CN112216862A - High-nickel ternary lithium ion battery electrolyte and ternary lithium ion battery - Google Patents

High-nickel ternary lithium ion battery electrolyte and ternary lithium ion battery Download PDF

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CN112216862A
CN112216862A CN201910626225.0A CN201910626225A CN112216862A CN 112216862 A CN112216862 A CN 112216862A CN 201910626225 A CN201910626225 A CN 201910626225A CN 112216862 A CN112216862 A CN 112216862A
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electrolyte
lithium ion
ion battery
total mass
carbonate
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潘立宁
朱学全
郭力
黄慧聪
王建斌
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Shanshan Advanced Materials Quzhou Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention belongs to the technical field of lithium ion batteries, and particularly relates to a ternary lithium ion battery non-aqueous electrolyte and a lithium ion battery. The ternary lithium ion battery electrolyte comprises a non-aqueous organic solvent, an electrolyte lithium salt and an additive, wherein the additive comprises a lithium oxalate phosphate additive with a structure shown in a formula (I), and can also comprise conventional additives such as Vinylene Carbonate (VC), Vinyl Ethylene Carbonate (VEC), 1, 3-Propane Sultone (PS), vinyl sulfate (DTD), tris (trimethylsilane) phosphate (TMSP) and the like. The combined common action of the uniquely combined conventional additive and the lithium oxalate phosphate additive with the structure shown in the formula (I) can inhibit the generation of cracks in particles of the anode material in the circulation process, reduce the dissolution of transition metal elements at high temperature, inhibit the reduction reaction decomposition of a solvent at a cathode interface, and effectively improve the circulation performance, the high-temperature storage performance and the low-temperature performance of the ternary lithium ion battery.

Description

High-nickel ternary lithium ion battery electrolyte and ternary lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a ternary lithium ion battery electrolyte and a ternary lithium ion battery.
Background
The lithium ion battery has the advantages of high working voltage, high energy density, long service life, wide working temperature range, environmental friendliness and the like, and is widely applied to the fields of 3C digital products, electric tools, electric automobiles, aerospace and the like. Especially in the 3C digital field, mobile electronic devices, especially smart phones, have been rapidly developed in recent years toward lighter and thinner, and higher requirements are put forward on the energy density of lithium ion batteries.
In order to increase the energy density of a lithium ion battery, a common measure is to increase the charge cut-off voltage of a positive electrode material, such as a commercial lithium cobalt oxide battery voltage from 4.2V → 4.35V → 4.4V → 4.45V → 4.48V → 4.5V. However, the positive electrode material has certain defects under high voltage, for example, the high-voltage positive electrode active material has strong oxidizability in a lithium-deficient state, and the electrolyte is easily oxidized and decomposed to generate a large amount of gas and heat; in addition, the high-voltage positive electrode active material itself is also unstable in a lithium-deficient state, and is prone to some side reactions such as oxygen release, transition metal ion elution, and the like.
Another method for increasing the energy density of a lithium ion battery is to increase the nickel content in the ternary material, such as the commercialized ternary material from NCM111 → NCM422 → NCM523 → NCM622 → NCM811, and as the nickel content increases, the energy density of the battery can be further increased, but there are some negative effects, such as too high alkalinity of the material, and lattice energy changes during charging and discharging, which leads to the collapse of the material structure and the dissolution of the entering ions.
Transition metal ions are separated from crystals along with the reaction and enter the electrolyte to catalyze the decomposition of the electrolyte and damage the passive film of the active material, and meanwhile, transition metal lithium ions can also occupy a lithium ion migration channel of the passive film on the surface of the negative electrode material to block the migration of the lithium ions, so that the service life of the battery is influenced, and when the lithium ion battery is used in a high-temperature and high-pressure state, the negative influence can be more obvious.
At present, the main method for solving the problems is to develop a new film forming additive, the new additive can form a passivation film by oxidation reduction on the interface of a positive electrode material and a negative electrode material, the formed passivation film is compact, good and elastic, and can expand and contract along with the expansion and contraction of the positive electrode material and the negative electrode material in the charging and discharging processes, so that the cracking degree of the passivation film is reduced, and the electrochemical performance of the ternary lithium ion battery is improved.
