CN111326799A - Flame-retardant high-voltage electrolyte for lithium ion battery and preparation method thereof - Google Patents
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Abstract
The invention relates to a flame-retardant high-voltage electrolyte for a lithium ion battery and a preparation method thereof, wherein the electrolyte consists of lithium salt, a flame-retardant solvent and an additive, the flame-retardant solvent consists of carbonates, fluorocarbonates and fluoroethers, the fluorinated solvent is taken as a main body, and a conventional carbonate solvent and the additive are combined, so that the electrolyte has good wettability and incombustibility and higher ionic conductivity by utilizing the good wettability and the strong interfacial film-forming property of the fluorinated solvent and the higher lithium salt solubility of the conventional carbonate solvent; the flame-retardant electrolyte can be applied to lithium ion batteries with metal lithium as a negative electrode and can also be applied to lithium ion batteries with graphite negative electrodes; the lithium ion battery can be applied to both conventional voltage lithium ion batteries and high-voltage lithium ion batteries, and has good electrode material compatibility and wide application range.
Description
Technical Field
The invention belongs to the field of new energy lithium batteries, and particularly relates to a flame-retardant high-voltage electrolyte for a lithium ion battery and a preparation method thereof.
Background
Compared with the traditional nickel-metal hydride battery, lead-acid battery, alkaline manganese dioxide battery and the like, the lithium battery has the advantages of high working voltage, long cycle life, high energy density, no memory effect and the like, is widely applied to small 3C digital products such as portable style computers and mobile communication and large-scale vehicles such as electric bicycles and electric automobiles, and presents a larger and larger application market. According to future development planning in China, the green and environment-friendly electric automobile can gradually replace the traditional fuel oil vehicle, so that the power lithium battery for the automobile has wide market and application prospects. However, the conventional lithium battery mainly uses flammable organic solvent as the solvent of the electrolyte, which causes the lithium battery to be easily ignited and burnt or explode under abuse conditions of high temperature, short circuit, impact and the like, for example, the current report of spontaneous combustion of electric vehicles is rare. Flammable organic electrolyte is one of the main causes of battery combustion and explosion, and is a bottleneck factor which restricts the further expansion of the application range of the lithium battery and the development of the lithium battery towards larger size and higher energy.
In addition, in order to increase the energy density of lithium batteries, the use of high-voltage positive electrode materials is one of the solutions. However, the voltage of the conventional electrolyte reaches 4.3V (vs. Li/Li)+) In addition, the electrolyte is oxidized and decomposed, and the cycle stability of the lithium ion battery under high voltage is greatly reduced along with the cycle, so that the common application of the high-voltage anode material is limited. Therefore, the development of the high-safety high-performance lithium battery electrolyte which is flame-retardant, even completely non-combustible, high-pressure-resistant, and good in compatibility with the anode and cathode materials of the battery has very important practical significance and application value.
The currently published and reported flame-retardant lithium battery electrolyte mainly uses organic phosphorus, cyclic phosphazene, halogenated alkane and the like as solvents or flame-retardant additives to achieve the purpose of flame retardance or flame retardance of the electrolyte, and the organic phosphorus compound used as the flame-retardant additive generally reduces the electrochemical performance of the electrolyte and has poor compatibility with graphite cathode materials. Patent application No. 201610893223.4 discloses a highly safe electrolyte and a lithium battery, which adopts the method that a proper amount of cyclic phosphazene compound is added in the electrolyte of the conventional lithium battery as a flame retardant additive to achieve the functions of flame retardation of the electrolyte and overcharge prevention of the battery, the flame retardant electrolyte is only suitable for a lithium manganate battery, has a small application range and cannot be applied to lithium cobaltate, nickel cobalt manganese ternary lithium batteries and the like; patent application No. 201711188603.9 discloses a flame-retardant lithium battery electrolyte, which is prepared by mixing halogenated solvents such as tribromoethane and dibromomethylfuran with common solvents, so that the use capacity of the lithium battery reaches more than 80% of the theoretical capacity, the risk of spontaneous combustion of the lithium battery can be reduced, but the battery capacity exertion is low, the battery capacity