CN104282952B - Electrolyte and battery - Google Patents

Electrolyte and battery Download PDF

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CN104282952B
CN104282952B CN201310717178.3A CN201310717178A CN104282952B CN 104282952 B CN104282952 B CN 104282952B CN 201310717178 A CN201310717178 A CN 201310717178A CN 104282952 B CN104282952 B CN 104282952B
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electrolyte
ions
negative electrode
battery
metal
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CN104282952A (en
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刘洋
陈璞
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Ruihai Po Qingdao Energy Technology Co ltd
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Positec Power Tools Suzhou Co Ltd
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Priority to CN201310717178.3A priority Critical patent/CN104282952B/en
Application filed by Positec Power Tools Suzhou Co Ltd filed Critical Positec Power Tools Suzhou Co Ltd
Priority to EP20191208.6A priority patent/EP3758126A1/en
Priority to PCT/CN2014/081029 priority patent/WO2014206352A1/en
Priority to EP18207997.0A priority patent/EP3486992B1/en
Priority to EP14816857.8A priority patent/EP3016199B1/en
Publication of CN104282952A publication Critical patent/CN104282952A/en
Priority to US14/980,257 priority patent/US9812738B2/en
Priority to US15/783,460 priority patent/US10418666B2/en
Priority to US16/534,555 priority patent/US10854928B2/en
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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
    • H01M10/05—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
    • 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
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/056—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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M2300/0025—Organic electrolyte
    • 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 Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to the field of batteries, and particularly discloses an electrolyte. The electrolyte solution includes at least one solvent capable of dissolving the electrolyte and ionizing the electrolyte; the electrolyte comprises first metal ions which can be reversibly extracted from and embedded into the positive electrode in the charging and discharging process and second metal ions which can be reduced and deposited into second metal in the negative electrode in the charging process; the second metal is reversibly oxidized and dissolved into second metal ions in the discharging process; the anion in the electrolyte comprises an alkyl sulfonate ion. The invention also discloses a battery, which comprises a positive electrode containing the positive active material capable of reversibly releasing and embedding the first metal ions, a negative electrode containing a carrier for charging and discharging the negative electrode, and the electrolyte. The electrolyte can effectively improve the solubility of the first metal ions and the second metal ions, inhibit the generation of gas and reduce the self-discharge of the battery; and the coating does not freeze at the temperature of minus 20 ℃, and has good low-temperature performance.

Description

Electrolyte and battery
Technical Field
The invention belongs to the field of batteries, and particularly relates to an electrolyte and a battery.
Background
Lead-acid batteries, which have been available for over a hundred years, have mature battery technology and occupy an absolute market share in the energy storage fields of automobile starting batteries, electric bicycles, UPSs and the like. The lead-acid battery has the advantages of low price and high cost performance although the cycle service life is short and the energy density is relatively low. Therefore, in recent years, nickel-metal hydride batteries, lithium ion batteries, sodium-sulfur batteries, and the like cannot replace lead-acid batteries in the field of energy storage.
An ion exchange battery has newly emerged. The working principle of the ion exchange battery is that the anode is based on the extraction-insertion reaction of first metal ions, the cathode is based on the deposition-dissolution reaction of second metal ions, and the electrolyte contains the first metal ions participating in the extraction-insertion reaction of the anode and the second metal ions participating in the deposition-dissolution reaction of the cathode. The theoretical energy density of the battery is 160Wh/Kg, and the actual energy density can reach 50-80 Wh/Kg. In summary, this type of battery is very promising as a next generation energy storage battery to replace lead-acid batteries, and has great commercial value.
However, at present, the electrolyte of the battery mostly adopts acetate, hydrochloride, sulfate and the like, and the acetate is poor in stability and is easy to oxidize to generate larger self-discharge; the hydrochloride corrodes the current collector of the positive electrode, the sulfate corrodes better comprehensive performance, but the corrosion to the negative electrode is still larger.
Disclosure of Invention
The invention aims to solve the technical problem of providing the electrolyte of the battery, which has good chemical stability and can inhibit the corrosion of the battery.
The present invention provides an electrolyte for a battery, the electrolyte comprising at least one solvent capable of dissolving an electrolyte and ionizing the electrolyte; the electrolyte comprises first metal ions which can be reversibly extracted from and embedded into the positive electrode in the charging and discharging process and second metal ions which can be reduced and deposited into second metal in the negative electrode in the charging process; the second metal is reversibly oxidized and dissolved into second metal ions in the discharging process; the anion in the electrolyte comprises an alkyl sulfonate ion.
Preferably, the alkyl sulfonate ion is a methyl sulfonate ion.
Preferably, the concentration of the alkyl sulfonate ions is 0.5-12 mol/L.
Preferably, the concentration of the first metal ions is 1-7 mol/L, and the concentration of the second metal ions is 1-4 mol/L.