Disclosure of Invention
In view of the defects of the prior art, an object of the present invention is to provide a ternary lithium ion battery electrolyte, in which an additive has good film-forming properties, can form a passivation film on an interface of a positive electrode material and a negative electrode material by oxidation reduction, and the formed passivation film is compact, good, and elastic, can expand and contract along with the expansion and contraction of the positive electrode material and the negative electrode material in the charging and discharging processes, so as to reduce the cracking degree of the passivation film, and effectively improve the cycle performance, rate capability, low-temperature discharge performance, and the like of the ternary lithium ion battery.
In order to achieve the above object, the electrolyte of the ternary lithium ion battery of the present invention comprises a non-aqueous organic solvent, an electrolyte lithium salt and an additive, wherein the additive comprises a lithium oxalate phosphate additive having a structure represented by formula (i):
Figure BDA0002127196070000021
wherein R is1、R2、R3And R4Each independently selected from any one of alkyl, fluoroalkyl, methoxy, ethoxy, fluorine atom, phenyl and cyclohexyl; optionally, R2And R3The linkage may be performed to form a ring structure or a bridged ring structure.
Preferably, the lithium oxalate phosphate additive with the structure shown in the formula (I) is selected from one or more of compounds (1) to (3):
Figure BDA0002127196070000031
more preferably, the content of the lithium oxalate phosphate additive with the structure shown in the formula (I) accounts for 0.5-2.0%, for example 1.0% of the total mass of the electrolyte.
Further, the additive also comprises conventional additives, wherein the conventional additives are one or more of Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), Vinyl Ethylene Carbonate (VEC), 1, 3-Propane Sultone (PS), 1, 3-Propene Sultone (PST), vinyl sulfate (DTD), tris (trimethylsilane) borate (TMSB), tris (trimethylsilane) phosphate (TMSP), citraconic anhydride, 1-propyl phosphoric anhydride, triacrylate and nitrile additives.
Preferably, the content of the conventional additive accounts for 0.2-5.0% of the total mass of the electrolyte; more preferably, when the conventional additive comprises vinylene carbonate, 1, 3-propane sultone and tris (trimethylsilane) borate, the addition amounts of the conventional additive are 0.2-0.5% of the total mass of the electrolyte; when the conventional additive contains vinyl sulfate, the addition amount of the conventional additive accounts for 1.0-2.0% of the total mass of the electrolyte; when the conventional additive comprises the rest of the additives, the addition amount of the conventional additive accounts for 0.5-1.0% of the total mass of the electrolyte.
Further preferably, the conventional additive comprises vinylene carbonate accounting for 0.5% of the total mass of the electrolyte and 1, 3-propane sultone accounting for 0.5% of the total mass of the electrolyte; or comprises vinylene carbonate accounting for 0.5 percent of the total mass of the electrolyte, 1, 3-propane sultone accounting for 0.5 percent of the total mass of the electrolyte and 1, 3-propylene sultone/tris (trimethylsilane) borate accounting for 0.5 percent of the total mass of the electrolyte; or comprises vinylene carbonate accounting for 0.5 percent of the total mass of the electrolyte, 1, 3-propane sultone accounting for 0.5 percent of the total mass of the electrolyte, 1, 3-propylene sultone/tris (trimethylsilane) borate accounting for 0.5 percent of the total mass of the electrolyte and vinyl sulfate accounting for 1.5 percent of the total mass of the electrolyte.
In the invention, the electrolyte lithium salt is a mixed lithium salt of lithium hexafluorophosphate and lithium difluorophosphate; preferably, the addition amount of the electrolyte lithium salt accounts for 12.5-15.0% of the total mass of the electrolyte; more preferably, the addition amount of the lithium difluorophosphate accounts for 0.5-1.0% of the total mass of the electrolyte, and the addition amount of the lithium hexafluorophosphate accounts for 12.0-14.0% of the total mass of the electrolyte; further preferably, the electrolyte lithium salt is lithium hexafluorophosphate accounting for 12.5% of the total mass of the electrolyte and lithium difluorophosphate accounting for 0.8% of the total mass of the electrolyte.
