CN114566706A - Lithium battery electrolyte and lithium battery - Google Patents
Lithium battery electrolyte and lithium battery Download PDFInfo
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- CN114566706A CN114566706A CN202210060911.8A CN202210060911A CN114566706A CN 114566706 A CN114566706 A CN 114566706A CN 202210060911 A CN202210060911 A CN 202210060911A CN 114566706 A CN114566706 A CN 114566706A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 67
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 66
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims abstract description 15
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims abstract description 15
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 14
- XNENYPKLNXFICU-UHFFFAOYSA-N P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound P(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C XNENYPKLNXFICU-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- 239000006259 organic additive Substances 0.000 claims abstract description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 14
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 14
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 12
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 11
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 11
- 239000012046 mixed solvent Substances 0.000 claims description 9
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 20
- 230000005012 migration Effects 0.000 abstract description 7
- 238000013508 migration Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
-
- 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
Abstract
The invention belongs to the technical field of lithium batteries, and mainly discloses a lithium battery electrolyte and a lithium battery, wherein the lithium battery electrolyte comprises the following components: lithium salts, organic solvents and additives; wherein the additive is a mixed additive comprising vinylene carbonate, 1, 3-propane sultone, fluoroethylene carbonate, lithium difluorophosphate, vinyl sulfate and tris (trimethylsilane) phosphite. The lithium battery electrolyte disclosed by the invention has the advantages that the migration rate of lithium ions in a low-temperature environment is improved by optimizing the electrolyte formula, so that the lithium battery has good cycle performance at a low temperature of-25 ℃.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a lithium battery electrolyte and a lithium battery.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, high charging and discharging efficiency and the like, and along with the development of the industry, higher requirements are provided for the high and low temperature charging and discharging performance of the lithium ion battery.
The electrolyte, which is used as a place for conducting energy carrier lithium ions between the positive and negative electrodes, is called "blood" of the lithium ion battery, and has a crucial influence on the life, safety, rate capability, and the like of the battery. However, when the lithium ion battery is used in winter or in severe cold areas, the battery can not provide enough electricity to cause the equipment to be unable to operate normally. Under the condition of low temperature, various performances of the lithium ion battery are strictThe important constraint is mainly due to: (1) under the ultralow temperature condition, the viscosity of the liquid electrolyte is sharply reduced, the ionic conductivity is remarkably reduced, the interfacial impedance of the electrode and the migration impedance of lithium ions are greatly increased, and are not matched with the electron rate of rapid migration of an external circuit, so that the interior of a lithium ion battery is seriously polarized, and a large amount of lithium ions are precipitated on the surface of a negative electrode; (2) the SEI film on the surface of the electrode is thickened at low temperature, and the impedance is obviously increased. The conventional improvement method is to add a certain amount of functional components such as film forming, flame retarding, overcharge resistance, etc. to the electrolyte as additives to improve the performance of the electrolyte. The electrolyte of the current commercial lithium ion battery generally adopts EC (ethylene carbonate) -based electrolyte, and the main component is LiPF (lithium ion Polymer)6(lithium hexafluorophosphate)/EC + DMC (other carbonate co-solvent). However, under low temperature operation, such as-10 ℃ to-30 ℃, how to select additives with specific functions and maintain high rate performance of the battery is still an important challenge in the field of lithium battery electrolytes.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide the lithium battery electrolyte, the migration rate of lithium ions in a low-temperature environment is improved by optimizing the electrolyte formula, the problems that the conventional lithium battery cannot normally discharge at the low temperature of lower than-20 ℃ and the high-rate discharge power is insufficient are solved, and the application range of the lithium battery in the alpine region is further widened.
Another object of the present invention is to provide a lithium battery comprising the above lithium battery electrolyte.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium battery electrolyte comprising the following components: lithium salts, organic solvents and additives;
wherein the additive is a mixed additive comprising vinylene carbonate, 1, 3-propane sultone, fluoroethylene carbonate, lithium difluorophosphate, vinyl sulfate and tris (trimethylsilane) phosphite.
Further, the lithium battery electrolyte comprises the following components in percentage by mass: 14% -20% of lithium salt, 75% -85% of organic solvent and 1.0% -5.0% of additive.
Furthermore, the mass ratio of the vinylene carbonate to the 1, 3-propane sultone to the fluoroethylene carbonate to the lithium difluorophosphate to the vinyl sulfate to the tris (trimethylsilane) phosphite is (4.5-5.5) to (2.5-3.5) to (4.5-5.5) to (4-6) to (8-12) to (1-2).
Preferably, the mass ratio of the vinylene carbonate, the 1, 3-propane sultone, the fluoroethylene carbonate, the lithium difluorophosphate, the vinyl sulfate and the tris (trimethylsilane) phosphite is 5: 3: 5: 10: 1.5.
Further, the lithium salt includes lithium hexafluorophosphate and lithium bis-fluorosulfonylimide.
Further, the concentration of the lithium hexafluorophosphate in the lithium battery electrolyte is 0.8-1.2 mol/L; the concentration of the lithium bis (fluorosulfonyl) imide in the lithium battery electrolyte is 0.3-0.4 mol/L.
Further, the organic solvent is a mixed solvent at least comprising ethylene carbonate, propylene carbonate, dimethyl carbonate and ethyl methyl carbonate.
Further, the mixed solvent comprises the following components in percentage by volume: 22.5-27.5% of ethylene carbonate, 2.5-7.5% of propylene carbonate, 27.5-32.5% of dimethyl carbonate and 37.5-42.5% of ethyl methyl carbonate.
Preferably, the mixed solvent comprises the following components in percentage by volume: 25% of ethylene carbonate, 5% of propylene carbonate, 30% of dimethyl carbonate and 40% of ethyl methyl carbonate.
The invention also provides a lithium battery adopting the lithium battery electrolyte, which has good low-temperature resistance and can still maintain good circulation rate at the temperature of minus 25 ℃.
Compared with the prior art, the invention has the following advantages:
the invention provides a lithium battery electrolyte, which comprises the following components: lithium salts, organic solvents and additives; the additive is a mixed additive comprising vinylene carbonate, 1, 3-propane sultone, fluoroethylene carbonate, lithium difluorophosphate, vinyl sulfate and tris (trimethylsilane) phosphite. According to the lithium battery electrolyte, the formula of the electrolyte is optimized, and particularly, the novel mixed additive is adopted, so that the solid-liquid phase interface impedance can be effectively reduced, the ionic conductivity of an SEI (solid electrolyte interphase) film on the surface of a negative electrode is improved, the electrolyte can inhibit the decomposition of the electrolyte, the electrolyte has high ionic conductivity, and the low-temperature cycle performance of the battery is remarkably improved.
Drawings
FIG. 1 is a-25 deg.C/1C discharge curve of example 1 of the present invention with comparative examples;
FIG. 2 is a-25 deg.C/3C discharge curve of example 1 of the present invention with comparative examples;
FIG. 3 is a-25 deg.C/5C discharge curve of example 1 of the present invention with comparative examples;
FIG. 4 is a-25 deg.C/1C charge curve of example 1 of the present invention with comparative examples.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments and examples in conjunction with the accompanying drawings, but the embodiments of the present invention are not limited thereto. All the raw materials and reagents used in the present invention are commercially available raw materials and reagents, unless otherwise specified. In the examples, the components are used in g and mL in parts by mass.
The invention provides a lithium battery electrolyte, which mainly comprises 14-20% of lithium salt, 75-85% of organic solvent and 1.0-5.0% of additive by mass.
Wherein the additive is a mixed additive comprising vinylene carbonate, 1, 3-propane sultone, fluoroethylene carbonate, lithium difluorophosphate, vinyl sulfate and tris (trimethylsilane) phosphite. The mixed additive is added into the lithium battery electrolyte, so that the migration rate of lithium ions in a low-temperature environment can be obviously improved. The function of the additive in the electrolyte is mainly used for improving the migration rate of lithium ions in a low-temperature environment, effectively reducing the impedance of a solid-liquid phase interface, improving the ionic conductivity of an SEI film on the surface of a negative electrode, and simultaneously reducing trace water and HF acid in the electrolyte to prevent overcharge and overdischarge.
Wherein the lithium salt comprises lithium hexafluorophosphate and lithium bis-fluorosulfonylimide. Lithium hexafluorophosphate is used as a common commercial electrolyte lithium salt at present, the electrochemistry is relatively stable, and the lithium hexafluorophosphate is easily dissolved in an organic solvent, but when the environmental temperature is lower than 0 ℃, the conductivity of the electrolyte is obviously reduced, and the ion migration rate is slowed down; the lithium bis (fluorosulfonyl) imide has excellent conductivity and good electrochemical stability, but the lithium bis (fluorosulfonyl) imide has the defects of high cost, low purity and easy corrosion to aluminum foil at present, so that the lithium bis (fluorosulfonyl) imide is mixed with lithium hexafluorophosphate according to a certain proportion to form a mixed lithium salt, the synergistic effect can be achieved, the electrochemical stability and the thermal stability of the battery are improved, and higher discharge capacity can be maintained at the temperature of-30-45 ℃. In one embodiment, the concentration of lithium hexafluorophosphate in the lithium battery electrolyte is 0.8-1.2 mol/L; the concentration of the lithium bifluorosulfonyl imide in the lithium battery electrolyte is 0.3-0.4 mol/L, and the concentrations of the lithium hexafluorophosphate and the lithium bifluorosulfonyl imide in the lithium battery electrolyte are controlled, so that the conductivity and the stability of the electrolyte can be improved, and the defects of high cost, corrosion of aluminum foil and the like can be overcome.
Wherein the organic solvent is a mixed solvent at least comprising ethylene carbonate, propylene carbonate, dimethyl carbonate and ethyl methyl carbonate. The advantages can be complemented by using a mixed solvent, namely a multi-component solvent system, and mixing the cyclic carbonate with the chain carbonate for use. In one embodiment, the mixed solvent comprises the following components in percentage by volume: 22.5-27.5% of ethylene carbonate, 2.5-7.5% of propylene carbonate, 27.5-32.5% of dimethyl carbonate and 37.5-42.5% of ethyl methyl carbonate. The solvent components in a specific proportion are mixed, so that the ionic conductivity of the electrolyte can be ensured, and the technical effects of low viscosity and low temperature resistance are achieved.
Furthermore, the environmental temperature of the lithium battery electrolyte is controlled to be 20-25 ℃, the humidity is less than or equal to 1 percent, the oxygen content is less than or equal to 1ppm, and the water content is less than or equal to 0.1ppm in the preparation process, so that the purity of the organic solvent and the electrochemical stability window are ensured, and the lithium salt is prevented from being decomposed to cause the failure of the electrolyte.
The following is a detailed description of the embodiments.
Example 1
The lithium battery electrolyte comprises the following components in parts by mass: 80% of organic solvent (the organic solvent comprises 25% of ethylene carbonate, 5% of propylene carbonate, 30% of dimethyl carbonate and 40% of ethyl methyl carbonate by volume percent), 0.5% of vinylene carbonate, 0.3% of 1, 3-propane sultone, 0.5% of fluoroethylene carbonate, 0.5% of lithium difluorophosphate and 1% of ethylene sulfate; tris (trimethylsilane) phosphite 0.15%.
Meanwhile, the lithium battery electrolyte also comprises 1mol/L lithium hexafluorophosphate and 0.35mol/L lithium bis (fluorosulfonyl) imide.
