CN113764739A - Wide-temperature-zone high-concentration double-salt flame-retardant electrolyte and application thereof in high-nickel lithium ion battery - Google Patents
Wide-temperature-zone high-concentration double-salt flame-retardant electrolyte and application thereof in high-nickel lithium ion battery Download PDFInfo
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a wide-temperature-zone high-concentration double-salt flame-retardant electrolyte, which consists of two main lithium salts and a flame-retardant organic solvent. Wherein the two main lithium salts are fluorinated alkoxy lithium borate and sulfonyl imide lithium, and the total concentration is 3-10 mol/L; the flame-retardant organic solvent is a mixed organic solvent of a phosphate compound and a low-freezing-point ester compound. The electrolyte provided by the invention has the advantages of excellent flame retardant property, wide working temperature range, high ionic conductivity, wide electrochemical window and the like. The invention also discloses the application of the electrolyte in the next generation of high nickel lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a wide-temperature-zone high-concentration double-salt flame-retardant electrolyte and application thereof in a high-nickel lithium ion battery.
Background
Lithium Ion Batteries (LIBs) have been commercialized successfully since the 90 s of the 20 th century, from portable consumer electronics to large Electric Vehicles (EVs) and renewable Energy Storage Systems (ESSs), throughout our daily lives. However, at present, the "mileage" problem of LIBs is increasingly prominent. High nickel material lithium nickel cobalt manganese oxygen (LiNi)1-x-yCoxMnyO2) And lithium nickel cobalt aluminum oxide (LiNi)0.8Co0.15Al0.05O2) Have high capacity, high voltage characteristics, and have attracted considerable interest as an option for increasing the energy density of LIBs (see Hyung-Joo Noh et al, j.power Sources 2013,233: 21-130; junhyeok Kim et al, adv. energy Mater.2018,8(6): 1702028). However, the large-scale commercialization of LIBs based on NCM or NCA has been severely hampered by the increased risk of thermal runaway (see Gaojie Xu et al, Energy Storage Materials 2020,31: 72-86). The electrolyte plays an important role in triggering thermal runaway of LIBs, and the traditional LiPF6Base carbonate electrolytes are thermally unstable and flammable (see Gaojie Xu et al, adv. energy Mater.2018,8(9): 1701398; Angew. chem. int. Ed.2020,59(9): 3400-. Therefore, one of the most important strategies to improve the safety of LIBs is to formulate flame retardant electrolytes with thermally stable lithium salts.
Phosphate ester compounds have been extensively studied as flame retardant solvents/additives for LIBs. But the electrochemical compatibility of the phosphate ester compound and the graphite negative electrode is poor (see Xianming Wang et al, J.electrochem. Soc.2001,148(10): A1066-A1071). With the rapid development of high-concentration electrolyte, research shows that the phosphate-based high-concentration electrolyte has higher compatibility with a graphite cathode (see Xianming Wang et al, J.electrochem. Soc.2006,153(1): A135-A139; Ziqi Zeng et al, nat. energy 2018,3(8): 674-681). However, the phosphate-based high-concentration electrolyte still has the disadvantages of high viscosity and low ionic conductivity. Therefore, a low-viscosity and low-freezing-point co-solvent is required to be used in combination with the phosphate ester compound to reduce the viscosity of the electrolyte and improve the ionic conductivity.
Disclosure of Invention
The invention aims to provide a wide-temperature-zone high-concentration flame-retardant electrolyte for a high-nickel lithium ion battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
a wide-temperature-zone high-concentration double-salt flame-retardant electrolyte consists of lithium salt and a flame-retardant organic solvent, wherein the lithium salt is fluoro alkoxy lithium borate and lithium sulfimide, and the flame-retardant organic solvent is a mixed organic solvent of a phosphate compound and a low-freezing-point (-100-0 ℃) ester compound; wherein the total concentration of the two lithium salts in the electrolyte is 3-10 mol/L.
The structure of the lithium fluoroalkoxyborate is shown as a general formula a or b:
wherein R is C1-C9 fluoroalkyl, C1-C9 alkyl substituted by at least one C5-C9 fluorocycloalkyl group, or C1-C9 fluoroalkyl substituted by at least one aryl group.
The R in the general formula of the lithium fluoroalkoxyborate can be the same or different
The lithium sulfonimide is bis (trifluoromethylsulfonyl) lithium imide (LiTFSI) or bis (fluorosulfonyl) lithium imide (LiFSI).
