CN117096452A - Electrolyte and double-ion battery containing same - Google Patents

Electrolyte and double-ion battery containing same Download PDF

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Publication number
CN117096452A
CN117096452A CN202310989311.4A CN202310989311A CN117096452A CN 117096452 A CN117096452 A CN 117096452A CN 202310989311 A CN202310989311 A CN 202310989311A CN 117096452 A CN117096452 A CN 117096452A
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China
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electrolyte
solvent
double
ion battery
positive electrode
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CN202310989311.4A
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Chinese (zh)
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王宏宇
王博宇
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Priority to CN202310989311.4A priority Critical patent/CN117096452A/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
    • H01M10/05—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
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents

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  • Chemical & Material Sciences (AREA)
  • 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)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

An electrolyte and a double-ion battery containing the same relate to the technical field of double-ion batteries and solve the problem that the performance and the service life of the existing double-ion battery cannot be considered. The electrolyte comprises electrolyte salt and solvent; the solvent comprises methyl ethyl carbonate (EMC) and at least one of dimethyl sulfone (DMS) or a derivative thereof; electrolyte salt of XPF 6 、XBF 4 At least one of them, XTFSI, XFSI, XDFOB, wherein X is Li, na or K. The battery cell comprises a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode and the electrolyte. The invention can realize the high capacity and high working voltage level of the double-ion battery at the same timeA table.

