CN114006044A - High-voltage electrolyte and application thereof - Google Patents
High-voltage electrolyte and application thereof Download PDFInfo
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- CN114006044A CN114006044A CN202111242972.8A CN202111242972A CN114006044A CN 114006044 A CN114006044 A CN 114006044A CN 202111242972 A CN202111242972 A CN 202111242972A CN 114006044 A CN114006044 A CN 114006044A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 75
- 239000000654 additive Substances 0.000 claims abstract description 39
- 230000000996 additive effect Effects 0.000 claims abstract description 38
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical group FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002608 ionic liquid Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- -1 bis (trifluoromethanesulfonimide) imide Chemical class 0.000 claims description 21
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 18
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 16
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 14
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 14
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 14
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 9
- JOTQIXXCBHIDKJ-UHFFFAOYSA-N 1-ethyl-3-methylimidazolidine Chemical compound CCN1CCN(C)C1 JOTQIXXCBHIDKJ-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 230000000052 comparative effect Effects 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 229910012258 LiPO Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000005677 organic carbonates Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001444 polymaleic acid Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- SJWDKHDXLCNJFV-UHFFFAOYSA-M S(=O)(=O)([O-])O.B(O)(F)F.[Li+] Chemical compound S(=O)(=O)([O-])O.B(O)(F)F.[Li+] SJWDKHDXLCNJFV-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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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
- H01M10/0567—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
- H01M10/052—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
- H01M10/056—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
-
- 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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- 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
The invention provides a high-voltage electrolyte and application thereof, wherein the electrolyte comprises a solvent, a lithium salt, a film forming additive and a film forming additive, the film forming additive is bis-trifluoromethanesulfonimide salt ionic liquid, the electrolyte contains bis-trifluoromethanesulfonimide salt ionic liquid and the film forming additive, and the bis-trifluoromethanesulfonimide salt ionic liquid can simultaneously improve the compatibility of the electrolyte and positive and negative electrode interfaces, remarkably improve the cycle stability of a battery at high voltage (>4.3V), and effectively improve the electrical property of the battery at the high voltage.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a high-voltage electrolyte and application thereof.
Background
With the pursuit of large-scale and high endurance of lithium ion batteries, the development of high energy density lithium ion batteries is urgent. The energy density of the material is determined by specific capacity and cut-off voltage, for a ternary system material, the specific capacity of the material is higher as the nickel content is higher, however, the interface stability of the anode and the electrolyte is poor as the nickel content is increased. Another effective and economical method is to increase the upper voltage limit to increase the energy density. Therefore, an electrolyte suitable for a high-voltage system needs to be developed to meet the requirements of people on the high-energy-density lithium ion battery. Through years of development and optimization, the current commercialized electrolyte mainly consists of three parts, namely an electrolyte, a solvent and an additive. The solvent is mainly organic carbonate and organic carboxylic ester, the organic carbonate can be divided into cyclic carbonate and linear carbonate, and the cyclic carbonate comprises Ethylene Carbonate (EC), Propylene Carbonate (PC) and fluoroethylene carbonate (FEC) and derivatives thereof. The linear carbonates include methylethyl carbonate (EMC), diethyl carbonate (DEC), and the like. Carboxylic acid esters including Propyl Propionate (PP), Propyl Acetate (PA), Ethyl Propionate (EP) are common. Neither cyclic carbonate nor linear carbonate alone can enable the cell to function properly. For this purpose, Ethylene Carbonate (EC) having a high dielectric constant is used in combination with a linear carbonate having a low viscosity to ensure excellent performance of the battery.
For high voltage (≧ 4.3V) systems, the primary failure modes of the battery are: (1) the anode side has stronger oxidation activity under high voltage, which causes a great deal of decomposition of solvent components in the electrolyte and forms a thicker CEI film to prevent the diffusion of ions. (2) At high voltages, oxygen evolution from the cathode material accelerates oxidation of electrolyte solvent components.
CN109301324A discloses a high-energy density lithium ion battery electrolyte, which is prepared from the following raw materials in percentage by weight: 20-60% of lithium salt, 20-60% of non-aqueous organic solvent and 0.5-10% of additive; the sum of the above components is equal to 100%; the lithium salt comprises lithium hexafluorophosphate, lithium bis-fluorosulfonyl imide and lithium difluoroborate sulfate. The electrolyte cannot be normally used under a high-pressure condition.