Preferably, the first metal ions are lithium ions and the second metal ions are zinc ions.
Preferably, the solvent is water or alcohol.
Preferably, the electrolyte further comprises an electrolyte additive comprising a bismuth compound.
Preferably, the bismuth compound is bismuth trioxide or bismuth nitrate.
Preferably, the bismuth compound accounts for 0.1-5% of the total weight of the electrolyte.
Preferably, the electrolyte further comprises one or more of sulfate ions, chloride ions, acetate ions and nitrate ions.
More preferably, the molar ratio of the sulfate ions to the alkyl sulfonate ions is 1:21 to 27: 7.
Preferably, the pH value of the electrolyte is 3-7.
The invention also provides a battery, which comprises a positive electrode, a negative electrode and electrolyte; the positive electrode comprises a positive active material capable of reversibly deintercalating and intercalating first metal ions; the negative electrode comprises a carrier for charging and discharging the negative electrode; the electrolyte is the electrolyte provided by the invention.
Preferably, the negative electrode includes a negative electrode additive including a bismuth compound.
Preferably, the bismuth compound is bismuth trioxide or bismuth nitrate.
Preferably, the bismuth compound accounts for 0.1-10% of the total weight of the negative electrode.
Compared with the prior art, the electrolyte is not easy to oxidize and has good chemical stability; the solubility of the first metal ions and the solubility of the second metal ions can be effectively improved; inhibiting the generation of gas and reducing the corrosion of the battery; reducing self-discharge of the battery; and the coating does not freeze at the temperature of minus 20 ℃, and has good low-temperature performance.
Drawings
FIG. 1 is a graph comparing the gas generation of example 1 of the present invention with that of comparative example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
An electrolyte for a battery, the electrolyte comprising at least one solvent capable of dissolving an electrolyte and ionizing the electrolyte; the electrolyte comprises first metal ions which can be reversibly extracted from and embedded into the positive electrode in the charging and discharging process and second metal ions which can be reduced and deposited into second metal in the negative electrode in the charging process; the second metal is reversibly oxidized and dissolved into second metal ions in the discharging process; the anion in the electrolyte comprises an alkyl sulfonate ion.
The purpose of the solvent in the electrolyte solution of the present invention is to dissolve the electrolyte and ionize the electrolyte in the solvent, thereby finally generating cations and anions in the electrolyte solution, which can move freely.
The solvent of the present invention is preferably water and/or an alcohol. Wherein the alcohol includes, but is not limited to, methanol or ethanol.
The first metal ions in the electrolyte can be reversibly extracted from and embedded into the positive electrode in the charge and discharge processes. Namely, when the battery is discharged, the first metal ions in the electrolyte are embedded into the positive electrode active material; when the battery is charged, the first metal ions are extracted from the positive electrode active material and enter the electrolyte.
Preferably, the first metal ions of the present invention are selected from lithium ions or sodium ions, more preferably lithium ions.
The second metal ions in the electrolyte can be reduced and deposited into the second metal at the negative electrode in the charging process, and the second metal can be reversibly oxidized and dissolved into the second metal ions in the discharging process. Namely, when the battery is charged, the second metal ions in the electrolyte are reduced into the second metal and are deposited on the negative electrode; when the battery discharges, the second metal is oxidized into second metal ions which are dissolved from the negative electrode and enter the electrolyte.
Preferably, the second metal ion is selected from manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin ion or lead ion; more preferably zinc ions.
In a preferred embodiment, the first metal ions are selected from lithium ions, while the second metal ions are selected from zinc ions, i.e. the cations in the electrolyte are lithium and zinc ions.
Wherein the anion in the electrolyte comprises an alkyl sulfonate ion.
Alkyl sulfonate ions include, but are not limited to, aliphatic sulfonate ions and are not limited to having functional groups or substituents on the aliphatic group. Preferably according to the following general formula:
R-SO3 -or Y-R' -SO3 -
In the above formula, Y represents a substituent such as-F, -OH, etc.
In the above formula, R may be a branched or unbranched aliphatic group; it may be an aliphatic group of 1 to 12 carbon atoms, preferably an aliphatic group of 1 to 6 carbon atoms, particularly preferably a methyl group, an ethyl group and an n-propyl group.
In the above formula, R' may be a branched or unbranched aliphatic group; can be an aliphatic group having 2 to 12 carbon atoms, preferably an aliphatic group having 2 to 6 carbon atoms, more preferably an unbranched aliphatic group having 2 to 6 carbon atoms; more preferably, the substituent is not attached to the same carbon atom as the sulfonic acid group.
Particularly preferably, the alkylsulfonate ion is a methylsulfonate ion, i.e., R is methyl.