Comparative example 1
The main difference between the comparative example 1 and the example 1 is that in the lithium battery electrolyte, the additive components are 0.5% by mass of vinylene carbonate, 0.5% by mass of fluoroethylene carbonate and 1% by mass of lithium difluorophosphate.
Comparative example 2
The main difference between comparative example 2 and example 1 is that in the lithium battery electrolyte, the additive components, by mass, are vinylene carbonate 0.5%, 1, 3-propane sultone 0.5%, fluoroethylene carbonate 0.5%, lithium difluorophosphate 1%, vinyl sulfate 1%, and tris (trimethylsilane) phosphite 0.15%.
Comparative example 3
Comparative example 3 is mainly different from example 1 in that, in the lithium battery electrolyte, the additive components, by mass, are vinylene carbonate 0.7%, 1, 3-propane sultone 0.1%, fluoroethylene carbonate 0.5%, lithium difluorophosphate 1%, vinyl sulfate 1%, and tris (trimethylsilane) phosphite 0.15%.
The electrolyte of the embodiment 1 and the comparative examples 1 to 3 is manufactured into the soft-package lithium ion battery by adopting a soft-package lamination process.
The preparation method of the soft package lithium ion battery comprises the following steps: and (3) laminating and assembling the lithium iron phosphate positive plate, the graphite negative plate and the PE + OBS diaphragm, baking until the moisture is qualified, injecting the electrolyte in the embodiment 1 and the comparative examples 1-3, performing hot pressing formation and high-temperature standing, packaging, grading, standing at normal temperature to obtain a finished battery, and performing a-25 ℃ multiplying power charge and discharge test on the lithium iron phosphate battery.
Example 2
The difference from the example 1 is that the lithium battery electrolyte comprises 1.2mol/L lithium hexafluorophosphate and 0.4mol/L lithium bis-fluorosulfonylimide
Example 3
The difference from the embodiment 1 is that the lithium battery electrolyte comprises 0.8mol/L lithium hexafluorophosphate and 0.3mol/L lithium bis-fluorosulfonylimide.
Example 4
The difference from the embodiment 1 is that the lithium battery electrolyte comprises 85% of organic solvent by mass, and the organic solvent comprises 22.5% of ethylene carbonate, 7.5% of propylene carbonate, 32.5% of dimethyl carbonate and 37.5% of ethyl methyl carbonate by volume percentage.
Example 5
The difference from the embodiment 1 is that the electrolyte of the lithium battery comprises 75% of organic solvent by mass, and the organic solvent comprises 27.5% of ethylene carbonate, 2.5% of propylene carbonate, 27.5% of dimethyl carbonate and 42.5% of ethyl methyl carbonate by volume percentage.
Example 6
The difference from the embodiment 1 is that the lithium battery electrolyte comprises, by mass, 0.55% of vinylene carbonate, 0.35% of 1, 3-propane sultone, 0.55% of fluoroethylene carbonate, 0.6% of lithium difluorophosphate and 1.2% of vinyl sulfate; tris (trimethylsilane) phosphite) 0.2%.
Example 7
The difference from the embodiment 1 is that the lithium battery electrolyte comprises 0.45 percent of vinylene carbonate, 0.25 percent of 1, 3-propane sultone, 0.45 percent of fluoroethylene carbonate, 0.4 percent of lithium difluorophosphate and 0.8 percent of vinyl sulfate in parts by mass; tris (trimethylsilane) phosphite) 0.1%.
-25 ℃ rate charge and discharge test: the SOC of the soft package lithium ion batteries prepared in the examples 1-7 and the comparative examples 1-3 is adjusted to 100% at the temperature of minus 25 ℃, the soft package lithium ion batteries are charged and discharged at different multiplying powers of minus 25 ℃ for 30min, the test is finished after the soft package lithium ion batteries are placed aside, and the test results are shown in the table 1.