Description

Electrolyte and double-ion battery containing same
Technical Field
The invention relates to the technical field of double-ion batteries, in particular to electrolyte and a double-ion battery containing the electrolyte.
Background
The Dual Ion Battery (DIB) relies on faraday reactions with both cations and anions at the anode and cathode, respectively, has the advantages of low cost, high power, environmental protection, etc., and is an ideal choice for smart grid applications. McCullough in 1989 first introduced nonaqueous DIB for rechargeable batteries, graphite was used as cathode and anode, and alkali metal cations (Li + 、Na + 、K + ) And anions (ClO) 4– 、PF 6– 、BF 4– ) Intercalation and deintercalation of graphite, respectively, occurs during the charge/discharge process. Since then, many studies have used different types of active substances (Ca 2+ Pyridine cations, etc.) and electrode materials (hard carbon, sn, hydrocarbons, metal organic frameworks, etc.) many types of DIB have been developed. These DIBs are significantly superior to conventional lithium ion batteries in terms of operating voltage platform, rate capability, environmental friendliness, and material cost.
In general, improvement of a dual-ion battery is generally performed from the viewpoint of improving the capacity density of the dual-ion battery, taking graphite as a most promising positive electrode material in the current dual-ion battery as an example, by adjusting an electrolyte through a conventional means, the graphite positive electrode for improving the capacity density of the dual-ion battery can obtain higher capacity density after storing more anions, and can generate more serious expansion, and along with long-cycle operation of the battery, graphene in a graphite structure can be peeled off, and the structure of the graphite positive electrode can be damaged, so that the service life of the battery is also influenced.
Although the electrolyte has a significant impact on the electrochemical performance and safety of DIB, less attention is paid. Unlike other metal ion battery electrolytes, DIB electrolytes not only act as a medium for ion migration during battery operation, but also provide active ions to be intercalated into the electrode, and thus it is feasible to achieve improved performance of a dual ion battery by rational design of electrolyte components, and there is an urgent need to develop a novel electrolyte that can compromise both performance and lifetime.
Disclosure of Invention
In order to solve the problem that the performance and the service life of the conventional double-ion battery cannot be considered, the invention provides electrolyte and a double-ion battery containing the electrolyte.
The technical scheme of the invention is as follows:
an electrolyte comprising an electrolyte salt and a solvent;
the solvent comprises methyl ethyl carbonate (EMC) and at least one of dimethyl sulfone (DMS) or a derivative thereof;
the electrolyte salt is XPF 6 、XBF 4 、XTFSI、XFSI、XDAt least one of FOB, wherein X is Li, na or K.
The electrolyte salt is more preferably XPF 6 At least one of XTFSI, XFSI.
Preferably, the dimethyl sulfone or derivative thereof has the following structural formula:
wherein R is 1 And R is 2 Are all selected from (CH) 2 ) x CH(CH 3 ) 2 Or (CH) 2 ) x CH 3 X=0, 1, 2 or 3.
Preferably, the dimethyl sulfone or derivative thereof is selected from (1)(2)/>(3)Or (4)/(S)>
Preferably, the electrolyte salt is present in the electrolyte at a molar concentration of 0.2mol/L to a saturation concentration, more preferably 0.75mol/L to 4mol/L.
Preferably, the EMC accounts for not less than 20% by mass of the solvent, more preferably not less than 50%.
Preferably, the solvent further comprises a diluent.
Preferably, the diluent is BTFETTEHFME/>TFEOTFETFE/>HPTAt least one of them.
Preferably, the volume percent of the diluent in the solvent is no more than 80%, more preferably no more than 60%.
The invention also provides a double-ion battery, which comprises a shell and a battery cell sealed in the shell, wherein the battery cell comprises an anode, a cathode, a diaphragm between the anode and the cathode and electrolyte, and the electrolyte is the electrolyte.
Preferably, the positive electrode is graphite, the negative electrode is a lithium sheet, and the separator is glass fiber.
Compared with the prior art, the invention has the following specific beneficial effects:
1. the invention provides an electrolyte for improving the working voltage platform of a double-ion battery by adjusting the strategy of an anion solvation structure in the electrolyte, wherein dimethyl sulfone (DMS) and derivatives thereof have high oxidation resistance, the dimethyl sulfone (DMS) and derivatives thereof can be used as electrolyte components to improve the oxidation resistance of the electrolyte, solvated anions can be reversibly stored or separated from a carbon material positive electrode only under high voltage, and the solvated anions of methyl ethyl carbonate (EMC) can be obtained in the carbon material positive electrode to obtain high capacity; when the two are matched as solvents, the solvation structure of anions is adjusted by adjusting the proportion of the two, so that a high capacity and a high working voltage platform of the double-ion battery can be simultaneously realized. The resulting developed bi-ionic cell can achieve a specific performance improvement without modification to the manufacturing process of the battery.
2. The invention also adopts a low-viscosity solvent with a wide electrochemical window and weak solvation effect with anions and cations as a diluent, so that the viscosity improvement caused by the concentration improvement of the electrolyte can be effectively reduced under the condition of not participating in the solvation structure of the anions and the cations.
Detailed Description
In order to make the technical solution of the present invention more clear, the following description will clearly and completely describe the technical solution of the embodiments of the present invention, and it should be noted that the following embodiments are only used for better understanding the technical solution of the present invention, and should not be construed as limiting the present invention.
Example 1.
In an inert atmosphere glove box having both a water content and an oxygen content of less than 1ppm, compound (2) was selectedAnd EMC were formulated as solvent in a mass ratio of 3:7, liPF was used without diluent 6 Dissolved therein at a molar concentration of 1mol/L to obtain 1M LiPF 6 Compound (2) electrolyte of EMC (3:7by weight.).
Button cells were assembled in a glove box using a CR2032 housing made of 316 stainless steel, wherein the negative electrode active material was a lithium sheet, the positive electrode active material was d50=8μm spherical natural graphite, and the separator was glass fiber.
The battery was set at 1C (1c=100 mAh g at room temperature -1 ) The charge and discharge test is carried out under the current density of (1), and the charge and discharge voltage range is 3V-5.3V.
Example 2.
In an inert atmosphere glove box having both a water content and an oxygen content of less than 1ppm, compound (2) was selectedAnd EMC were formulated as main solvent in a mass ratio of 3:7, liPF was used without diluent 6 Dissolved therein at a molar concentration of 2mol/L to obtain 2M LiPF 6 Compound (2) electrolyte of EMC (3:7by weight.).