The methyl sulfonate ions are adopted in the electrolyte, so that the solubility of the first metal ions and the solubility of the second metal ions can be further enhanced, and the cost is lower than that of other alkyl sulfonates.
Preferably, the anions in the electrolyte contain only alkyl sulfonate ions and no other anions. I.e., the electrolyte is composed entirely of alkyl sulfonate. Thus, the low-temperature performance of the electrolyte is more excellent, and the concentration of the first metal ions and the second metal ions in the electrolyte is higher.
More preferably, the electrolyte is zinc and lithium alkyl sulfonates.
Of course, the anion in the electrolyte may contain other anions in addition to the alkylsulfonate ion. The other anion may be any anion that does not substantially affect the positive-negative reactions, and the dissolution of the electrolyte in the solvent. Examples of the ion include sulfate ion, chloride ion, nitrate ion, acetate ion, formate ion, phosphate ion, and a mixture thereof.
In a preferred embodiment, the electrolyte further comprises one or more of sulfate ions, chloride ions, acetate ions, and nitrate ions.
Particularly preferably, the molar ratio of the sulfate ions to the alkyl sulfonate ions is 1:21 to 27: 7.
More preferably, the anion in the electrolyte consists of an alkyl sulfonate ion and a sulfate ion.
The concentration of each ion in the electrolyte can be changed and adjusted according to different conditions such as different electrolytes, solvents, application fields of the battery and the like.
Preferably, the concentration of the first metal ions in the electrolyte is 1-7 mol/L.
Preferably, the concentration of the second metal ions in the electrolyte is 1-4 mol/L.
Preferably, the concentration of the alkyl sulfonate ion in the electrolyte is 0.5-12 mol/L.
In order to further improve the performance of the battery, the electrolyte preferably further includes an electrolyte additive.
In a preferred embodiment, the electrolyte additive is a bismuth compound.
The method for adding the bismuth compound into the electrolyte can select different adding modes according to different conditions of the electrolyte or the diaphragm. Methods of addition include, but are not limited to, direct addition to the electrolyte or dropwise addition to the separator as a suspension. More preferably, the bismuth compound is directly added to the electrolyte solution, and then the electrolyte solution is dropped onto the separator.
Preferably, the bismuth compound is selected from bismuth trioxide and/or bismuth nitrate.
The dosage of the bismuth compound used in the electrolyte is preferably as follows:
when the bismuth trioxide is used independently, the bismuth trioxide accounts for 0.01-5% of the total weight of the electrolyte.
When the bismuth nitrate is used independently, the bismuth nitrate accounts for 0.01-5% of the total weight of the electrolyte.
It is of course also possible to use mixtures of bismuth trioxide and bismuth nitrate.
In order to enhance certain performance (such as low-temperature performance, high-temperature performance, rate discharge performance, etc.) of the battery or adapt the battery to different use environments, the electrolyte of the present invention may further include other additives, such as a low-temperature additive, a high-temperature resistant additive, an overcharge additive, etc., according to different situations.
In order to optimize the performance of the battery, the pH value range of the electrolyte is preferably 3-7.
The pH value range of the electrolyte is 3-7, so that the concentration of second metal ions in the electrolyte can be effectively ensured, the capacity and the rate discharge performance of the battery are ensured, and the problem of proton co-embedding can be avoided.
The electrolyte contains alkyl sulfonate ions and has the following advantages: firstly, the alkyl sulfonate ions can effectively improve the solubility of the first metal ions (such as lithium ions) and the second metal ions (such as zinc ions) in the electrolyte, and the increase of the ion concentration in the electrolyte can effectively improve the high-rate charge and discharge performance of the battery. Second, the alkyl sulfonate ion can suppress the generation of gas. Thirdly, the alkyl sulfonate ions can also effectively reduce the self-discharge rate of the battery. The reason is that the alkyl sulfonate ions can increase the oxygen evolution overpotential of the electrolyte and lower the oxidation-reduction potential of the positive active material. Fourthly, compared with other anion salts, the electrolyte of the alkyl sulfonate ions is not frozen at the temperature of minus 20 ℃, so that the battery has better low-temperature performance.
The preparation method of the electrolyte can adopt different methods to prepare the electrolyte according to different actual conditions. Preferably, it is prepared in the following manner.
The method comprises the following steps: the alkyl sulfonate is directly dissolved in the solvent.
And weighing a certain amount of lithium methanesulfonate and zinc methanesulfonate according to the concentration of each ion in the electrolyte required to be prepared, dissolving in water, and stirring to completely dissolve the lithium methanesulfonate and the zinc methanesulfonate to prepare the electrolyte. In the generated electrolyte, the anion is methylsulfonate ion, and the cation is zinc ion and lithium ion.
The second method comprises the following steps: the metal is reacted with an alkyl sulfonic acid.