CN108470927A discloses a preparation method and application of a high-energy-density vanadium electrolyte. The method comprises the steps of firstly obtaining low-molecular-weight (400-800) polymaleic acid, then reacting the polymaleic acid with vanadium pentoxide, sulfur powder and sulfuric acid, controlling the reaction end point, degassing to remove impurities, and adjusting the concentration to prepare the high-concentration vanadium electrolyte (with the valence of 3.5). The preparation method of the electrolyte is complex and difficult to control, and good performance cannot be maintained under high pressure.
The electrolyte can not maintain good electrochemical performance under the condition of high pressure (more than or equal to 4.3V), so that the development of the electrolyte with high energy density and good electrochemical performance still maintained under high pressure is necessary.
Disclosure of Invention
The invention aims to provide a high-voltage electrolyte and application thereof, wherein the electrolyte contains bis-trifluoromethanesulfonimide salt ionic liquid and a film-forming additive, and the bis-trifluoromethanesulfonimide salt ionic liquid can simultaneously improve the compatibility of the electrolyte and positive and negative electrode interfaces, remarkably improve the cycling stability of a battery at high voltage (not less than 4.3V), and effectively improve the electrical property of the battery at the high voltage.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high-voltage electrolyte, which includes a solvent, a lithium salt, a film-forming additive and a film-decorating additive, wherein the film-decorating additive is bis-trifluoromethanesulfonimide ionic liquid.
The high-voltage electrolyte contains a film forming additive and bis (trifluoromethanesulfonimide) imide ionic liquid serving as a film decorating additive, and the film forming performance of the positive electrode side can be improved, the consumption of the electrolyte is reduced, and the charge transfer impedance is reduced at the same time.
Preferably, the bis (trifluoromethanesulfonyl) imide salt ionic liquid comprises any one or a combination of at least two of 1-ethyl-3-methylimidazoline bis (trifluoromethanesulfonyl) imide, N-propyl-N-methylpyrrole bis (trifluoromethanesulfonyl) imide or N-methyl-N-propyl piperidine bis (trifluoromethanesulfonyl) imide.
Preferably, the mass fraction of the bis-trifluoromethanesulfonimide salt ionic liquid is 1-5% based on 100% of the mass of the solvent and the additive in the electrolyte, for example: 1%, 2%, 3%, 4%, 5%, etc.
Preferably, the solvent comprises any one or a combination of at least two of ethylene carbonate, ethyl methyl carbonate, diethyl carbonate or propylene carbonate, preferably ethylene carbonate, ethyl methyl carbonate, diethyl carbonate and propylene carbonate.
Preferably, the mass fraction of the ethylene carbonate is 20-30% based on 100% of the mass of the solvent and the additive in the electrolyte, for example: 20%, 22%, 23%, 25%, 28%, 30%, etc.
Preferably, the mass fraction of the ethyl methyl carbonate is 30-50%, for example: 30%, 35%, 40%, 45%, 50%, etc.
Preferably, the mass fraction of the diethyl carbonate is 20-30%, for example: 20%, 22%, 23%, 25%, 28%, 30%, etc.
Preferably, the mass fraction of the propylene carbonate is 5-10%, for example: 5%, 6%, 7%, 8%, 9%, 10%, etc.
Preferably, the lithium salt comprises lithium hexafluorophosphate.
Preferably, the electrolyte further includes a lithium salt additive.
Preferably, the lithium salt additive comprises lithium bistrifluoromethylsulphonylimide and/or lithium difluorophosphate, preferably lithium bistrifluoromethylsulphonylimide and lithium difluorophosphate.
Preferably, the concentration of the lithium hexafluorophosphate is 0.5-1.2 mol/L, for example: 0.5mol/L, 0.6mol/L, 0.8mol/L, 1mol/L or 1.2mol/L, etc.
Preferably, the mass fraction of the lithium bis (trifluoromethyl) sulfonyl imide is 1-3% based on 100% of the mass of the solvent and the additive in the electrolyte, for example: 1%, 1.5%, 2%, 2.5%, 3%, etc.
Preferably, the mass fraction of the lithium difluorophosphate is 0.5-1% based on 100% of the mass of the solvent and the additive in the electrolyte, such as: 0.5%, 0.6%, 0.7%, 0.8%, or 1%, etc.
Preferably, the film forming additive comprises vinyl sulfate and/or vinylene carbonate, preferably vinyl sulfate and vinylene carbonate.
Preferably, the mass fraction of the vinyl sulfate is 1-2% based on 100% of the mass of the solvent and the additive in the electrolyte, for example: 1%, 1.2%, 1.5%, 1.8%, 2%, etc.
Preferably, the mass fraction of the vinylene carbonate is 1-3% based on 100% of the solvent and the additive in the electrolyte, for example: 1%, 1.5%, 2%, 2.5%, 3%, etc.