Button cells were assembled in a glove box using a CR2032 housing made of 316 stainless steel, wherein the negative electrode active material was a lithium sheet, the positive electrode active material was d50=8μm spherical natural graphite, and the separator was glass fiber.
The battery was set at 1C (1c=100 mAh g at room temperature -1 ) The charge and discharge test is carried out on the current density of the battery, and the charge and discharge voltage range is 3V-5.3V.
Example 3.
In an inert atmosphere glove box having both a water content and an oxygen content of less than 1ppm, compound (2) was selectedAnd EMC is prepared into a main solvent according to the mass ratio of 3:7, the main solvent and TTE are prepared into a final solvent according to the volume ratio of 1:1, and LiPF is prepared 6 Dissolved therein at a molar concentration of 2mol/L to obtain 2M LiPF 6 [ Compound (2): EMC (3:7 by wt.) |TTE (1:1 by vol.)]Is used as an electrolyte.
Button cells were assembled in a glove box using a CR2032 housing made of 316 stainless steel, wherein the negative electrode active material was a lithium sheet, the positive electrode active material was d50=8μm spherical natural graphite, and the separator was glass fiber.
The battery was set at 1C (1c=100 mAh g at room temperature -1 ) The charge and discharge test is carried out on the current density of the battery, and the charge and discharge voltage range is 3V-5.3V.
Example 4.
In an inert atmosphere glove box having both a water content and an oxygen content of less than 1ppm, compound (4) was selectedAnd EMC is prepared into a main solvent according to the mass ratio of 2:8, the main solvent and TFETFE are prepared into a final solvent according to the volume ratio of 1:1, and LiPF is prepared 6 Dissolved therein at a molar concentration of 2mol/L to obtain 2M LiPF 6 [ Compound (4): EMC (2:8 by wt.) |TFETFE (1:1 by vol.)]Is used as an electrolyte.
Button cells were assembled in a glove box using a CR2032 housing made of 316 stainless steel, wherein the negative electrode active material was a lithium sheet, the positive electrode active material was d50=8μm spherical natural graphite, and the separator was glass fiber.
The battery was set at 1C (1c=100 mAh g at room temperature -1 ) The charge and discharge test is carried out on the current density of the battery, and the charge and discharge voltage range is 3V-5.3V.
Example 5.
At the water contentAnd oxygen content of less than 1ppm, and selecting the compound (2)And EMC is prepared into a main solvent according to the mass ratio of 3:7, the main solvent and TFETFE are prepared into a final solvent according to the volume ratio of 1:1, and LiTFSI and LiPF are prepared 6 Dissolving in the solution at molar concentrations of 2mol/L and 1mol/L to obtain 2M LiTFSI+1M LiPF 6 [ Compound (2): EMC (3:7 by wt.) |TFETFE (1:1 by vol.)]Is used as an electrolyte.
Button cells were assembled in a glove box using a CR2032 housing made of 316 stainless steel, wherein the negative electrode active material was a lithium sheet, the positive electrode active material was d50=8μm spherical natural graphite, and the separator was glass fiber.
The battery was set at 1C (1c=100 mAh g at room temperature -1 ) The charge and discharge test is carried out on the current density of the battery, and the charge and discharge voltage range is 3V-5.3V.
Example 6.
In an inert atmosphere glove box having both a water content and an oxygen content of less than 1ppm, compound (2) was selectedAnd EMC is configured into a main solvent according to the mass ratio of 3:7, the main solvent and TFETFE are configured into a final solvent according to the volume ratio of 1:1, liTFSI, liFeSI and LiPF are prepared 6 Respectively dissolved in the water at a volume molar concentration of 1mol/L to prepare 1M LiTFSI+1M LiFSI+1M LiPF 6 [ Compound (2): EMC (2:8 by wt.) |TFETFE (1:1 by vol.)]Is used as an electrolyte.
Button cells were assembled in a glove box using a CR2032 housing made of 316 stainless steel, wherein the negative electrode active material was a lithium sheet, the positive electrode active material was d50=8μm spherical natural graphite, and the separator was glass fiber.
The battery was set at room temperature at 1C (1c=100 mAhg -1 ) The charge and discharge test is carried out on the current density of the battery, and the charge and discharge voltage range is 3V-5.3V.
Comparative example 1.
In an inert atmosphere glove box with water content and oxygen content below 1ppm, EMC is selected as the organic solvent,LiPF is put into 6 Dissolved therein at a molar concentration of 1mol/L to obtain 1M LiPF 6 Electrolyte of EMC.
Button cells were assembled in a glove box using a CR2032 housing of 304 stainless steel, wherein the negative electrode active material was a lithium sheet, the positive electrode active material was d50=8μm spherical natural graphite, and the separator was glass fiber.
The battery was set at 1C (1c=100 mAh g at room temperature -1 ) The charge and discharge test is carried out on the current density of the battery, and the charge and discharge voltage range is 3V-5.2V.
Comparative example 2.
In an inert atmosphere glove box having both a water content and an oxygen content of less than 1ppm, compound (2) was selectedLiPF as an organic solvent 6 Dissolved therein at a molar concentration of 1mol/L to obtain 1M LiPF 6 An electrolyte of the compound (2).
Button cells were assembled in a glove box using a CR2032 housing made of 316 stainless steel, wherein the negative electrode active material was a lithium sheet, the positive electrode active material was d50=8μm spherical natural graphite, and the separator was glass fiber.
The battery was set at 1C (1c=100 mAh g at room temperature -1 ) The charge and discharge test is carried out on the current density of the battery, and the charge and discharge voltage range is 3V-5.3V.
The results of the charge and discharge tests in the above examples and comparative examples are shown in table 1.
TABLE 1
In the comparative example, two solvent components are respectively used as single solvents to prepare electrolyte and charge and discharge tests are carried out in the double-ion battery, and from the test results, it can be seen that methyl ethyl carbonate (EMC) can be used as single solventThe high capacity is obtained in the carbon material anode, namely the capacity density is higher, but the median voltage is lower, and when the carbon material anode is independently used as a solvent, the charge-discharge cut-off voltage can only reach 5.2V due to poor oxidation resistance; when (when)When the double-ion battery is used as the electrolyte solvent, the cut-off voltage of the double-ion battery can reach 5.3V, and solvated anions can be stored or separated from the carbon material anode reversibly under high voltage, so that the double-ion battery has the advantages of higher working voltage and lower discharge capacity density. When the two are matched as solvents, the solvation structure of anions is adjusted by adjusting the proportion of the two, so that a high capacity and a high working voltage platform of the double-ion battery can be simultaneously realized. The viscosity of the electrolyte at higher concentrations in examples 5 and 6 increases significantly, so that the introduction of the diluent can reduce the viscosity. The diluent adopts a low-viscosity solvent with a wide electrochemical window and weak solvation with anions and cations, so that the viscosity improvement caused by the concentration improvement of the electrolyte can be effectively reduced under the condition of not participating in the solvation structure of the anions and the cations.