Weighing a certain amount of metal zinc, dissolving the metal zinc in methanesulfonic acid with a certain concentration, stirring until the metal zinc is completely dissolved, then adding lithium hydroxide, and stirring until the metal zinc is completely dissolved to prepare the electrolyte. The dosage of the methanesulfonic acid basically ensures complete reaction with the metallic zinc and the lithium hydroxide, so that the metallic zinc is converted into zinc ions to be present in the electrolyte, and the lithium hydroxide and the methanesulfonic acid are neutralized to generate the lithium methylsulfonate.
The third method comprises the following steps: the metal oxide is reacted with an alkyl sulfonic acid.
Weighing a certain amount of zinc oxide, dissolving the zinc oxide in methanesulfonic acid with a certain concentration, stirring until the zinc oxide is completely dissolved, then adding lithium hydroxide, and stirring until the lithium hydroxide is completely dissolved to prepare the electrolyte. Wherein the amount of methanesulfonic acid is substantially sufficient to completely react with zinc oxide and lithium hydroxide, such that the zinc oxide reacts with the methanesulfonic acid to form lithium methylsulfonate, and the lithium hydroxide neutralizes the methanesulfonic acid to form lithium methylsulfonate.
The method four comprises the following steps: the metal carbonate is reacted with an alkyl sulfonic acid.
Weighing a certain amount of zinc carbonate, dissolving the zinc carbonate in methanesulfonic acid with a certain concentration, stirring until the zinc carbonate is completely dissolved, then adding lithium hydroxide, and stirring until the lithium hydroxide is completely dissolved to prepare the electrolyte. The dosage of the methanesulfonic acid is basically ensured to be completely reacted with the zinc carbonate and the lithium hydroxide, so that the zinc carbonate and the methanesulfonic acid are reacted to generate lithium methylsulfonate, and the lithium hydroxide and the methanesulfonic acid are neutralized to generate the lithium methylsulfonate.
By applying the electrolyte, a battery can be prepared. The battery comprises a positive electrode, a negative electrode and electrolyte; the positive electrode comprises a positive active material capable of reversibly deintercalating and intercalating a first metal ion; the negative electrode comprises a carrier for charging and discharging the negative electrode; the electrolyte is provided by the invention.
The charge and discharge principle of the battery is as follows: during charging, the positive active material is separated from the first metal ions, and simultaneously, the positive active material is oxidized and emits electrons; the electrons reach the negative electrode of the battery through an external circuit, and meanwhile, the second metal ions in the electrolyte obtain electrons on the negative electrode, and the electrons are reduced into second metal to be deposited on the negative electrode. During discharging, the second metal deposited on the cathode is oxidized, loses electrons and is converted into second metal ions to enter the electrolyte; the electrons reach the positive electrode through an external circuit, the positive electrode active material receives the electrons and is reduced, and the first metal ions are embedded into the positive electrode active material.
Wherein, the positive active substance in the positive electrode participates in the positive reaction and can reversibly remove and embed the first metal ions.
Preferably, the positive electrode active material is capable of reversibly deintercalating and intercalating lithium ions, or sodium ions.
The positive electrode active material may be a material conforming to the general formula Li1+xMnyMzOkThe spinel-structured compound capable of reversibly deintercalating and intercalating lithium ions, wherein x is more than or equal to-1 and less than or equal to 0.5, y is more than or equal to 1 and less than or equal to 2.5, z is more than or equal to 0 and less than or equal to 0.5, k is more than or equal to 3 and less than or equal to 6, and M is selected from at least one of Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si and Al. Preferably, the positive electrode active material contains LiMn2O4. More preferably, the positive electrode active material contains doped or coating-modified LiMn2O4。
The positive electrode active material may be a material conforming to the general formula Li1+xMyM′zM″cO2+nA compound having a layered structure capable of reversibly deintercalating-intercalating lithium ions, wherein-1<x is less than or equal to 0.5, y is less than or equal to 0 and less than or equal to 1, z is less than or equal to 0 and less than or equal to 1, c is less than or equal to 0 and less than or equal to 1, n is less than or equal to 0.2 and less than or equal to 0.2, and M, M 'and M' are respectively selected from at least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al. Preferably, the positive electrode active material contains LiCoO2。
The positive electrode active material may also be a compound of formula LixM1-yM′y(XO4)nWherein 0 is 0, is a compound of olivine structure capable of reversibly deintercalating-intercalating lithium ions<X is less than or equal to 2, y is less than or equal to 0 and less than or equal to 0.6, n is less than or equal to 1 and less than or equal to 1.5, M is selected from Fe, Mn, V or Co, M' is selected from at least one of Mg, Ti, Cr, V or Al, and X is selected from at least one of S, P or Si. Preferably, the positive electrode active material contains LiFePO4。
In the current battery industry, almost all positive active materials are subjected to modification treatment such as doping and coating. However, the chemical general expression of the material is complex caused by means of doping, coating modification and the likeHetero, e.g. LiMn2O4Cannot represent the general formula of the lithium manganate widely used at present, but is represented by the general formula Li1+xMnyMzOkFor example, various modified LiMn are widely included2O4A positive electrode active material. Likewise, LiFePO4And LiCoO2Are also to be understood broadly to include modifications by various doping, cladding, etc., of the general formula corresponding to Li, respectivelyxM1-yM′y(XO4)nAnd Li1+xMyM′zM″cO2+nThe positive electrode active material of (1).