In a second aspect, the present invention provides a lithium ion battery, where the lithium ion battery includes the high voltage electrolyte according to the first aspect, and the working voltage of the lithium ion battery is 4.3-4.5V, for example: 4.3V, 4.35V, 4.4V, 4.45V or 4.5V, etc.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-voltage electrolyte can improve the stability of the interface between the anode and the electrolyte under high voltage, improve the performance of the battery, improve the film-forming performance of the anode side, reduce the consumption of the electrolyte and reduce the charge transfer impedance.
(2) The capacity retention rate of the high-voltage electrolyte can reach over 69.3 percent when the high-voltage electrolyte is circulated for 1000 circles under high voltage (4.4V).
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. 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
The present embodiment provides a high voltage electrolyte, which comprises the following components:
in the electrolyte, lithium hexafluorophosphate (LiPF)6)1 mol/L; in the electrolyte, 25g of Ethylene Carbonate (EC); 35g of Ethyl Methyl Carbonate (EMC), 25g of diethyl carbonate (DEC); 6g of Propylene Carbonate (PC); 2g of lithium bis (fluoromethylsulfonyl) imide (LiFSI); lithium difluorophosphate (LiPO)2F2)0.8 g; 0.8g of vinyl sulfate (DTD); vinylene Carbonate (VC)0.8 g; 4.6g of 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide (EMI-TFSI).
Example 2
In the electrolyte, lithium hexafluorophosphate (LiPF)6)1 mol/L; in the electrolyte, 25g of Ethylene Carbonate (EC); 35g of Ethyl Methyl Carbonate (EMC), 25g of diethyl carbonate (DEC); 5.2g of Propylene Carbonate (PC); 3.5g of lithium bis (fluoromethylsulfonyl) imide (LiFSI); lithium difluorophosphate (LiPO)2F2)0.8 g; 1g of vinyl sulfate (DTD); vinylene Carbonate (VC)1 g; 3.5g of N-propyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide (Py-TFSI).
Example 3
In the electrolyte, lithium hexafluorophosphate (LiPF)6)1 mol/L; in the electrolyte, 25g of Ethylene Carbonate (EC); 35g of Ethyl Methyl Carbonate (EMC), 25g of diethyl carbonate (DEC); 5.2g of Propylene Carbonate (PC); 3.5g of lithium bis (fluoromethylsulfonyl) imide (LiFSI); lithium difluorophosphate (LiPO)2F2)0.8 g; 1g of vinyl sulfate (DTD); vinylene Carbonate (VC)1 g; N-methyl-N-propylpiperidine bis (trifluoromethanesulfonyl) imide (PP)13-TFSI)3.5g。
Example 4
This example differs from example 1 only in that the mass of 1-ethyl-3-methylimidazolidine bis (trifluoromethylsulfonyl) imide (EMI-TFSI) was 0.5g and the mass of ethylene carbonate was 29.1g, and the other conditions and parameters were exactly the same as those of example 1.
Example 5
This example differs from example 1 only in that the mass of 1-ethyl-3-methylimidazolidine bis (trifluoromethylsulfonyl) imide (EMI-TFSI) was 8g and the mass of ethylene carbonate was 21.6g, and the other conditions and parameters were exactly the same as those of example 1.
Comparative example 1
This comparative example differs from example 1 only in that 1-ethyl-3-methylimidazolidine bis (trifluoromethylsulfonyl) imide (EMI-TFSI) was not added, and the other conditions and parameters were exactly the same as those of example 1.
Comparative example 2
This comparative example differs from example 1 only in that 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide (EMI-TFSI) was replaced by 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF)4) Other conditions and parameters were exactly the same as those in example 1.
Comparative example 3
This comparative example differs from example 1 only in that no film-forming additives (vinyl sulfate (DTD) and Vinylene Carbonate (VC)) are added, and the other conditions and parameters are exactly the same as those of example 1.
And (3) performance testing:
the electrolytes obtained in examples 1 to 5 and comparative examples 1 to 3 were formed into batteries, which were charged to 4.4V at a constant current and a constant voltage at 1C and discharged to 2.75V at 1C, and the charge and discharge cycles were repeated for 1000 weeks according to this procedure, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the capacity retention ratio of the high voltage electrolyte of the present invention can reach 69.3% or more after 1000 cycles under high voltage (4.4V) as obtained from examples 1 to 5.