In the present invention, the non-aqueous organic solvent includes a cyclic carbonate-based solvent selected from at least one of Ethylene Carbonate (EC) and Propylene Carbonate (PC), and a chain carbonate-based solvent selected from one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC); preferably, the content of the non-aqueous organic solvent accounts for 75-85% of the total mass of the electrolyte; more preferably, the nonaqueous organic solvent comprises ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, and the mass ratio of the ethylene carbonate to the diethyl carbonate to the ethyl methyl carbonate is (25-35): (15-25): (45-55), for example, mixing the three materials according to the mass ratio of 30: 20: 50 are mixed.
The invention also aims to provide a ternary lithium ion battery which comprises a battery core formed by laminating or winding a positive plate, a separation film and a negative plate, and the ternary lithium ion battery electrolyte.
Preferably, the positive electrode active material of the positive electrode sheet is LiNi1-x-y-zCoxMnyAlzO2Or LiAmBnPO4Wherein: x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x + y + z is more than or equal to 0 and less than or equal to 1, A, B is Fe, Mn, Co or V, m is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, the negative active material of the negativewThe silicon-carbon composite material is compounded with graphite, wherein w is more than 1 and less than 2.
More preferably, the positive electrode active material LiNi0.6Co0.2Mn0.2O2The preparation method of the positive plate comprises the following steps: LiNi as positive electrode active material0.6Co0.2Mn0.2O2The conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 96: 2: 2, fully stirring and uniformly mixing in an N-methyl pyrrolidone solvent system, coating on an aluminum foil, drying and cold pressing to obtain a positive plate; the preparation method of the negative active material comprises the following steps: mixing the negative electrode active materialArtificial graphite, acetylene black serving as a conductive agent, Styrene Butadiene Rubber (SBR) serving as a binder and sodium carboxymethyl cellulose (CMC) serving as a thickening agent according to a mass ratio of 96: 2: 1: 1, fully stirring and uniformly mixing in a deionized water solvent system, coating on a copper foil, drying, and cold pressing to obtain the negative plate.
In the invention, the charge cut-off voltage of the ternary lithium ion battery is equal to 4.2V.
The invention has the beneficial effects that:
1. the conventional additive in the electrolyte can form an excellent interface protective film on the surface of an electrode, reduce the reaction activity of an electrode material and the electrolyte and stabilize the microstructure of the electrode material, thereby improving the electrochemical performance of the high-voltage lithium ion battery; meanwhile, the formed solid electrolyte membrane has low impedance, which is beneficial to improving the internal dynamic characteristics of the lithium ion battery;
2. the lithium oxalate phosphate with the structure shown in the formula (I) has very high reduction potential (more than or equal to 1.7vs Li/Li)+) The organic matter formed by reduction of the reduction product (inorganic matter) and Vinylene Carbonate (VC) or fluoroethylene carbonate (FEC) and the like are complemented and interacted, so that the formed passivation film has more compact and stable characteristics after the formation and the capacity grading of the battery, and the electrochemical performance of the battery is improved.
3. Through numerous tests, the combined action of the conventional additive and the lithium oxalate phosphate additive with the structure shown in the formula (I) is unexpectedly found out, so that a film can be formed on the surface of a positive electrode material, the generation of cracks in particles of the positive electrode material in the circulating process is inhibited, the dissolution of transition metal elements at high temperature is reduced, an SEI film can be formed on the surface of a negative electrode material, the reduction reaction decomposition of a solvent at a negative electrode interface is inhibited, and the interface impedance can be reduced, so that the circulating performance, the high-temperature storage performance and the low-temperature performance of a ternary lithium ion battery are effectively improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.
As used herein, the terms "comprises," "comprising," "includes," "including," "contains," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular. Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Example 1
Preparing an electrolyte: in a glove box filled with argon, ethylene carbonate, diethyl carbonate and ethyl methyl carbonate are mixed according to the mass ratio of EC: DEC: EMC 30: 20: 50, slowly adding 12.5 wt% of lithium hexafluorophosphate and 0.8 wt% of lithium difluorophosphate into the mixed solution, finally adding a lithium oxalate phosphate additive (compound 1) accounting for 1.0 wt% of the total mass of the electrolyte, and uniformly stirring to obtain the lithium ion battery electrolyte of the example 1.