When the positive electrode active material is a material capable of reversibly deintercalating and intercalating lithium ions, it is preferable to use, for example, LiMn2O4、LiFePO4、LiCoO2、LiMxPO4、LiMxSiOy(wherein M is a variable valence metal). In addition, when the positive electrode active material is a material capable of reversibly deintercalating and intercalating sodium ions, it is preferable to use NaVPO4F, and the like.
The anode also comprises an anode current collector for loading the anode active substance, and the material of the anode current collector is selected from one of carbon-based materials, metals or alloys.
The positive current collector is only used as a carrier for electron conduction and collection and does not participate in electrochemical reaction, namely, the positive current collector can stably exist in electrolyte within the working voltage range of the battery without side reaction basically, so that the battery is ensured to have stable cycle performance.
Preferably, the anode current collector is passivated, and the main purpose of the passivation is to form a layer of passivated oxide film on the surface of the anode current collector, so that the passivation layer can play a role in stably collecting and conducting electrons in the charging and discharging processes of the battery, and cannot participate in the battery reaction, thereby ensuring the stable performance of the battery. The passivation treatment method of the positive electrode current collector comprises chemical passivation treatment or electrochemical passivation treatment.
The chemical passivation treatment comprises oxidizing the positive current collector by an oxidant to form a passivation film on the surface of the positive current collector. The principle of choice of the oxidizing agent is oxygenThe agent can form a layer of passive film on the surface of the positive current collector without dissolving the positive current collector. The oxidant is selected from, but not limited to, concentrated nitric acid or ceric sulfate (Ce (SO)4)2)。
Specifically, the chemical passivation treatment steps are as follows: and (3) placing the positive current collector into an oxidant solution, maintaining for 0.5-1 hour to form a passivation film on the surface of the positive current collector, and finally taking out the positive current collector, cleaning and drying.
The electrochemical passivation treatment comprises the steps of carrying out electrochemical oxidation on the positive current collector or carrying out charge and discharge treatment on the battery containing the positive current collector, so that a passivation film is formed on the surface of the positive current collector.
In a preferred embodiment, the electrochemical oxidation of the positive current collector is performed directly, i.e. pre-passivation, before the positive current collector is used for battery assembly. Specifically, a positive current collector is used as a working electrode, a proper counter electrode and a proper reference electrode are selected to form a three-electrode system, and the positive current collector is oxidized; the applied voltage is 2.1-2.4V. The positive current collector may be a metal, such as metallic aluminum; the positive current collector may also be an alloy, such as stainless steel or an aluminum alloy. Of course, a two-electrode system using the positive current collector as the working electrode may be adopted to oxidize the positive current collector, and the applied voltage is 2.1-2.4V.
In a preferred embodiment, the battery containing the positive electrode current collector can be charged and discharged to passivate the positive electrode current collector, the voltage during charging is charged to 2.1-2.4V, the voltage during discharging is discharged to 1.35-1.45V, and the charging and discharging times are not less than 1.
In a specific embodiment, when the positive electrode is prepared, in addition to the positive electrode active material, a positive electrode conductive agent and a positive electrode binder may be added to improve the performance of the positive electrode according to actual conditions.
The positive electrode conductive agent is selected from one or more of conductive polymers, activated carbon, graphene, carbon black, graphite, carbon fibers, metal powder, and metal flakes.
The positive electrode binder may be selected from one of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimide, polyester, polyether, fluorinated polymer, polydivinyl polyethylene glycol, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, or a mixture and derivative of the above polymers. More preferably, the positive electrode binder is selected from Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), or Styrene Butadiene Rubber (SBR).
And in the negative electrode of the battery, the substance for generating electrochemical reaction is a second metal, the second metal can be oxidized and dissolved into a second metal ion, and the second metal ion can be reversibly reduced and deposited into the second metal.
Preferably, the negative electrode further comprises a negative electrode additive, wherein the negative electrode additive comprises a bismuth compound, and the way of adding the bismuth compound to the negative electrode is slightly different according to different conditions of the negative electrode. The method of addition may be selected from physical methods including but not limited to suspension coating, vacuum plating, magnetron sputtering; chemical methods include electrochemical plating and the like.