The concentration ratio of the fluorinated alkoxy lithium borate to the sulfonyl imide lithium is 1: 4-4: 1, preferably, the concentration ratio of the lithium fluoroalkoxyborate to the lithium sulfonimide is 2: 3-3: 2.
the phosphate compound is one or more of trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP), tris (2,2, 2-trifluoroethyl) phosphate (TFP), bis (2,2, 2-trifluoroethyl) -methyl phosphate (BMP), (2,2, 2-trifluoroethyl) -diethyl phosphate (TDP), tris (2,2, 2-difluoroethyl) phosphate (TFHP), tripropyl phosphate (TPrP), tris (3,3, 3-trifluoropropyl) phosphate (3F-TPrP), tris (2,2,3, 3-tetrafluoropropyl) phosphate (4F-TPrP), and tris (2,2,3,3, 3-pentafluoropropyl) phosphate (5F-TPrP); preferably trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP), tris (2,2, 2-trifluoroethyl) phosphate (TFP) or bis (2,2, 2-trifluoroethyl) -methyl phosphate (BMP).
The low freezing point ester compound is one or more of Propylene Carbonate (PC), diethyl carbonate (DEC), gamma-butyrolactone (GBL), Methyl Formate (MF), Ethyl Formate (EF), Propyl Formate (PF), Butyl Formate (BF), Methyl Acetate (MA), Ethyl Acetate (EA), Propyl Acetate (PA), Butyl Acetate (BA), Methyl Propionate (MP), Ethyl Propionate (EP), Propyl Propionate (PP), Butyl Propionate (BP), Methyl Butyrate (MB), Ethyl Butyrate (EB), Propyl Butyrate (PB) and butyl butyrate; preferably Propylene Carbonate (PC), diethyl carbonate (DEC), gamma-butyrolactone (GBL), Methyl Formate (MF), Ethyl Formate (EF), Methyl Acetate (MA) or Ethyl Acetate (EA).
The volume ratio of the phosphate ester compound to the low freezing point ester compound is 1: 9-9: 1, preferably, the volume ratio of the phosphate ester compound to the low freezing point ester compound is 2: 3-3: 2.
a wide-temperature-zone high-concentration double-salt flame-retardant electrolyte is applied to a high-nickel lithium ion battery.
The high-nickel lithium ion battery comprises an anode, a cathode and electrolyte, wherein the electrolyte is the wide-temperature-area high-concentration double-salt flame-retardant electrolyte.
The positive electrode is lithium nickel cobalt manganese oxygen (LiNi)1-x-yCoxMnyO2) Lithium nickel cobalt aluminum oxide (Li)xNi1-y-zCoyAlzO2X is more than or equal to 1 and less than or equal to 1.08, y is more than 0.05 and less than or equal to 0.15, and z is more than 0 and less than or equal to 0.05); the negative electrode is graphite.
The invention has the advantages that:
the electrolyte contains two main salts and a flame-retardant organic solvent, wherein the lithium salt contains dihydroxy chelating fluoroalkoxyl lithium fluoroalkoxyborate, the dihydroxy chelating fluoroalkoxyl lithium borate and double salt lithium sulfimide are mixed at high concentration to form a boron-containing and sulfur-containing fluorine-containing compound SEI layer to achieve the effect of protecting an electrode, and then the lithium salt is mixed with a phosphate compound and a low-freezing-point (-100 ℃ -0 ℃) ester compound according to a certain proportion so that the lithium salt can have excellent performances such as high ionic conductivity, high safety, high compatibility and the like which are suitable for a high-nickel lithium ion battery.
1) The wide-temperature-range high-concentration double-salt flame-retardant electrolyte provided by the invention has good compatibility with a graphite cathode, can effectively improve the safety performance of a high-nickel lithium ion battery, and has the advantages of excellent flame-retardant performance, wide working temperature range, high ionic conductivity, wide electrochemical window and the like.
2) The wide-temperature-region high-concentration double-salt flame-retardant electrolyte provided by the invention uses thermally stable double-salt lithium sulfonimide and fluoro-alkoxy lithium borate to form a synergistic effect on a battery interface, so that the improvement of the electrochemical performance of the battery is promoted.
3) The wide-temperature-zone high-concentration double-salt flame-retardant electrolyte provided by the invention has higher compatibility with high-nickel lithium ions of NCM/MCMB and NCA/MCMB, and shows excellent application prospect in next-generation high-nickel lithium ion batteries.
Drawings
FIG. 1 is a graph comparing the cycle performance of an MCMB/Li half cell assembled with the electrolytes of example 1 and comparative example 1 according to the present invention.
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.
According to the high-concentration flame-retardant electrolyte, the lithium sulfimide and the lithium fluoroalkoxyborate are used as double main salts of the electrolyte, the mixed organic solvent of the phosphate compound and the low-freezing-point ester compound is used as a solvent of the electrolyte, and the low-viscosity low-freezing-point cosolvent and the phosphate compound are matched for use, so that the viscosity of the electrolyte is reduced, and the ionic conductivity is improved; meanwhile, the lithium fluoride double-salt fluoro alkoxy borate and the lithium sulfimide form a synergistic effect on a battery interface with the thermally stable double-salt fluoro alkoxy borate and the thermally stable lithium sulfimide, and an SEI (solid electrolyte interphase) layer containing boron, sulfur and fluorine compounds is formed on a graphite cathode, so that the decomposition of a solvent is greatly inhibited, and the improvement of the electrochemical performance is further promoted; further, the electrolyte obtained by the invention can realize the excellent performance of the high-nickel anode/graphite cathode battery within a wide temperature range (-30-90 ℃).
Example 1
Slowly dissolving two main lithium salts of lithium bis (trifluoromethylsulfonyl) imide and lithium bis (tetrafluorobutyldioxy) borate in a volume ratio of 1: 1, trimethyl phosphate (TMP) and gamma-butyrolactone (GBL) organic solvent, so that the final concentration of lithium bis (trifluoromethylsulfonyl) imide in the system is 2 mol/L; the final concentration of lithium bis (tetrafluorobutyldioxy) borate is 2 mol/L; and then the system is stirred at room temperature until the high-concentration flame-retardant electrolyte is obtained after uniform mixing.
Example 2
Slowly dissolving two main lithium salts of lithium bis (fluorosulfonyl) imide and lithium bis (tetrafluorobutyldioxy) borate in a solvent with a volume ratio of 1: 1 in trimethyl phosphate (TMP) and gamma-butyrolactone (GBL) organic solvents, so that the final concentration of lithium bis (fluorosulfonyl) imide in the system is 2.5mol/L, and the final concentration of lithium bis (tetrafluorobutyldioxy) borate is 2.5 mol/L; and then stirring at room temperature until the mixture is uniformly mixed to obtain the high-concentration flame-retardant electrolyte.
Example 3
Slowly dissolving two main lithium salts of lithium bis (trifluoromethylsulfonyl) imide and lithium bis (tetrafluorobutyldioxy) borate in a volume ratio of 3: 1: 1, triphenyl phosphate (TPP), Propylene Carbonate (PC) and Methyl Formate (MF) organic solvents, so that the final concentration of lithium bis (trifluoromethylsulfonyl) imide in the system is 2mol/L, and the final concentration of lithium bis (tetrafluorobutyldioxy) borate is 2 mol/L; and then stirring at room temperature until the mixture is uniformly mixed to obtain the high-concentration flame-retardant electrolyte.
Example 4
Slowly dissolving two main lithium salts of lithium bis (trifluoromethylsulfonyl) imide and lithium bis (hexafluoro-2, 3-bis (trifluoromethyl) -2, 3-butyldioxy) borate in a volume ratio of 2: 3 in a tri (2,2, 2-trifluoroethyl) phosphate (TFP) and a gamma-butyrolactone (GBL) organic solvent, so that the final concentration of lithium bis (trifluoromethylsulfonyl) imide in the system is 2mol/L, and the final concentration of lithium bis (hexafluoro-2, 3-bis (trifluoromethyl) -2, 3-butyldioxy) borate in the system is 3 mol/L; and then stirring at room temperature until the mixture is uniformly mixed to obtain the high-concentration flame-retardant electrolyte.
Comparative example 1
Lithium bis (trifluoromethylsulfonyl) imide was dissolved in a solvent at a volume ratio of 1: 1 in trimethyl phosphate (TMP) and gamma-butyrolactone (GBL) organic solvents, so that the final concentration of lithium bis (trifluoromethylsulfonyl) imide in the system is 4mol/L, and stirring is carried out at room temperature until the lithium bis (trifluoromethylsulfonyl) imide is uniformly mixed to obtain the flame-retardant electrolyte.
Comparative example 2
Lithium hexafluorophosphate salt was slowly dissolved in a volume ratio of 1: 1: 1 Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) in an organic solvent to make the final concentration of lithium hexafluorophosphate in the system be 1mol/L, and then stirring at room temperature until the lithium hexafluorophosphate and the lithium hexafluorophosphate are uniformly mixed to obtain the electrolyte.
Comparative example 3
Slowly dissolving two main lithium salts of lithium bis (trifluoromethylsulfonyl) imide and lithium bis (tetrafluorobutyldioxy) borate in a volume ratio of 1: 1, trimethyl phosphate (TMP) and Ethylene Carbonate (EC) organic solvent, so that the final concentration of lithium bis (trifluoromethylsulfonyl) imide in the system is 2 mol/L; the final concentration of lithium bis (tetrafluorobutyldioxy) borate is 2 mol/L; and then the system is stirred at room temperature until the high-concentration flame-retardant electrolyte is obtained after uniform mixing.
And (3) flame retardant test:
the electrolytes of examples 1 to 4 and comparative examples 1 to 2 were subjected to a flame-retardant test: a glass fiber paper having a thickness of 5mm was cut into a 15X 20mm long strip, the glass fiber strip was sufficiently soaked in an electrolyte, and the glass fiber strip was taken out and ignited by a lighter, and the test results are shown in Table 1.
TABLE 1
| Sample (I) | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| Flame retardancy | Non-combustible | Non-combustible | Non-combustible | Non-combustible | Non-combustible | Inflammable |
As can be seen from Table 1, the electrolyte using the flame-retardant solvent of the present invention does not burn in the ignition test of the lighter, indicating that the electrolyte of the present invention has excellent flame-retardant properties.
And (3) testing the performance of the assembled battery:
1) manufacturing a lithium battery:
manufacturing an MCMB/Li half cell:
taking a 300 mu m lithium sheet as a positive electrode, and cutting a positive electrode wafer with the diameter of 14mm in a glove box by using a punching machine; mixing graphite (MCMB), conductive carbon black (Super P) and Styrene Butadiene Rubber (SBR) according to a weight ratio of 85:5:10, adding water, uniformly stirring to prepare negative electrode slurry, coating the negative electrode slurry on a copper foil current collector, drying at 120 ℃, rolling, and cutting into a negative electrode wafer with the diameter of 16mm by using a punching machine; the positive and negative plates were separated by glass fiber, and then the electrolytes of example 1 and comparative example 1 were injected, respectively, to prepare button cells.
Preparing a NCM622/MCMB full battery:
mixing lithium nickel manganese cobalt oxide (NCM622), conductive carbon black (Super P) and polyvinylidene fluoride according to a weight ratio of 85:5:10, adding N-methyl pyrrolidone, uniformly stirring to prepare anode slurry, coating the anode slurry on an aluminum foil current collector, drying at 120 ℃, rolling and then using a punching machine to obtain an anode wafer with the diameter of 14 mm; mixing graphite (MCMB), conductive carbon black (Super P) and Styrene Butadiene Rubber (SBR) according to a weight ratio of 85:5:10, adding water, uniformly stirring to prepare negative electrode slurry, coating the negative electrode slurry on a copper foil current collector, drying at 120 ℃, rolling, and cutting into a negative electrode wafer with the diameter of 16mm by using a punching machine; the positive and negative plates were separated by glass fibers and then separately injected with the electrolytes of examples 1-4 and comparative examples 1-3 to make button cells.
Battery information:
2) and (3) testing the compatibility of graphite:
MCMB/Li half-cells were assembled using the electrolytes of example 1 and comparative example 1, and the compatibility of the electrolytes with graphite electrodes was evaluated.
As can be seen from fig. 1, the electrolyte of example 1 provided by the present invention has good electrochemical compatibility with the MCMB negative electrode, while the MCMB/Li half-cell using the electrolyte of comparative example 1 has poor cycle performance.
And (3) testing the battery performance:
the lithium batteries of the batteries 1 to 6 corresponding to the solutions of examples 1 to 4 and comparative examples 2 to 3 were subjected to a charge-discharge cycle test at room temperature (25 ℃), the test voltage range was 2.7V to 4.3V, the batteries were charged and discharged at a rate of 0.5C, and the discharge capacity and the capacity retention ratio of the batteries after 200 cycles were shown in table 2.
TABLE 2
| Battery with a battery cell | Battery 1 | Battery 2 | Battery 3 | Battery 4 | Battery 5 | Battery 6 |
| Discharge capacity/mAh/g | 135.7 | 131.6 | 129.2 | 133.8 | 63.2 | 89.6 |
| Capacity retention ratio/%) | 86 | 82.3 | 80.7 | 84.6 | 42.1 | 66.2％ |
As can be seen from Table 2, the electrolytes of examples 1-4, which are prepared by mixing the specific bi-main salt and the flame-retardant organic solvent, show good cycle performance at normal temperature.
3) High temperature performance:
the electrolytes of examples 1 to 4 and comparative examples 2 to 3 correspond to batteries 1 to 6, and lithium batteries were subjected to charge-discharge cycle tests at a high temperature of 60 ℃, the test voltage range was 2.7V to 4.3V, the batteries were charged and discharged at a rate of 0.5C, and the capacity retention ratios of the batteries after 200 cycles were shown in table 3. The electrolyte of the invention is proved to have good high-temperature performance.
4) Low temperature performance:
the electrolytes of examples 1 to 4 and comparative examples 2 to 3 correspond to batteries 1 to 6, and lithium batteries were subjected to charge-discharge cycle tests at a low temperature of 0 ℃, the test voltage range was 2.7V to 4.3V, the batteries were charged and discharged at a rate of 0.1C, and the capacity retention ratios of the batteries after 90 cycles of the cycles were shown in table 3. The lithium battery was charged at 0.1C at room temperature and discharged at-10 deg.C, -20 deg.C and-30 deg.C at 0.1C, and the battery capacity retention rate was as shown in Table 3. The data demonstrate that the electrolyte of the present invention has good low temperature performance.
TABLE 3
As can be seen from the experimental data in table 3, the electrolyte provided by the present invention has good high temperature performance and good low temperature performance.
Finally, it is to be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing examples, those skilled in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced and improved; any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A wide-temperature-zone high-concentration double-salt flame-retardant electrolyte consists of lithium salt and a flame-retardant organic solvent, and is characterized in that: the lithium salt is fluorinated alkoxy lithium borate and lithium sulfimide, and the flame-retardant organic solvent is a mixed organic solvent of a phosphate compound and a low-freezing-point ester compound; wherein the total concentration of the two lithium salts in the electrolyte is 3-10 mol/L.
2. The wide temperature zone high concentration double salt flame retardant electrolyte of claim 1, wherein: the structure of the lithium fluoroalkoxyborate is shown as a general formula a or b:
wherein R is C1-C9 fluoroalkyl, C1-C9 alkyl substituted by at least one C5-C9 fluorocycloalkyl group, or C1-C9 fluoroalkyl substituted by at least one aryl group.
3. The wide temperature zone high-concentration double-salt flame-retardant electrolyte as claimed in claim 2, wherein: the R in the general formula of the lithium fluoroalkoxyborate can be same or different and is-CH2CF2CF2CH2-*，
4. The wide temperature zone high concentration double salt flame retardant electrolyte of claim 1, wherein: the lithium sulfonimide is bis (trifluoromethylsulfonyl) lithium imide (LiTFSI) or bis (fluorosulfonyl) lithium imide (LiFSI).
5. The wide temperature zone high concentration double salt flame retardant electrolyte of claim 1, wherein: the concentration ratio of the fluorinated alkoxy lithium borate to the sulfonyl imide lithium is 1: 4-4: 1.
6. the wide-area, high-concentration, double-salt flame-retardant electrolyte of claim 1, wherein: the phosphate compound is one or more of trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP), tris (2,2, 2-trifluoroethyl) phosphate (TFP), bis (2,2, 2-trifluoroethyl) -methyl phosphate (BMP), (2,2, 2-trifluoroethyl) -diethyl phosphate (TDP), tris (2,2, 2-difluoroethyl) phosphate (TFHP), tripropyl phosphate (TPrP), tris (3,3, 3-trifluoropropyl) phosphate (3F-TPrP), tris (2,2,3, 3-tetrafluoropropyl) phosphate (4F-TPrP), and tris (2,2,3,3, 3-pentafluoropropyl) phosphate (5F-TPrP).
7. The wide temperature zone high concentration double salt flame retardant electrolyte of claim 1, wherein: the low freezing point ester compound is one or more of Propylene Carbonate (PC), diethyl carbonate (DEC), gamma-butyrolactone (GBL), Methyl Formate (MF), Ethyl Formate (EF), Propyl Formate (PF), Butyl Formate (BF), Methyl Acetate (MA), Ethyl Acetate (EA), Propyl Acetate (PA), Butyl Acetate (BA), Methyl Propionate (MP), Ethyl Propionate (EP), Propyl Propionate (PP), Butyl Propionate (BP), Methyl Butyrate (MB), Ethyl Butyrate (EB), Propyl Butyrate (PB) and butyl butyrate.
8. The wide temperature zone high concentration double salt flame retardant electrolyte of claim 1, wherein: the volume ratio of the phosphate ester compound to the low freezing point ester compound is 1: 9-9: 1.
9. the wide temperature zone high-concentration double-salt flame-retardant electrolyte as claimed in claim 1, wherein: the electrolyte is applied to a high-nickel lithium ion battery.
10. The high-nickel lithium ion battery comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that: the electrolyte is the high-concentration double-salt flame-retardant electrolyte in the wide temperature range of claim 1.
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