Preparing a lithium ion battery:
LiNi as positive electrode active material0.6Co0.2Mn0.2O2The conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 96: 2: 2, fully stirring and uniformly mixing in an N-methyl pyrrolidone solvent system, coating on an aluminum foil, drying, and cold pressing to obtain the positive plate.
Preparing negative active material artificial graphite, conductive agent acetylene black, binder Styrene Butadiene Rubber (SBR), and thickener carboxymethylcellulose sodium (CMC) according to a mass ratio of 96: 2: 1: 1, fully stirring and uniformly mixing in a deionized water solvent system, coating on a copper foil, drying, and cold pressing to obtain the negative plate.
Polyethylene (PE) is used as a base film, and a nano aluminum oxide coating is coated on the base film to be used as an isolating film.
And sequentially laminating the positive plate, the isolating membrane and the negative plate, winding the positive plate, the isolating membrane and the negative plate along the same direction to obtain a bare cell, placing the bare cell in an outer package, injecting the prepared electrolyte, and performing processes of packaging, shelving at 45 ℃, high-temperature clamp formation, secondary packaging, capacity grading and the like to obtain the ternary high-voltage lithium ion battery.
Examples 2 to 8 and comparative examples 1 to 7
Examples 2 to 8 and comparative examples 1 to 7 were the same as example 1 except that the components of the electrolyte were added in the proportions shown in Table 1.
TABLE 1 composition ratios of the components of the electrolytes of examples 1-8 and comparative examples 1-7
Figure BDA0002127196070000071
Figure BDA0002127196070000081
Effects of the embodiment
The following performance tests were performed on the batteries of examples 1 to 8 and comparative examples 1 to 7, respectively, and the test results are shown in table 2.
1) And (3) testing the normal-temperature cycle performance of the ternary lithium ion battery: and (3) charging the battery after capacity grading to 4.2V at a constant current and a constant voltage of 1C and stopping the current to 0.05C at 25 ℃, then discharging to 3.0V at a constant current of 1C, and calculating the capacity retention rate of the 1000 th cycle after 1000 cycles of cycle of charge/discharge according to the cycle. The calculation formula is as follows:
the 1000 th cycle capacity retention ratio (%) (1000 th cycle discharge capacity/first cycle discharge capacity) × 100%.
2) And (3) testing the gas production rate and the capacity residual rate of the ternary lithium ion battery at a constant temperature of 60 ℃: firstly, the battery is circularly charged and discharged for 1 time (4.2V-3.0V) at the normal temperature at 0.5C, and the discharge capacity C of the battery before storage is recorded0Then charging the battery to 4.2V full-voltage state at constant current and constant voltage, and testing the thickness V of the battery before high-temperature storage by using a drainage method1Then the battery is put into a thermostat with the temperature of 60 ℃ for storage for 7 days, the battery is taken out after the storage is finished, and the volume V of the battery after the storage is tested after the battery is cooled for 8 hours2Calculating the gas production rate of the battery after the battery is stored for 7 days at the constant temperature of 60 ℃; after the battery is cooled for 24H at room temperature, the constant current discharge is carried out on the battery to 3.0V at 0.5C again, and the discharge capacity C after the battery is stored is recorded1And calculating the capacity residual rate of the battery after 7 days of constant-temperature storage at 60 ℃, wherein the calculation formula is as follows:
the gas production of the battery is V after 7 days of storage at 60 DEG C2-V1；
The residual capacity rate after 7 days of constant temperature storage at 60 ℃ is C1/C0*100％。
3) And (3) testing the 45 ℃ cycle performance of the ternary lithium ion battery: and (3) charging the battery after capacity grading to 4.2V at a constant current and a constant voltage of 1C at 45 ℃, stopping the current to 0.05C, then discharging to 3.0V at a constant current of 1C, and calculating the capacity retention rate of the 500 th cycle after the battery is cycled according to the cycle and is charged/discharged for 500 cycles. The calculation formula is as follows:
the 500 th cycle capacity retention ratio (%) (500 th cycle discharge capacity/first cycle discharge capacity) × 100%.