In the first preferred embodiment, the negative electrode includes only the negative electrode current collector, and the negative electrode current collector serves only as a carrier for electron conduction and collection, and does not participate in the electrochemical reaction. In this case, the negative electrode current collector is a carrier for charging and discharging the negative electrode.
In this embodiment, the bismuth compound is added to the negative electrode by a method including, but not limited to, adding the bismuth compound to a dispersant to prepare a dispersion, coating the dispersion on a negative electrode current collector, and finally removing the dispersant.
The material of the negative current collector is selected from at least one of metal Ni, Cu, Ag, Pb, Mn, Sn, Fe, Al or passivated metal, or simple substance silicon, or a carbon-based material, wherein the carbon-based material comprises a graphite material, such as commercial graphite pressed foil, and the weight ratio of graphite is 90-100%. The material of the negative electrode current collector may also be selected from stainless steel or passivated stainless steel. Stainless steel includes, but is not limited to, stainless steel mesh and stainless steel foil, and as such, stainless steel may be of the 300 series type, such as stainless steel 304 or stainless steel 316L.
The negative electrode current collector may be selected from metals containing a plating/coating layer having a high hydrogen evolution potential, thereby reducing the occurrence of negative electrode side reactions. The plating/coating is selected from at least one of simple substances, alloys or oxides containing C, Sn, In, Ag, Pb and Co. The thickness range of the plating/coating is 1-1000 nm. For example: and plating tin, lead or silver on the surface of the negative current collector of the copper foil or the graphite foil.
In a second preferred embodiment, the negative electrode includes a negative electrode active material supported on a negative electrode current collector in addition to the negative electrode current collector. In this case, the negative electrode active material is a carrier for charging and discharging the negative electrode.
The negative electrode active material is a second metal including its simple substance. Preferably, the negative electrode active material is Zn, Ni, Fe, Cr, Cu, Mn, Sn, or Pb.
Reference may be made to the first preferred embodiment for the negative current collector, which is not described in detail here!
The second metal is present in the form of flakes or powder.
When the second metal sheet is used as the negative active material, the second metal sheet and the negative current collector form a composite layer.
In this case, the bismuth compound is added to the negative electrode by a method including, but not limited to, adding the bismuth compound to a dispersant to prepare a dispersion, coating the dispersion on a second metal sheet, and finally removing the dispersant.
When the second metal powder is used as the negative active material, the bismuth compound is added to the negative electrode in a manner including, but not limited to, mixing the bismuth compound and the second metal powder to prepare a slurry, and then coating the slurry on a negative current collector to prepare a negative electrode.
In a specific embodiment, when the negative electrode is prepared, in addition to the negative electrode active material second metal powder, a negative electrode conductive agent and a negative electrode binder may be added as necessary to improve the performance of the negative electrode according to the actual situation.
In the third preferred embodiment, the second metal sheet is directly used as the negative electrode, and the second metal sheet serves as both the negative electrode current collector and the negative electrode active material. In this case, the second metal piece is a carrier for charging and discharging the negative electrode.
In this embodiment, the bismuth compound is added to the negative electrode by a method including, but not limited to, adding the bismuth compound to a dispersant to prepare a dispersion, coating the dispersion on the second metal sheet, and finally removing the dispersant.
Of course, in order to further improve the battery performance, a bismuth compound is added to the negative electrode and the electrolyte.
Preferably, the bismuth compound is selected from bismuth trioxide and/or bismuth nitrate.
The amount of the bismuth compound used in the negative electrode is preferably as follows:
when the bismuth trioxide is used independently, the bismuth trioxide accounts for 0.1-10% of the total weight of the negative electrode.
When the bismuth nitrate is used independently, the bismuth nitrate accounts for 0.1-10% of the total weight of the negative electrode.
It is of course also possible to use mixtures of bismuth trioxide and bismuth nitrate.
The battery may be free of separator. Of course, in order to provide better safety performance, it is preferable to further provide a separator between the positive electrode and the negative electrode in the electrolytic solution. The diaphragm can avoid short circuit caused by connection of the anode and the cathode caused by other accidental factors.
The separator of the present invention is not particularly limited as long as it allows an electrolyte to pass therethrough and is electrically insulating. Various separators used in organic lithium ion batteries can be applied to the present invention. The diaphragm can also be made of other materials such as a microporous ceramic separator.
The invention is further illustrated and described below with reference to specific examples.
Example 1
Weighing zinc methanesulfonate and lithium methanesulfonate, dissolving in deionized water to obtain electrolyte solution A1, wherein the electrolyte solution is 2mol/L zinc methanesulfonate and 2mol/L lithium methanesulfonate.
Example 2
Weighing zinc methanesulfonate and lithium methanesulfonate, dissolving in deionized water to obtain electrolyte solution A2, wherein the electrolyte solution is 2mol/L zinc methanesulfonate and 5mol/L lithium methanesulfonate.