Compared with the examples 4 to 5, the mass fraction of the bis (trifluoromethanesulfonimide) imide salt ionic liquid affects the high-voltage performance of the prepared electrolyte, the mass fraction of the bis (trifluoromethanesulfonimide) imide salt ionic liquid is controlled to be 1-5%, the high-voltage performance of the prepared electrolyte is good, if the mass fraction of the bis (trifluoromethanesulfonimide) imide salt ionic liquid is too high, the conductivity of the obtained electrolyte is reduced, the electrical performance is poor, and if the mass fraction of the bis (trifluoromethanesulfonimide) imide salt ionic liquid is too low, the ionic liquid cannot form a stable enough interface film.
Compared with the comparative example 1, the electrolyte is added with the film decorating additive (bis (trifluoromethanesulfonimide) salt ionic liquid) to improve the interface stability of the negative electrode by the synergistic effect of the film decorating additive and Vinylene Carbonate (VC) on the negative electrode side, and meanwhile, the film is oxidized on the positive electrode side to form a film, so that the decomposition of the electrolyte under high voltage is reduced.
Compared with the comparative example 2, the performance of the electrolyte prepared by replacing the bis (trifluoromethanesulfonimide) imide salt ionic liquid disclosed by the invention with other ionic liquids is obviously reduced, because the ionic liquid disclosed by the application has a higher oxidation potential and is more stable under high pressure, the occurrence of side reactions can be avoided, and the circulation performance of the electrolyte under high pressure is further improved.
Compared with the comparative example 3, the electrolyte of the invention is added with a proper film forming additive, and the film forming additive and the film decorating additive act together, so that the film forming performance of the positive electrode side can be improved, the consumption of the electrolyte is reduced, the charge transfer impedance is reduced, and the cycle performance of the electrolyte is effectively improved.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The high-voltage electrolyte is characterized by comprising a solvent, a lithium salt, a film forming additive and a film decorating additive, wherein the film decorating additive is bis (trifluoromethanesulfonimide) imide ionic liquid.
2. The electrolyte of claim 1, wherein the bis-trifluoromethanesulfonimide ionic liquid comprises any one of or a combination of at least two of 1-ethyl-3-methylimidazoline bis (trifluoromethanesulfonyl) imide, N-propyl-N-methylpyrrole bis (trifluoromethanesulfonyl) imide, or N-methyl-N-propyl piperidine bis (trifluoromethanesulfonyl) imide.
3. The high-voltage electrolyte according to claim 1 or 2, wherein the mass fraction of the bis-trifluoromethanesulfonimide salt-type ionic liquid is 1-5% based on 100% by mass of the solvent and the additive in the electrolyte.
4. The high voltage electrolyte of any one of claims 1-3, wherein the solvent comprises any one of ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, or propylene carbonate, or a combination of at least two thereof, preferably ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, and propylene carbonate.
5. The high-voltage electrolyte as claimed in claim 4, wherein the mass fraction of the ethylene carbonate is 20 to 30% based on 100% by mass of the solvent and the additive in the electrolyte;
preferably, the mass fraction of the methyl ethyl carbonate is 30-50%;
preferably, the mass fraction of the diethyl carbonate is 20-30%;
preferably, the mass fraction of the propylene carbonate is 5-10%.
6. The high voltage electrolyte of any one of claims 1-5, wherein the lithium salt comprises lithium hexafluorophosphate;
preferably, the electrolyte further comprises a lithium salt additive;
preferably, the lithium salt additive comprises lithium bistrifluoromethylsulphonylimide and/or lithium difluorophosphate, preferably lithium bistrifluoromethylsulphonylimide and lithium difluorophosphate.
7. The high voltage electrolyte of claim 6, wherein the concentration of lithium hexafluorophosphate is 0.5 to 1.2 mol/L;
preferably, the mass fraction of the lithium bis (trifluoromethyl) sulfonyl imide is 1-3% by taking the mass of the solvent and the additive in the electrolyte as 100%;
preferably, the mass fraction of the lithium difluorophosphate is 0.5-1% based on 100% of the mass of the solvent and the additive in the electrolyte.
8. The high voltage electrolyte of any one of claims 1 to 7, wherein the film forming additive comprises vinyl sulfate and/or vinylene carbonate, preferably vinyl sulfate and vinylene carbonate.
9. The high-voltage electrolyte as claimed in claim 8, wherein the mass fraction of the vinyl sulfate is 1 to 2% based on 100% by mass of the solvent and the additive in the electrolyte;
preferably, the mass fraction of the vinylene carbonate is 1-3% based on 100% of the mass of the solvent and the additive in the electrolyte.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the high voltage electrolyte according to any one of claims 1 to 9, and the working voltage of the lithium ion battery is 4.3 to 4.5V.
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