Table 2 results of testing cycle performance and high-temperature storage performance of batteries of examples and comparative examples
Figure BDA0002127196070000091
As can be seen from the comparison of the results of the cell performance test of comparative example 1 and examples 1-3 in Table 2: the lithium oxalate phosphate additive with the structure shown in the formula (I) can obviously improve the cycle performance of the battery and the capacity retention rate after high-temperature storage. Through Cyclic Voltammetry (CV), the substance can be preferentially reduced to form a film on a negative electrode graphite interface by a solvent, and the reduction potential is more than or equal to 1.7V vsLi+and/Li, and the resistance of the formed SEI film is low.
As can be seen from the comparison of comparative examples 4-7 with the battery performance test results of example 2 in Table 2: the addition amount of the sulfate additive is 0.5-2.0%, the addition amounts in other ranges can not achieve the electrochemical performance effect, when the addition amount is too small, a passive film formed by the substances on the interface of a positive electrode material and a negative electrode material is not stable enough, and when the addition amount exceeds the addition amount, the passive film becomes thick, the impedance is increased, the risk of gas generation of a battery is caused, the separation between a diaphragm and a pole piece is caused, and the electrochemical performance of the ternary lithium ion battery is deteriorated.
As can be seen from the comparison of the results of the battery performance tests of examples 4-8 and example 2 in Table 2: through the combined action of the conventional additive combination and the lithium oxalate phosphate additive with the structure shown in the formula (I), the invention not only can form a film on the surface of a positive electrode material, inhibit the generation of cracks in particles of the positive electrode material in the circulation process, reduce the dissolution of transition metal elements at high temperature, but also can form an SEI film on the surface of a negative electrode material, inhibit the reduction reaction of a solvent at a negative electrode interface, and simultaneously can reduce the interface impedance, thereby effectively improving the circulation performance and the high-temperature storage performance of a high-voltage lithium ion battery.
Compared with the single use of LiPF6As example 8 of the conductive lithium salt, the novel conductive lithium salt lithium difluoride with good film-forming characteristics is added in example 7 of the present invention, and the combined use of multiple novel film-forming lithium salts effectively improves the cycle performance and the high-temperature storage performance of the high-voltage lithium ion battery.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The ternary lithium ion battery electrolyte is characterized by comprising a non-aqueous organic solvent, an electrolyte lithium salt and an additive, wherein the additive comprises a lithium oxalate phosphate additive with a structure shown in a formula (I):
Figure FDA0002127196060000011
wherein R is1、R2、R3And R4Each independently selected from any one of alkyl, fluoroalkyl, methoxy, ethoxy, fluorine atom, phenyl and cyclohexyl; optionally, R2And R3The linkage may be performed to form a ring structure or a bridged ring structure.
2. The ternary lithium ion battery electrolyte of claim 1, wherein the lithium oxalate phosphate additive having the structure represented by formula (i) is selected from one or more of compounds (1) to (3):
Figure FDA0002127196060000012
preferably, the content of the lithium oxalate phosphate additive with the structure shown in the formula (I) accounts for 0.5-2.0%, for example 1.0% of the total mass of the electrolyte.
3. The ternary lithium ion battery electrolyte of claim 1, further comprising conventional additives, wherein the conventional additives are one or more of Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), Vinyl Ethylene Carbonate (VEC), 1, 3-Propane Sultone (PS), 1, 3-Propene Sultone (PST), vinyl sulfate (DTD), tris (trimethylsilane) borate (TMSB), tris (trimethylsilane) phosphate (TMSP), citrated anhydride, 1-propyl phosphoric anhydride, triacrylate, and nitrile additives; preferably, the content of the conventional additive accounts for 0.2-5.0% of the total mass of the electrolyte; more preferably, when the conventional additive comprises vinylene carbonate, 1, 3-propane sultone and tris (trimethylsilane) borate, the addition amounts of the conventional additive are 0.2-0.5% of the total mass of the electrolyte; when the conventional additive contains vinyl sulfate, the addition amount of the conventional additive accounts for 1.0-2.0% of the total mass of the electrolyte; when the conventional additive comprises the rest of the additives, the addition amount of the conventional additive accounts for 0.5-1.0% of the total mass of the electrolyte.