Example 3
Weighing zinc methanesulfonate and lithium methanesulfonate, dissolving in deionized water, and adding bismuth trioxide to prepare electrolyte with zinc methanesulfonate of 3mol/L, lithium methanesulfonate of 2mol/L and bismuth trioxide content of 1wt%, which is recorded as A3.
Example 4
Weighing zinc methanesulfonate, lithium methanesulfonate, zinc sulfate and lithium sulfate, dissolving in deionized water to prepare electrolyte solution of 1mol/L zinc methanesulfonate, 1mol/L lithium methanesulfonate, 1mol/L zinc sulfate and 0.5mol/L lithium sulfate, and recording the electrolyte solution as A4.
Example 5
Weighing zinc sulfate and lithium sulfate, dissolving in deionized water, and preparing into a solution S1 of 2mol/L zinc sulfate and 1mol/L lithium sulfate. Weighing zinc methanesulfonate and lithium methanesulfonate, dissolving in deionized water, and preparing into a solution S2 of 2mol/L zinc methanesulfonate and 3mol/L lithium methanesulfonate.
The solution S1 and the solution S2 were mixed at a volume ratio of 10:90 to obtain an electrolyte designated A5.
Example 6
In contrast to example 5, the volume ratio of solution S1 to solution S2 was 25:75, and was designated A6.
Example 7
In contrast to example 5, the volume ratio of solution S1 to solution S2 was 50:50 and was designated A7.
Example 8
In contrast to example 5, the volume ratio of solution S1 to solution S2 was 90:10 and was designated A8.
Comparative example 1
Weighing zinc sulfate and lithium sulfate, dissolving in deionized water, and preparing into electrolyte solution of 2mol/L zinc sulfate and 1mol/L lithium sulfate, and recording as AC 1.
Preparation of the Battery
Mixing the lithium manganate LMO, the conductive agent graphite, the binder SBR and the CMC in water according to a mass ratio of 90:5:2.5:2.5 to form uniform anode slurry, coating the slurry on two surfaces of an anode current collector (50 mu m stainless steel wire mesh) coated with a conductive film to form an active material layer, tabletting, and cutting into pieces of 8 multiplied by 10cm (for testing gas content) or 6 multiplied by 6cm (for testing gas content)Testing other performances of the battery) to obtain a positive plate, wherein the thickness of the positive plate is 0.4mm, and the surface density of the positive active material is 750g/m2。
A zinc foil 50 μm thick was used as the negative electrode. The separator is an AGM glass fiber separator, and the sizes of the separator and the negative electrode are equivalent to those of the positive electrode.
And assembling the positive electrode, the negative electrode and the separator with electrolyte A1-A8 and AC1 respectively to form the battery. The batteries thus obtained were designated B1-B8 and BC1, respectively.
And (3) performance testing:
low temperature freezing test:
the electrolyte A1-A4 and AC1 were left at-20 ℃ for 12 hours, and then taken out to observe whether the electrolyte was frozen or not, and the test results are shown in Table 1.
TABLE 1 electrolyte Low temperature Freeze test results
Electrolyte solution A1 A2 A3 A4 AC1
Whether or not to freeze Does not freeze Does not freeze Does not freeze Does not freeze Freezing of
As can be seen from table 1, the electrolytes of examples 1 to 4 are still not frozen after being placed for 12 hours, while the electrolyte of comparative example 1 is frozen after 12 hours, which shows that the electrolyte of alkylsulfonate ions can effectively inhibit low-temperature freezing, improve the low-temperature performance of the electrolyte, and enhance the low-temperature weather resistance of the battery.
And (3) testing the gas content:
the batteries B1 and BC1 were left at 60 ℃ for 1 day, and the amount of gas generated from the batteries was collected. The results are shown in FIG. 1. The dots in fig. 1 represent cell BC1 and the squares represent cell B1.
As can be seen from fig. 1, the amount of gas generated per day by cell BC1 is much greater than that of cell B1, almost 2 times that of cell B1. This shows that the electrolyte provided by the present invention can effectively suppress the generation of gas in the battery compared to the sulfate electrolyte.
5g of zinc powder was weighed, added to 20ml of electrolytes A1 and A3, left at 50 ℃ for several days, and the gas production was measured. The results are shown in Table 2.
TABLE 2 gas production rates of electrolytes A1 and A3
Electrolyte solution Day 1 Day 2 Day 3 Day 4 Day 5
A1 29ml 42ml 38ml 23ml 35ml
A3 22ml 27ml 15ml 11ml 10ml
As can be seen from table 2, the amount of gas generated by the electrolyte A3 is much smaller than that of the electrolyte a1, which indicates that the bismuth compound added to the electrolyte acts together with the alkylsulfonate ion to effectively further reduce the amount of gas generated by the cell.