cannot be fully exerted, and the energy density of the battery is reduced; patent application No. 201810315555.3 discloses a high safety type lithium battery electrolyte, which achieves the effects of flame retardance and overcharge prevention of the electrolyte by adding a phosphorus flame retardant additive and a benzene overcharge prevention additive into a conventional electrolyte. Patent application No. 201810390538.6 discloses a phosphine based flame-retardant high-nickel ternary lithium battery electrolyte, which consists of a conventional solvent, lithium salt and a flame-retardant additive, wherein the flame-retardant additive is a phosphite ester compound with high phosphorus content, the prepared electrolyte has good flame-retardant effect, good compatibility with a metal lithium negative electrode material, and the performance of the battery is basically normal; however, the invention patent uses phosphine and benzene compounds with higher toxicity, so that the application range of the invention is greatly limited; the invention is only suitable for the lithium battery with the negative electrode of the lithium metal, and has smaller application range. Patent application No. 201910286078.7 discloses a flame retardant electrolyte for metal lithium battery and its preparation method and application, wherein the electrolyte is composed of a phosphorus-containing compound such as phosphate or phosphite or a mixture thereof as a solvent, the solvent has good flame retardancy, the lithium salt is a mixture of lithium bistrifluoromethanesulfonylimide and lithium nitrate, and an organic compound capable of ring-opening polymerization such as vinylene carbonate and lithium hexafluorophosphate is used as an additive, the electrolyte has good flame retardancy when used in metal lithium battery, the battery capacity is normally exerted, and the cycle life is good. However, in the electrolyte of the invention, phosphate esters are used as a solvent, and although the electrolyte has better flame retardance, the solvent has higher viscosity and higher cost, and is only suitable for lithium batteries using metal lithium as a negative electrode, but not suitable for lithium batteries using graphite as a negative electrode, and has certain application limitation. Patent application No. 201910646351.2 discloses a high voltage electrolyte additive, a high voltage electrolyte containing the same, and a lithium ion battery, wherein a benzene series high voltage electrolyte additive is added in a conventional electrolyte, the additive can be decomposed preferentially before a basic solvent is decomposed, a layer of dense interfacial film is formed on the surface of an electrode, the decomposition of the electrolyte can be inhibited, and the circulation stability of the lithium ion battery under the high voltage (4.5V-4.8V) condition is improved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a flame-retardant high-voltage electrolyte for a lithium ion battery and a preparation method thereof.
The technical scheme adopted by the invention is as follows: a flame-retardant solvent consists of carbonates, fluoro-carbonates and fluoro-ethers; the volume ratio of the carbonate, the fluoro carbonate and the fluoro ether is 1-10: 2-12: 1-16.
Preferably, the fluoroether is linear fluoroether, and the structural formula is:
R1-O-R2；
wherein R is1And R2Is one of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl and isopentyl, or is one of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl and isopentyl groups in which some or all of the hydrogen atoms are replaced by fluorine.
Preferably, the fluoroether is one or more of 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether, 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 1,1,2,3, 3-hexafluoropropyl-2, 2, 2-trifluoroethyl ether, 1,1,1,3,3, 3-hexafluoropropyl-methyl ether, and 1,1,1,2,3, 3-hexafluoropropyl-2, 2,3, 3-tetrafluoropropyl ether.
Preferably, the carbonate is one or a mixture of more of Ethylene Carbonate (EC), 1, 2-dimethylethylene carbonate (1,2-BC), Propylene Carbonate (PC), Butylene Carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), di-n-propyl carbonate (DPC), diisopropyl carbonate (DIPC), dibutyl carbonate (DBC), Ethyl Propyl Carbonate (EPC), Methyl Propyl Carbonate (MPC) and derivatives thereof.
Preferably, the fluorocarbonates are mixtures of one or more of fluoroethylene carbonate (FEC), trifluoromethyl ethylene carbonate (CF3-EC), methyl trifluoroethyl carbonate (FEMC), bis trifluoroethyl carbonate (DFDEC), dimethyl Fluorocarbonate (FDMC) and derivatives thereof.
The flame-retardant high-voltage electrolyte for the lithium ion battery consists of lithium salt, a flame-retardant solvent and an additive;
preferably, the lithium salt concentration is 0.8-2mol/L, and the additive accounts for 0.1% -10% of the total volume or the total weight.
Preferably, the lithium salt is lithium hexafluorophosphate (LiPF)6) Lithium hexafluoroarsenate (LiAsF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) Lithium nitrate (LiNO)3) Lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium bistrifluorosulfonylimide (LiFSI), lithium bis (oxalato) borate (LiBOB) and lithium difluoro (oxalato) borate (LiODFB).