Claims (10)

1. An electrolyte solution comprising an electrolyte salt and a solvent;
the solvent comprises methyl ethyl carbonate and at least one of dimethyl sulfone or a derivative thereof;
the electrolyte salt is XPF 6 、XBF 4 At least one of them, XTFSI, XFSI, XDFOB, wherein X is Li, na or K.
2. The electrolyte of claim 1, wherein the dimethyl sulfone or derivative thereof has the following structural formula:
wherein R is 1 And R is 2 Are all selected from (CH) 2 ) x CH(CH 3 ) 2 Or (CH) 2 ) x CH 3 X=0, 1, 2 or 3.
3. The electrolyte according to claim 1, wherein the dimethyl sulfone or the derivative thereof is
4. The electrolyte of claim 1, wherein the electrolyte salt is present in the electrolyte at a molar concentration of 0.2mol/L to a saturation concentration.
5. The electrolyte according to claim 1, wherein the mass percentage of the methyl ethyl carbonate in the solvent is not less than 20%.
6. The electrolyte of any one of claims 1-5 wherein the solvent further comprises a diluent.
7. The electrolyte of claim 6 wherein the diluent is BTFETTE/>HFMETFEO/>TFETFE/>HPTAt least one of them.
8. The electrolyte of claim 6 wherein the diluent is present in the solvent in an amount of no more than 80% by volume.
9. A bi-ionic cell comprising a housing and a cell sealed within the housing, the cell comprising a positive electrode, a negative electrode, a separator between the positive and negative electrodes, and an electrolyte, wherein the electrolyte is the electrolyte of any one of claims 1-8.
10. The bi-ionic cell of claim 9, wherein the positive electrode is graphite, the negative electrode is a lithium sheet, and the separator is glass fiber.
CN202310989311.4A 2023-08-08 2023-08-08 Electrolyte and double-ion battery containing same Pending CN117096452A (en)

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