Self-discharge performance test:
the positive electrode sheet was prepared as described above, and the positive electrode sheet was placed in the electrolyte solution a1 and AC1, respectively, and left at 60 ℃ for 1 day, and the self-discharge rate of the positive electrode was measured. The results are shown in Table 3.
TABLE 3 Positive electrode Capacity Retention ratios of electrolytes A1 and AC1
Electrolyte solution Capacity retention ratio/%)
A1 96.5
AC1 90.4
As can be seen from table 3, the capacity retention rate of the positive electrode sheet in the electrolyte solution a1 was much larger than that of the positive electrode sheet in the electrolyte solution AC 1.
The batteries B5 to B8 and BC1 were stored at 60 ℃ for 24 hours, respectively, and then subjected to a discharge-charge cycle once, and then storage, discharge-charge and so on were repeated 9 times, and the remaining capacities of the batteries were tested. The results are shown in Table 4.
TABLE 4 self-discharge at 60 ℃ of batteries B5-B8
Battery with a battery cell Capacity retention rate
B5 94.3%
B6 96.1%
B7 94.0%
B8 90.0%
BC1 87.0%
As can be seen from table 4, the capacity retention rates of the batteries B5-B8 relative to the battery BC1 were all greatly improved. This shows that the electrolyte added with the alkylsulfonate can effectively suppress the self-discharge of the battery.
And (3) rate discharge performance test:
cells B1 and BC1 were cycled 3 times at 0.2C, 1C, and 3C, respectively, and finally at 1C.
According to the test, the 3C specific discharge capacity of the battery B1 is 52.8 percent and the 1C specific discharge capacity is 95 percent based on the 0.2C specific discharge capacity. The specific discharge capacities of the batteries BC1, 3C and 1C were 35% and 60%, respectively. The electrolyte provided by the invention can effectively improve the high-rate cycle performance of the battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (14)

1. An electrolyte for a battery, characterized by: the electrolyte solution includes at least one solvent capable of dissolving an electrolyte and ionizing the electrolyte; the electrolyte comprises first metal ions which can be reversibly extracted from and embedded into the positive electrode in the charging and discharging process and second metal ions which can be reduced and deposited into second metal in the negative electrode in the charging process; the second metal is reversibly oxidized and dissolved into second metal ions in the discharging process; the anion in the electrolyte comprises alkyl sulfonate ions, and the concentration of the alkyl sulfonate ions is 0.5-12 mol/L; the electrolyte also includes an electrolyte additive that includes a bismuth compound.
2. The electrolyte of claim 1, wherein: the alkyl sulfonate ion is a methyl sulfonate ion.
3. The electrolyte of claim 1, wherein: the concentration of the first metal ions is 1-7 mol/L, and the concentration of the second metal ions is 1-4 mol/L.
4. The electrolyte of claim 1, wherein: the first metal ions are lithium ions, and the second metal ions are zinc ions.
5. The electrolyte of claim 1, wherein: the solvent is water or alcohol.
6. The electrolyte of claim 1, wherein: the bismuth compound is bismuth trioxide or bismuth nitrate.
7. The electrolyte of claim 1, wherein: the bismuth compound accounts for 0.01-5% of the total weight of the electrolyte.
8. The electrolyte of claim 1, wherein: the electrolyte also comprises one or more of sulfate ions, chloride ions, acetate ions and nitrate ions.
9. The electrolyte of claim 8, wherein: the molar ratio of the sulfate ions to the alkyl sulfonate ions is 1: 21-27: 7.
10. The electrolyte of claim 1, wherein: the pH value of the electrolyte is 3-7.
11. A battery includes a positive electrode, a negative electrode, and an electrolyte; the positive electrode comprises a positive active material capable of reversibly deintercalating and intercalating first metal ions; the negative electrode includes a carrier for charging and discharging the negative electrode; characterized in that the electrolyte is according to any one of claims 1 to 10.
12. The battery of claim 11, wherein: the negative electrode includes a negative electrode additive that includes a compound of bismuth.
13. The battery of claim 12, wherein: the bismuth compound is bismuth trioxide or bismuth nitrate.
14. The battery of claim 13, wherein: the bismuth compound accounts for 0.1-10% of the total weight of the negative electrode.
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CN102035007A (en) * 2009-09-25 2011-04-27 中国人民解放军63971部队 Water-soluble organic couple redox flow battery
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CN101208818A (en) * 2005-04-26 2008-06-25 鲍尔热尼系统公司 Nickel zinc battery design
CN102035007A (en) * 2009-09-25 2011-04-27 中国人民解放军63971部队 Water-soluble organic couple redox flow battery
CN103107373A (en) * 2011-11-14 2013-05-15 苏州宝时得电动工具有限公司 Battery

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