative electrode chamber is immersed with a magnesium negative electrode.
Wherein the ionic liquid electrolyte is prepared by mixing anhydrous aluminum chloride and 1-propyl-3-methylimidazole chloride according to the molar ratio of 1.5:1 for reaction.
The battery assembling method specifically comprises the following steps:
(1) placing a graphite positive electrode, 1-ethyl-3-methylimidazole dibromo-iodide salt and an ionic liquid electrolyte in a glove box filled with argon;
(2) using a Selemion film and a sealing ring for lamination and assembly;
(3) inserting a graphite positive electrode into a positive electrode chamber, injecting 1-ethyl-3-methylimidazol dibromoiodide into the positive electrode chamber of the battery, injecting an ionic liquid electrolyte into a negative electrode chamber of the battery, immersing a magnesium negative electrode into the ionic liquid electrolyte, and then sealing, forming and cleaning to obtain the battery.
According to the invention, the ionic liquid is used as the electrolyte, the bromine-containing ionic liquid is used as the positive active material, the aluminum or magnesium is used as the negative electrode, and the aluminum and magnesium electrodes have no passivation film in the ionic liquid, so that the reversibility is high; the invention is a cheap, environment-friendly and high-energy-ratio battery system.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (9)

1. A battery comprising a positive compartment and a negative compartment separated by a cation exchange membrane;
the electrolyte in the positive electrode chamber is bromine-containing ionic liquid, and the ionic liquid electrolyte is injected into the negative electrode chamber;
the bromine-containing ionic liquid is obtained by reacting a bromine simple substance with an organic salt;
a positive electrode is inserted into the positive electrode chamber; the positive electrode is a carbon electrode;
a negative electrode is inserted into the negative electrode chamber; the negative electrode is any one of magnesium or aluminum;
the ionic liquid electrolyte is obtained by reacting anhydrous aluminum halide with organic salt.
2. The battery of claim 1, wherein the organic salt has the formula [ X [ ]]+Z-(ii) a Wherein, [ X ]]+Represents an organic cation, Z-Represents an anion.
3. The battery of claim 2, wherein the organic cation is any one of imidazolium, pyridinium, pyrrolidinium, piperidinium, morpholinium, quaternary ammonium, or quaternary phosphonium ions or a combination of at least two thereof.
4. The battery of claim 3, wherein the organic cation is a quaternary ammonium ion.
5. The battery of claim 2, wherein the anion is F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3SO2)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -Any one or a combination of at least two of them.
6. The cell of claim 1 wherein the cation exchange membrane is any one of a Nafion membrane, a Selemion membrane or a Daramic membrane.
7. The battery of claim 1 wherein the anhydrous aluminum halide has the formula AlT3Wherein T represents any one or a combination of at least two of F, Cl, Br or I.
8. The cell of claim 7, wherein the anhydrous aluminum halide is AlBr3、AlCl3、AlI3、AlF3、AlClBr2、AlCl2Br、AlClI2、AlICl2、AlIBr2、AlI2Br、AlFBr2、AlF2Br、AlFCl2、AlF2Cl、AlFI2Or AlF2Any one of or a combination of at least two of I.
9. The method of assembling a battery according to any one of claims 1 to 8, comprising the steps of:
(1) placing the anode, the bromine-containing ionic liquid and the ionic liquid electrolyte in a glove box filled with argon;
(2) laminating and assembling by using a cation exchange membrane and a sealing ring;
(3) inserting the positive electrode into a positive electrode chamber, and injecting bromine-containing ionic liquid into the positive electrode chamber; and injecting the ionic liquid electrolyte into the negative electrode chamber, immersing the metal negative electrode into the ionic liquid electrolyte, and then sealing, forming and cleaning to obtain the battery.
CN201610620673.6A 2016-07-29 2016-07-29 Battery using bromine-containing ionic liquid as positive electrode active material and assembling method thereof Active CN107665987B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610620673.6A CN107665987B (en) 2016-07-29 2016-07-29 Battery using bromine-containing ionic liquid as positive electrode active material and assembling method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610620673.6A CN107665987B (en) 2016-07-29 2016-07-29 Battery using bromine-containing ionic liquid as positive electrode active material and assembling method thereof

Publications (2)

Publication Number Publication Date
CN107665987A CN107665987A (en) 2018-02-06
CN107665987B true CN107665987B (en) 2020-03-27

Family

ID=61122101

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610620673.6A Active CN107665987B (en) 2016-07-29 2016-07-29 Battery using bromine-containing ionic liquid as positive electrode active material and assembling method thereof

Country Status (1)

Country Link
CN (1) CN107665987B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104078705A (en) * 2014-07-03 2014-10-01 南京中储新能源有限公司 Secondary aluminium cell and electrolyte thereof
CN104091966A (en) * 2014-07-08 2014-10-08 南京中储新能源有限公司 Aluminum-containing electrolyte and secondary aluminium battery using same
JP2014222609A (en) * 2013-05-13 2014-11-27 学校法人 関西大学 Aluminum secondary battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014222609A (en) * 2013-05-13 2014-11-27 学校法人 関西大学 Aluminum secondary battery
CN104078705A (en) * 2014-07-03 2014-10-01 南京中储新能源有限公司 Secondary aluminium cell and electrolyte thereof
CN104091966A (en) * 2014-07-08 2014-10-08 南京中储新能源有限公司 Aluminum-containing electrolyte and secondary aluminium battery using same

Also Published As

Publication number Publication date
CN107665987A (en) 2018-02-06

Similar Documents

Publication Publication Date Title
Chao et al. Toward high-voltage aqueous batteries: super-or low-concentrated electrolyte?
KR101503879B1 (en) Magnesium hybrid battery and its fabrication method
Yun et al. Materials and device constructions for aqueous lithium–sulfur batteries
US9941559B2 (en) Water enhanced ionic liquid electrolytes for metal-air batteries
JP5449522B2 (en) Air battery
CN106025249B (en) A kind of room temperature liquid metal battery
CN109314240B (en) Aqueous secondary battery
Dai et al. The emerging of aqueous zinc‐based dual electrolytic batteries
US9666916B2 (en) Biphase electrolyte for a metal-air battery
CN105098291A (en) Liquid metal-gas battery and preparation method thereof
WO2023044969A1 (en) Zinc-based electrochemical energy storage device
US3625764A (en) Electrode for electric storage batteries containing zinc halide in aqueous solution, of the type having a soluble cathode and a dissolved anode
CN105745727A (en) Capacitor and method for manufacturing same
CN105284000A (en) Molten salt battery
Yu et al. A mediator-ion nitrobenzene-iodine nonaqueous redox flow battery with asymmetric solvents
JP5763161B2 (en) Air battery
US20160156063A1 (en) In-situ magnesium-metal generated rechargeable magnesium battery
JP2018028966A (en) Nonaqueous electrolyte solution and power storage device using the same
CN107665987B (en) Battery using bromine-containing ionic liquid as positive electrode active material and assembling method thereof
CN107665981B (en) It is a kind of using the ionic liquid containing chlorine as the battery of positive active material and its assemble method
JP5617131B2 (en) Electrolyte for magnesium secondary battery, magnesium secondary battery and method for producing electrolyte
Yu et al. A unique single‐ion mediation approach for crossover‐free nonaqueous redox flow batteries with a Na+‐ion solid electrolyte
CN107799759B (en) Iodide square battery and assembling method thereof
CN107666016B (en) It is a kind of using the ionic liquid containing iodine as the battery of positive active material and its assemble method
JP6875818B2 (en) Electrolyte and electrochemical device using it

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant