CN112310473A - High-low temperature lithium ion battery electrolyte and lithium ion battery - Google Patents
High-low temperature lithium ion battery electrolyte and lithium ion battery Download PDFInfo
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- 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
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Abstract
The invention belongs to the technical field of lithium ion batteries, and discloses a high-low temperature lithium ion battery electrolyte and a lithium ion battery. The electrolyte comprises a non-aqueous organic solvent, lithium salt and additives, wherein the additives at least comprise an inorganic lithium salt additive M, a non-metal oxide additive X and a sulfur organic additive S. The inorganic lithium salt type additive M in the invention can participate in the formation of an interface protective film on the interface of the pole piece; the non-metal oxide additive X can further react with lithium hexafluorophosphate and the inorganic lithium salt M to form a novel anion group in situ, and participate in the basic composition of inorganic components of the SEI film; the sulfur compound S can form a multi-dimensional SEI film with an organic structure, and the composite film formed by organic combination of the three additives has good permeability, has excellent characteristics of difficult dissolution at high temperature and no shrinkage at low temperature, gives consideration to high and low temperatures and cycle characteristics, and can be widely applied to various battery systems.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a high-low temperature type lithium ion battery electrolyte and a lithium ion battery.
Background
At present, the lithium ion battery is widely applied to the fields of 3C digital markets, electric automobiles, military industry and aerospace and the like, different application scenes determine that the lithium ion battery needs to meet different working condition requirements, and the goal of meeting the long cycle characteristic at high and low temperatures is almost pursued in all application fields at present. The performance requirements of the lithium ion battery in a high-temperature environment are mainly reflected in long-term storage performance at a high temperature of more than 60 ℃, short-term storage performance at a temperature of more than 80 ℃, long cycle life at a temperature of more than 45 ℃, thermal shock test performance and the like; the low-temperature requirements are mainly embodied in various special requirements of low-temperature below-20 ℃ for discharge efficiency and inflection point voltage of different currents, low-temperature charge and discharge performance below 0 ℃ and no lithium precipitation during low-temperature cold start and low-temperature charging.
The high and low temperature performance of the lithium ion battery is mainly related to the components and the proportion of the solvent system and the additive. The studies on high and low temperature properties are mainly focused on the stability and resistance of SEI films. Inorganic salt in the SEI film has good ionic conductivity, is not easy to dissolve and lose efficacy at high temperature, organic components are difficult to stably exist in a positive electrode interface, are easy to decompose under the action of heating or electrochemistry at high temperature, and are easy to shrink and gather at low temperature to increase interface impedance; too many inorganic components can cause poor mechanical toughness, the long service life of the battery is difficult to guarantee, and a battery system which meets the requirements of high and low temperature and simultaneously considers long circulation is still a difficult problem to be solved by the prior electrolyte technology.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provides a high-low temperature type lithium ion battery electrolyte and a lithium ion battery. The electrolyte provided by the invention comprises a non-aqueous organic solvent, lithium salt and additives, wherein the additives at least comprise an inorganic lithium salt additive M, a non-metal oxide additive X and a sulfur organic additive S.
In order to achieve the purpose of the invention, the electrolyte of the high-low temperature lithium ion battery comprises a non-aqueous organic solvent, lithium salt and an additive, wherein the additive comprises an inorganic lithium salt additive M, a non-metal oxide additive X and a sulfur organic additive S.
In the present invention, the inorganic lithium salt additive M is selected from one or more of a phosphorus-containing lithium salt additive, a boron-containing lithium salt additive and a nitrogen-containing lithium salt additive.
Preferably, the lithium salt containing phosphorus in the inorganic lithium salt additive M includes lithium Difluorophosphate (DFP), lithium difluorobis (oxalato) phosphate, lithium tetrafluorooxalato phosphate, lithium tris (oxalato) phosphate; the boron-containing lithium salt additive comprises lithium difluorooxalato borate (DFOB), lithium tetrafluoroborate, lithium bis-oxalato borate (BOB); the nitrogen-containing lithium salt comprises bis (fluorosulfonyl) imide lithium (FSI) and bis (trifluoromethyl) sulfonyl imide lithium; further preferably, the addition amount of the inorganic lithium salt additive M is 0.3 to 20% by weight of the total weight of the electrolyte.