4. The ternary lithium ion battery electrolyte according to claim 1 or 3, wherein the conventional additive comprises vinylene carbonate accounting for 0.5% of the total mass of the electrolyte and 1, 3-propane sultone accounting for 0.5% of the total mass of the electrolyte; or comprises vinylene carbonate accounting for 0.5 percent of the total mass of the electrolyte, 1, 3-propane sultone accounting for 0.5 percent of the total mass of the electrolyte and 1, 3-propylene sultone/tris (trimethylsilane) borate accounting for 0.5 percent of the total mass of the electrolyte; or comprises vinylene carbonate accounting for 0.5 percent of the total mass of the electrolyte, 1, 3-propane sultone accounting for 0.5 percent of the total mass of the electrolyte, 1, 3-propylene sultone/tris (trimethylsilane) borate accounting for 0.5 percent of the total mass of the electrolyte and vinyl sulfate accounting for 1.5 percent of the total mass of the electrolyte.
5. The ternary lithium ion battery electrolyte of claim 1 wherein the electrolyte lithium salt is a mixed lithium salt of lithium hexafluorophosphate and lithium difluorophosphate; preferably, the addition amount of the electrolyte lithium salt accounts for 12.5-15.0% of the total mass of the electrolyte; more preferably, the addition amount of the lithium difluorophosphate accounts for 0.5-1.0% of the total mass of the electrolyte, and the addition amount of the lithium hexafluorophosphate accounts for 12.0-14.0% of the total mass of the electrolyte; further preferably, the electrolyte lithium salt is lithium hexafluorophosphate accounting for 12.5% of the total mass of the electrolyte and lithium difluorophosphate accounting for 0.8% of the total mass of the electrolyte.
6. The ternary lithium ion battery electrolyte of claim 1, wherein the non-aqueous organic solvent comprises a cyclic carbonate-based solvent selected from at least one of Ethylene Carbonate (EC) and Propylene Carbonate (PC), and a chain carbonate-based solvent selected from one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC); preferably, the content of the non-aqueous organic solvent accounts for 75-85% of the total mass of the electrolyte; more preferably, the nonaqueous organic solvent comprises ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, and the mass ratio of the ethylene carbonate to the diethyl carbonate to the ethyl methyl carbonate is (25-35): (15-25): (45-55), for example, mixing the three materials according to the mass ratio of 30: 20: 50 are mixed.
7. A ternary lithium ion battery, which is characterized by comprising a battery core formed by laminating or winding a positive plate, a separation film and a negative plate and the ternary lithium ion battery electrolyte as claimed in any one of claims 1 to 6.
8. The ternary lithium ion battery of claim 7, wherein the positive electrode of the positive plate is a positive electrodeThe active material is LiNi1-x-y-zCoxMnyAlzO2Or LiAmBnPO4Wherein: x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x + y + z is more than or equal to 0 and less than or equal to 1, A, B is Fe, Mn, Co or V, m is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, the negative active material of the negativewThe silicon-carbon composite material is compounded with graphite, wherein w is more than 1 and less than 2.
9. The ternary lithium ion battery according to claim 7 or 8, wherein the positive electrode active material LiNi is0.6Co0.2Mn0.2O2The preparation method of the positive plate comprises the following steps: LiNi as positive electrode active material0.6Co0.2Mn0.2O2The conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 96: 2: 2, fully stirring and uniformly mixing in an N-methyl pyrrolidone solvent system, coating on an aluminum foil, drying and cold pressing to obtain a positive plate; the preparation method of the negative active material comprises the following steps: preparing negative active material artificial graphite, conductive agent acetylene black, binder Styrene Butadiene Rubber (SBR), and thickener carboxymethylcellulose sodium (CMC) according to a mass ratio of 96: 2: 1: 1, fully stirring and uniformly mixing in a deionized water solvent system, coating on a copper foil, drying, and cold pressing to obtain the negative plate.
10. The ternary lithium ion battery of claim 7, wherein the charge cut-off voltage of the ternary lithium ion battery is equal to 4.2V.
CN201910626225.0A 2019-07-11 2019-07-11 High-nickel ternary lithium ion battery electrolyte and ternary lithium ion battery Pending CN112216862A (en)

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