TABLE 1 lithium iron phosphate battery-25 deg.C different multiplying power discharge test recording table
From the data in table 1, the results of different-rate discharge tests at-25 ℃ for lithium batteries indicate that the batteries in examples 1 to 7 have higher discharge capacity retention rate (> 80%) under different rates, show good low-temperature resistance, and are significantly better than the comparative examples, wherein example 1 is a preferred example of the present invention, and shows excellent discharge capacity retention rate under the conditions of 0.1C, 0.2C, 0.5C, 1C, 3C, and 5C rates.
As can be seen from FIGS. 1 to 4, the lithium battery prepared in example 1 has a 1C/3C/5C discharge platform and a 1C charge platform which are higher than those of comparative examples 1 to 3 at a low temperature of-25 ℃, and has excellent low-temperature output characteristics.
The test results in table 1 and fig. 1-4 show that the low-temperature rate discharge performance of the soft-package lithium iron phosphate battery prepared by using the electrolyte in example 1 is significantly higher than that of the battery prepared by using each pair of proportional electrolytes. It is also shown that the mixed additive provided in the present invention needs to be used under specific kinds and amount ratio conditions, otherwise the battery performance is affected.
The above embodiments are the best mode for the invention, but the invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the invention should be construed as equivalents thereof, and they are all included in the scope of the invention.
Claims (10)
1. The lithium battery electrolyte is characterized by comprising the following components: lithium salts, organic solvents and additives;
wherein the additive is a mixed additive comprising vinylene carbonate, 1, 3-propane sultone, fluoroethylene carbonate, lithium difluorophosphate, vinyl sulfate and tris (trimethylsilane) phosphite.
2. The lithium battery electrolyte as claimed in claim 1, comprising, in mass percent: 14% -20% of lithium salt, 75% -85% of organic solvent and 1.0% -5.0% of additive.
3. The lithium battery electrolyte as claimed in claim 1, wherein the weight ratio of vinylene carbonate, 1, 3-propane sultone, fluoroethylene carbonate, lithium difluorophosphate, vinyl sulfate and tris (trimethylsilane) phosphite is (4.5-5.5): (2.5-3.5): (4.5-5.5): (4-6): (8-12): 1-2).
4. The lithium battery electrolyte as claimed in claim 3, wherein the mass ratio of vinylene carbonate, 1, 3-propane sultone, fluoroethylene carbonate, lithium difluorophosphate, vinyl sulfate and tris (trimethylsilane) phosphite is 5: 3: 5: 10: 1.5.
5. The lithium battery electrolyte of claim 1 wherein the lithium salt comprises lithium hexafluorophosphate and lithium bis-fluorosulfonylimide.
6. The lithium battery electrolyte as claimed in claim 5, wherein the concentration of the lithium hexafluorophosphate in the lithium battery electrolyte is 0.8 to 1.2 mol/L; the concentration of the lithium bis (fluorosulfonyl) imide in the lithium battery electrolyte is 0.3-0.4 mol/L.
7. The electrolyte for a lithium battery according to claim 1, wherein the organic solvent is a mixed solvent including at least ethylene carbonate, propylene carbonate, dimethyl carbonate and ethyl methyl carbonate.
8. The lithium battery electrolyte as claimed in claim 7, wherein the mixed solvent comprises, in volume percent: 22.5-27.5% of ethylene carbonate, 2.5-7.5% of propylene carbonate, 27.5-32.5% of dimethyl carbonate and 37.5-42.5% of ethyl methyl carbonate.
9. The lithium battery electrolyte as claimed in claim 8, wherein the mixed solvent comprises, in volume percent: 25% of ethylene carbonate, 5% of propylene carbonate, 30% of dimethyl carbonate and 40% of methyl ethyl carbonate.
10. A lithium battery comprising the lithium battery electrolyte as claimed in any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117393860A (en) * | 2023-12-12 | 2024-01-12 | 天津力神电池股份有限公司 | Quick-charging electrolyte, battery filling method and battery |
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