Preferably, the additive is a mixture of one or more of vinyl sulfate, vinyl sulfite, vinylene carbonate, 1, 3-propanesultone, vinyl 4-methylsulfite, β -sulfopropionic anhydride, trimethyl phosphate, triethyl phosphate, tris (2,2, 2-trifluoroethyl) phosphite, tris (2,2, 2-trifluoroethyl) phosphate, succinonitrile, adiponitrile, tris (4-fluorophenyl) phosphine, tris (2,2,3,3, 3-pentafluoropropyl) phosphate, pentafluoroethoxycyclophosphazene, tris (trimethylsilane) phosphite, tris (trimethylsilane) phosphate, 1,3 propanediol cyclic sulfate, methanedisulfonylidine, lithium difluorooxalate, lithium bistrifluoromethanesulfonylimide, lithium bisfluorosulfonylimide, lithium bisoxalato borate, lithium difluorophosphate, lithium hexafluorophosphate and lithium nitrate.
The preparation method of the flame-retardant high-voltage electrolyte for the lithium ion battery comprises the steps of dissolving lithium salt in a flame-retardant solvent, adding an additive after the lithium salt is completely dissolved, and uniformly stirring to form the flame-retardant high-voltage electrolyte for the lithium ion battery;
preferably, the specific steps are as follows:
step 1: dissolving lithium salt in a flame-retardant solvent, wherein the concentration of the lithium salt is 0.8-2mol/L, and the volume of each component in the flame-retardant solvent accounts for the total volume of the solution: 5-50% of carbonate, 10-60% of fluoro carbonate and 5-80% of fluoroether, and stirring to completely dissolve the lithium salt;
step 2: and (2) adding an additive into the solution formed in the step (1), wherein the additive accounts for 0.1-10% of the total volume or the total weight of the solution, and continuously stirring for 10 hours to form the uniform flame-retardant electrolyte solution for the high-voltage lithium battery.
The invention has the advantages and positive effects that: the flame-retardant high-pressure electrolyte takes a fluoro-solvent as a main body, combines a conventional carbonate solvent and an additive, and has good wettability and incombustibility and higher ionic conductivity (more than or equal to 5mS/cm) by utilizing the good wettability, incombustibility and stronger interfacial film-forming property of the fluoro-solvent and the higher lithium salt solubility of the conventional carbonate solvent;
the flame-retardant electrolyte can be applied to lithium ion batteries with metal lithium as a negative electrode and can also be applied to lithium ion batteries with graphite negative electrodes; the lithium ion battery can be applied to both conventional voltage lithium ion batteries and high-voltage lithium ion batteries, and has good compatibility of electrode materials and wide application range;
the electrolyte provided by the invention can enable the lithium battery to have excellent cycle life and better rate performance, and meanwhile, the safety of the battery is greatly improved, and the electrolyte has important practical significance for solving the safety anxiety and service life anxiety of the conventional lithium battery.
Drawings
FIG. 1 shows the cycle life curves of Li/Li symmetrical batteries assembled according to example 1 and comparative example 1 of the present invention;
FIG. 2 charge and discharge curves of an assembled NCM811/Li half-cell of example 1 of the present invention;
FIG. 3 assembled NCM811/Li half-cell cycle life curve of example 1 in the present invention;
FIG. 4 cycle life curve of assembled 5.5Ah NCM811/SiC flexible packaged full cell of example 1 of the present invention;
FIG. 5 HVLCO/Li half-cell charge-discharge curves assembled in example 1 of the present invention;
FIG. 6 is a combustion test conducted in example 1 of the present invention and comparative example 1.
Detailed Description
Aiming at the defects in the prior art, the invention provides the electrolyte for the lithium battery, which is flame-retardant, even completely non-combustible and has certain high-pressure resistance. The electrolyte disclosed by the invention not only has the characteristics of non-combustibility, high ionic conductivity, small viscosity and high pressure resistance (4.5V), but also has the characteristics of good compatibility with positive and negative electrode materials of a battery, particularly good compatibility with graphite negative electrode materials, and is simple in preparation process, low in cost and suitable for large-scale commercial production. The flame-retardant high-voltage lithium battery electrolyte can greatly improve the safety of the lithium battery on the premise of not reducing the electrochemical performance of the lithium battery, has important value and significance for improving the energy density and safety of the lithium battery for 3C equipment such as a power battery, a mobile phone and the like, and has wide application prospect.
In some embodiments of the invention, the flame-retardant high-voltage electrolyte for the lithium ion battery comprises lithium salt, a flame-retardant solvent and an additive, wherein the concentration of the lithium salt is 0.8-2mol/L, and the additive accounts for 0.1-10% of the total volume or the total weight; wherein the flame-retardant solvent consists of carbonates, fluoro-carbonates and fluoroethers, and the volume ratio of the carbonates to the fluoro-carbonates to the fluoroethers is 1-10: 2-12: 1-16.
Wherein, the fluoroether is fluoroether with linear structure, and the structural formula is as follows:
R1-O-R2；
wherein R is1And R2Is methyl, ethyl, propyl, isopropyl, butyl, sec-butylOne of isobutyl, tert-butyl, pentyl and isopentyl, or one of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl and isopentyl groups in which some or all of the hydrogen atoms are replaced by fluorine. Specifically, the fluoroether may be one or a mixture of 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether, 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 1,1,2,3,3, 3-hexafluoropropyl-2, 2, 2-trifluoroethyl ether, 1,1,1,3,3, 3-hexafluoropropyl-methyl ether, and 1,1,1,2,3, 3-hexafluoropropyl-2, 2,3, 3-tetrafluoropropyl ether.
The carbonate is one or more of Ethylene Carbonate (EC), 1, 2-dimethyl ethylene carbonate (1,2-BC), Propylene Carbonate (PC), Butylene Carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), di-n-propyl carbonate (DPC), diisopropyl carbonate (DIPC), dibutyl carbonate (DBC), Ethyl Propyl Carbonate (EPC), Methyl Propyl Carbonate (MPC) and derivatives thereof.
The fluorocarbonates are one or more of fluoroethylene carbonate (FEC), trifluoromethyl ethylene carbonate (CF3-EC), methyl trifluoroethyl carbonate (FEMC), bis trifluoroethyl carbonate (DFDEC), dimethyl Fluorocarbonate (FDMC) and derivatives thereof.
The lithium salt is lithium hexafluorophosphate (LiPF)6) Lithium hexafluoroarsenate (LiAsF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) Lithium nitrate (LiNO)3) Lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium bistrifluorosulfonylimide (LiFSI), lithium bis (oxalato) borate (LiBOB) and lithium difluoro (oxalato) borate (LiODFB).
The additive is one or a mixture of more of vinyl sulfate, vinyl sulfite, vinylene carbonate, 1, 3-propane sultone, 4-methyl vinyl sulfite, β -sulfopropionic anhydride, trimethyl phosphate, triethyl phosphate, tris (2,2, 2-trifluoroethyl) phosphite, tris (2,2, 2-trifluoroethyl) phosphate, succinonitrile, adiponitrile, tris (4-fluorophenyl) phosphine, tris (2,2,3,3, 3-pentafluoropropyl) phosphate, pentafluoroethoxycyclophosphazene, tris (trimethylsilane) phosphite, tris (trimethylsilane) phosphate, 1,3 propanediol cyclic sulfate, methanedisulfonylidine, lithium difluorooxalate borate, lithium bistrifluoromethanesulfonylimide, lithium bisfluorosulfonylimide, lithium bisoxalato borate, lithium difluorophosphate, lithium hexafluorophosphate and lithium nitrate.
The preparation method of the flame-retardant high-voltage electrolyte for the lithium ion battery comprises the steps of dissolving lithium salt in a flame-retardant solvent, adding an additive after the lithium salt is completely dissolved, and uniformly stirring to form the flame-retardant high-voltage electrolyte for the lithium ion battery;
the method comprises the following specific steps:
step 1: dissolving lithium salt in a flame-retardant solvent, wherein the concentration of the lithium salt is 0.8-2mol/L, and the volume of each component in the flame-retardant solvent accounts for the total volume of the solution: 5-50% of carbonate, 10-60% of fluoro carbonate and 5-80% of fluoroether, and stirring to completely dissolve the lithium salt;
step 2: and (2) adding an additive into the solution formed in the step (1), wherein the additive accounts for 0.1-10% of the total volume or the total weight of the solution, and continuously stirring for 10 hours to form the uniform flame-retardant electrolyte solution for the high-voltage lithium battery.
The following examples and comparative examples further illustrate specific embodiments of the present invention, but the present invention is not limited to the following examples. The following examples are all routine experimental methods without specific description; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
taking a certain amount of lithium hexafluorophosphate (LiPF)6) Dissolving in flame-retardant solvent, stirring and dissolving to obtain LiPF6The molar concentration of (a) is 1 mol/L. The solvent consists of fluoroethylene carbonate (FEC), dimethyl carbonate (DMC) and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether (HFE), wherein the FEC accounts for 30% of the total volume of the solution, the DMC accounts for 30% of the volume, and the HFE accounts for 40% of the volume. After lithium hexafluorophosphate is completely dissolved, 1% by mass of tris (2,2, 2-trifluoroethyl) phosphite is added, and the mixture is continuously stirred for 10 hours, so that the flame-retardant high-pressure lithium battery electrolyte provided by the invention is obtained.
Example 2:
taking a certain amount of lithium hexafluorophosphate (LiPF)6) Dissolving in flame-retardant solvent, stirring and dissolving to obtain LiPF6The molar concentration of (A) is 1.2 mol/L. The solvent consists of fluoroethylene carbonate (FEC), Ethyl Methyl Carbonate (EMC) and 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether (HFE), wherein the FEC accounts for 30% of the total volume of the solution, the DMC accounts for 32% by volume, and the HFE accounts for 38% by volume. After lithium hexafluorophosphate is completely dissolved, vinylene carbonate with the volume fraction of 1% is added, and the mixture is continuously stirred for 10 hours, so that one of the flame-retardant high-voltage lithium battery electrolyte provided by the invention is obtained.
Example 3:
taking a certain amount of lithium hexafluoroarsenate (LiAsF)6) Dissolving in flame-retardant solvent, stirring and dissolving to obtain LiPF6The molar concentration of (a) is 1 mol/L. The solvent consisted of fluoroethylene carbonate (FEC), diethyl carbonate (DEC) and 1,1,1,3,3, 3-hexafluoropropyl-methyl ether (HFE), with FEC accounting for 20% of the total volume of the solution, DEC accounting for 30% by volume and HFE accounting for 50% by volume. After the lithium salt is completely dissolved, adding 1% by volume of tris (trimethylsilane) phosphite and 1, 3% by volume of propylene glycol cyclic sulfate, and continuously stirring for 10 hours to obtain the flame-retardant high-voltage lithium battery electrolyte provided by the invention.
Example 4:
dissolving a certain amount of lithium bistrifluoromethanesulfonylimide (LiTFSI) in a flame-retardant solvent, and stirring to dissolve the LiTFSI, wherein the molar concentration of the LiTFSI is 1 mol/L. The solvent consisted of fluoroethylene carbonate (FEC), diethyl carbonate (DEC) and 1,1,2,3,3, 3-hexafluoropropyl-2, 2, 2-trifluoroethyl ether (HFE), with FEC accounting for 20% by volume of the total solution, DEC accounting for 25% by volume and HFE accounting for 55% by volume. After the lithium salt is completely dissolved, 1, 3-propane sultone and lithium bis (oxalato) borate with the mass fraction of 1 percent are added, and the mixture is continuously stirred for 10 hours to obtain the flame-retardant high-voltage lithium battery electrolyte.
Example 5:
taking a certain amount of lithium perchlorate (LiClO)4) Dissolving in flame-retardant solvent, stirring and dissolving to obtain LiClO4The molar concentration of (A) is 1.2 mol/L. The solvent is prepared from fluoroethylene carbonate (FEC), dibutyl carbonate (DBC) and 1,1,1,2,3, 3-hexafluoropropyl-2, 2,3, 3-tetrafluoropropyl ether (HF)E) The composition was 28% FEC, 40% DEC and 32% HFE by volume based on the total volume of the solution. to-be-LiClO4After the lithium bifluoride sulfimide is completely dissolved, 1% of lithium bifluoride sulfimide in mass percentage is added, and the mixture is continuously stirred for 10 hours to obtain the flame-retardant high-voltage lithium battery electrolyte.
Comparative example 1:
certain commercial electrolyte A, the electrolyte composition is LiPF of 1mol/L6And the solvent is EC + DEC + DMC (mass ratio of 1:1: 1).
The above-mentioned embodiments are only for illustrating the technical idea and features of the present invention, and not for limiting the technical scope of the present invention, and the purpose thereof is to make those skilled in the art understand the content of the present invention and to implement it accordingly, and all equivalent changes or modifications made according to the spirit of the present invention are within the protection scope of the present invention.
The electrochemical properties of the above examples and comparative examples were tested without specific reference according to the following experimental methods: the metal lithium sheet or graphite material is used as a negative electrode, the PP/PE/PP three-layer composite membrane is used as a diaphragm, and the positive electrode material can be lithium cobaltate, lithium iron phosphate, high nickel ternary material (NCM811), High Voltage Lithium Cobaltate (HVLCO) and the like. The graphite negative electrode material can be natural graphite, artificial graphite, mesocarbon microbeads and the like. The positive and negative pole pieces are prepared by mixing positive and negative pole materials, a conductive agent and a bonding agent according to a certain proportion to form uniform slurry, uniformly coating the slurry on an aluminum foil and a copper foil, and drying and rolling the slurry in vacuum to obtain the positive and negative pole pieces. Button cell assembly was performed in a glove box and flexible packaged cells were completed in a dry room with a relative humidity of less than 1%. Assembling an NCM811/Li and HVLCO/Li half-cell and an NCM 811/graphite flexible package full-cell by using the flame-retardant high-voltage electrolyte provided by the invention; Li/Li symmetrical batteries are respectively assembled by the flame-retardant high-voltage electrolyte and a certain commercial electrolyte provided by the invention, and the stability of the battery to metal lithium is tested. The prepared battery is tested for electrical property by using a full-automatic charge-discharge tester.
TABLE 1 comparison of electrochemical performances of NCM811/Li half-cells assembled in examples and comparative examples
As can be seen from table 1, the flame-retardant high-voltage electrolyte has an obvious advantage in cycle life when used in a lithium ion battery using metallic lithium as a negative electrode, because a large amount of fluorinated solvent is used, the fluorinated solvent and the metallic lithium chemically react on the surface of the metallic lithium, and a layer of dense LiF-rich interface protective film (SEI) is generated on the surface of the metallic lithium, and the SEI film improves the cycle stability of the metallic lithium, thereby greatly prolonging the cycle life of the metallic lithium battery. To further verify the advantage of the flame retardant electrolyte in lithium metal cycling stability, Li/Li symmetric batteries were assembled with example 1 and comparative example 1, respectively, at 0.5mA/cm2The current density of (a) was charged and discharged, and the potential polarization was significantly increased after 400h cycling of the cell assembled in comparative example 1; after the battery assembled in example 1 is cycled for 1500 hours, the potential polarization is not obviously increased, which shows that the flame-retardant electrolyte has good stabilizing effect on the lithium metal, as shown in fig. 1. The room-temperature ionic conductivity of the flame-retardant high-voltage electrolyte in example 1 can reach 5.5mS/cm through a test, and as can be seen from fig. 2 and fig. 3, in a lithium battery using metal lithium as a negative electrode, the battery material capacity can be fully exerted, the cycle performance is good, the rate capability is good due to high ionic conductivity, and the capacity retention rate reaches 85.8% after the battery using metal lithium as the negative electrode is cycled for 200 times at a rate of 0.5C.
The flame-retardant high-voltage electrolyte can be applied to metal lithium batteries and lithium ion batteries with graphite as a negative electrode. As can be seen from fig. 4, the soft-package full-cell with silicon carbon as the negative electrode normally develops capacity, the cycle performance is good, and the capacity retention rate can reach 90% after 200 cycles. The poor compatibility of the flame-retardant electrolyte solution with the phosphorus flame-retardant additive and graphite negative electrodes generally leads to poor cycle performance of the battery. The flame-retardant high-pressure electrolyte mainly adopts a self-non-combustible fluorinated solvent to realize the flame retardance of the electrolyte, and a flame-retardant additive is not used; in some embodiments of the invention, the negative electrode film-forming additive is used, and the additive can react on the surface of the graphite negative electrode to generate a firm and compact SEI film before the electrolyte solvent reacts on the surface of the graphite negative electrode, so that the continuous reduction reaction of the electrolyte solvent on the surface of the graphite negative electrode is prevented, the cycle life of the battery is greatly prolonged, and the flame-retardant high-voltage electrolyte can be applied to a lithium ion battery taking graphite as the negative electrode. Most commercial lithium ion batteries at present adopt graphite materials as battery cathodes, so that the flame-retardant high-voltage electrolyte has important practical value.
The flame-retardant high-voltage electrolyte can also be applied to a high-voltage lithium ion battery, as shown in fig. 5, the high-voltage electrolyte is applied to an HVLCO/Li battery, the charging and discharging voltage range is 3V-4.5V, the capacity of a positive electrode material is normally exerted, and the cycling stability is good, so that the electrolyte can generate a stable interface film on the surfaces of the positive and negative electrode materials under the combined action of a fluorinated solvent and an additive, the interface film has stable electrochemical properties under high voltage (4.5V), can isolate the electrode material from contacting with the electrolyte to continuously generate chemical reaction, has the function of stabilizing the crystal structure of the positive and negative electrode materials, is not oxidized and decomposed under high voltage, has stable electrochemical properties, and has better cycle life.
As shown in FIG. 6, in the process of continuous firing of a flame gun for 10-30S, the flame-retardant high-voltage electrolyte is always non-combustible and shows good non-combustibility; and the common commercial electrolyte is burnt for 1-2s to start continuous combustion. Certain embodiments of the present invention provide electrolytes with outstanding safety advantages compared to common commercial electrolytes.
In conclusion, the flame-retardant high-voltage electrolyte provided by the invention is simple in preparation process, low in cost, suitable for large-scale application, excellent in flame-retardant safety and good in electrochemical performance. The lithium ion battery cathode can be applied to lithium ion batteries taking metal lithium as a cathode, and can also be applied to lithium ion batteries with graphite cathodes. In the aspect of application of the metal lithium battery, the electrochemical performance is superior to that of the conventional commercial electrolyte, and the cycle life is longer; in the application aspect of lithium ion batteries taking graphite as a negative electrode, the electrochemical performance is basically equivalent to that of the conventional electrolyte. In addition, the flame-retardant electrolyte can also be applied to a 4.5V high-voltage lithium ion battery, and has good cycle stability. The flame-retardant high-voltage electrolyte provides reliable technical support for improving the safety and application range of the lithium battery, and lays a foundation for larger-scale application of power batteries, solid-state lithium batteries and the like in the fields of electric automobiles, energy storage power stations, portable 3C electronic equipment and the like.
The embodiments of the present invention have been described in detail, but the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. A flame-retardant solvent is characterized in that: consisting of carbonates, fluorocarbonates and fluoroethers; the volume ratio of the carbonate, the fluoro carbonate and the fluoro ether is 1-10: 2-12: 1-16.
2. The flame-retardant solvent according to claim 1, characterized in that: the fluoroether is linear fluoroether, and the structural formula is as follows:
R1-O-R2；
wherein R is1And R2Is one of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl and isopentyl, or is one of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl and isopentyl groups in which some or all of the hydrogen atoms are replaced by fluorine.
3. The flame-retardant solvent according to claim 2, characterized in that: the fluoroether is one or more of 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether, 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 1,1,2,3,3, 3-hexafluoropropyl-2, 2, 2-trifluoroethyl ether, 1,1,1,3,3, 3-hexafluoropropyl-methyl ether and 1,1,1,2,3, 3-hexafluoropropyl-2, 2,3, 3-tetrafluoropropyl ether.
4. The flame-retardant solvent according to claim 1, characterized in that: the carbonate is one or more of ethylene carbonate, 1, 2-dimethyl ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl propyl carbonate, methyl propyl carbonate and derivatives thereof.
5. The flame-retardant solvent according to claim 1, characterized in that: the fluoro carbonic ester is one or more of fluoro ethylene carbonate, trifluoromethyl ethylene carbonate, methyl trifluoro ethyl carbonic ester, bis trifluoro ethyl carbonic ester, fluoro dimethyl carbonate and its derivative.
6. A flame-retardant high-voltage electrolyte for a lithium ion battery comprising the flame-retardant solvent according to any one of claims 1 to 5, characterized in that: the flame-retardant lithium salt battery is composed of lithium salt, the flame-retardant solvent and an additive; the concentration of the lithium salt is 0.8-2mol/L, and the additive accounts for 0.1-10% of the total volume or the total weight.
7. The flame-retardant high-voltage electrolyte for the lithium ion battery according to claim 6, wherein: the lithium salt is one or a mixture of more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium perchlorate, lithium nitrate, lithium bistrifluoromethanesulfonylimide, lithium difluorosulfonylimide, lithium bisoxalato borate and lithium difluorooxalato borate.
8. The flame-retardant high-voltage electrolyte for lithium ion batteries according to claim 6, wherein the additive is one or more selected from the group consisting of vinyl sulfate, vinyl sulfite, vinylene carbonate, 1, 3-propanesultone, 4-methyl vinyl sulfite, β -sulfopropionic anhydride, trimethyl phosphate, triethyl phosphate, tris (2,2, 2-trifluoroethyl) phosphite, tris (2,2, 2-trifluoroethyl) phosphate, succinonitrile, adiponitrile, tris (4-fluorophenyl) phosphine, tris (2,2,3,3, 3-pentafluoropropyl) phosphate, pentafluoroethoxycyclophosphazene, tris (trimethylsilane) phosphite, tris (trimethylsilane) phosphate, 1, 3-propanediol cyclic sulfate, methanedisulfonylidene, lithium difluorooxalatoborate, lithium bistrifluoromethanesulfonylimide, lithium bisfluorosulfonylimide, lithium bisoxalatoborate, lithium difluorophosphate, lithium hexafluorophosphate and lithium hexafluorophosphate.
9. The method for preparing the flame-retardant high-voltage electrolyte for the lithium ion battery according to any one of claims 6 to 8, which is characterized by comprising the following steps: and dissolving the lithium salt in the flame-retardant solvent, adding the additive after the lithium salt is completely dissolved, and uniformly stirring to form the flame-retardant high-voltage electrolyte for the lithium ion battery.
10. The method for preparing the flame-retardant high-voltage electrolyte for the lithium ion battery according to claim 9, wherein the method comprises the following steps: the method comprises the following specific steps:
step 1: dissolving lithium salt in a flame-retardant solvent, wherein the concentration of the lithium salt is 0.8-2mol/L, and the volume of each component in the flame-retardant solvent accounts for the total volume of the solution: 5-50% of carbonate, 10-60% of fluoro carbonate and 5-80% of fluoroether, and stirring to completely dissolve the lithium salt;
step 2: and (2) adding an additive into the solution formed in the step (1), wherein the additive accounts for 0.1-10% of the total volume or the total weight of the solution, and continuously stirring for 10 hours to form the uniform flame-retardant electrolyte solution for the high-voltage lithium battery.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103579676A (en) * | 2013-10-10 | 2014-02-12 | 珠海市赛纬电子材料有限公司 | Non-aqueous electrolyte for high-voltage lithium ion batteries |
| US20160190650A1 (en) * | 2014-12-30 | 2016-06-30 | Samsung Electronics Co., Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery employing the same |
| CN107293792A (en) * | 2017-08-21 | 2017-10-24 | 宁波诺丁汉大学 | A kind of nonaqueous electrolytic solution and nickelic tertiary cathode material battery |
| CN109301324A (en) * | 2018-09-11 | 2019-02-01 | 天津市捷威动力工业有限公司 | A kind of lithium ion battery with high energy density electrolyte |
| WO2020021530A1 (en) * | 2018-07-23 | 2020-01-30 | Bar-Ilan University | Electrolyte solutions for high voltage lithium-ion cells |
-
2020
- 2020-03-09 CN CN202010156619.7A patent/CN111326799A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103579676A (en) * | 2013-10-10 | 2014-02-12 | 珠海市赛纬电子材料有限公司 | Non-aqueous electrolyte for high-voltage lithium ion batteries |
| US20160190650A1 (en) * | 2014-12-30 | 2016-06-30 | Samsung Electronics Co., Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery employing the same |
| CN107293792A (en) * | 2017-08-21 | 2017-10-24 | 宁波诺丁汉大学 | A kind of nonaqueous electrolytic solution and nickelic tertiary cathode material battery |
| WO2020021530A1 (en) * | 2018-07-23 | 2020-01-30 | Bar-Ilan University | Electrolyte solutions for high voltage lithium-ion cells |
| CN109301324A (en) * | 2018-09-11 | 2019-02-01 | 天津市捷威动力工业有限公司 | A kind of lithium ion battery with high energy density electrolyte |
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