In the invention, the non-metallic oxide additive X is selected from one or more of phosphorus trifluoride oxide, sulfur dioxide, sulfur trioxide, carbon dioxide, nitric oxide, nitrogen dioxide, dinitrogen trioxide, phosphorus pentoxide, phosphorus trioxide and phosphorus oxychloride; preferably, the addition amount of the non-metal oxide additive X accounts for 0.1-5% of the total weight of the electrolyte; more preferably, the purity of the non-metal oxide is 99.9% or more, and the non-metal oxide is introduced into the electrolyte system after being mixed and diluted with nitrogen gas.
In the invention, the sulfur organic additive S is one or more of a ring-shaped sulfur-containing compound and a chain-shaped sulfur-containing compound; preferably, the cyclic sulfur-containing compound comprises one or more of 1, 3-Propane Sultone (PS), 1, 4-butane sultone, 1, 3-propene sultone, vinyl sulfate, ethyl sulfite, methylene methanedisulfonate, sultone, 3a,6 a-dihydro- [1,3,2] dioxolo [4,5-d ] [1,3,2] dioxathiol-2, 2,5, 5-tetraoxy, 4-methyl vinyl sulfate, 4-butyl vinyl sulfate, DTD, 4-fluoro-1, 3-propane sultone.
Preferably, the chain sulfur-containing compound includes p-methylphenyl isocyanate, trifluoromethanesulfonic anhydride, lithium ethylsulfate, lithium methylsulfate, lithium trifluoromethanesulfonate, allyllithium sulfate, bis (trimethylsilyl) sulfate (BTS), t-butyldimethylsilyltrifluoromethanesulfonate, trimethylsilylsulfonate, and a sulfone-based chain sulfur-containing additive having the structural formula N:
wherein R is1、R2Each independently selected from alkyl, fluorine-containing alkyl, phenyl substituent, alkenyl, alkynyl, nitrile group and trimethylsilyl; further preferably, the sulfone-based chain sulfur-containing additive having the structural formula N is selected from one or more of the following compounds:
further, in order to improve the comprehensive performance of batteries of different systems, the additive also comprises one or more of tris (trimethylsilyl) phosphate (TMSP), Succinonitrile (SN), vinylene carbonate, fluoroethylene carbonate (FEC), 1, 2-difluoroethylene carbonate, 4-trifluoromethyl ethylene carbonate, vinyl ethylene carbonate, ethylene glycol bis (propionitrile) ether (DENE), citraconic anhydride and succinic anhydride, and the addition amount of the additive accounts for 0.1-20% of the total weight of the electrolyte.
Further preferably, when the battery system is a high-nickel system and the positive electrode 811 type, the lithium salt is LiPF accounting for 10-20% of the total weight of the electrolyte6The non-aqueous organic solvent comprises ethylene carbonate, ethylene carbonate and methyl ethyl carbonate which are uniformly mixed according to the mass ratio of 30:20: 50; wherein, the additive comprises the following components:
the additive M is DFOB accounting for 0.2-1% of the total weight of the electrolyte and DFP accounting for 0.3-1% of the total weight of the electrolyte, and the additive X is SO accounting for 0.1-1% of the total weight of the electrolyte2And accounts for 0 of the total weight of the electrolyte.5% CO2POF accounting for 0.5 percent of the total weight of the electrolyte3Or NO accounting for 0.5 percent of the total weight of the electrolyte2The additive S is PS accounting for 0.5 percent of the total weight of the electrolyte and DTD accounting for 0.5 percent of the total weight of the electrolyte;
or the additive M is FSI accounting for 2% of the total weight of the electrolyte and DFP accounting for 1% of the total weight of the electrolyte, and the additive X is CO accounting for 0.1-0.6% of the total weight of the electrolyte2The additive S is PS accounting for 0.5 percent of the total weight of the electrolyte and DTD accounting for 0.5 percent of the total weight of the electrolyte, or DTD accounting for 1 percent of the total weight of the electrolyte and a sulfuryl chain-shaped sulfur-containing additive with a structural formula N accounting for 0.5 percent of the total weight of the electrolyte;
or the additive M is DFOB/BOB accounting for 0.5 percent of the total weight of the electrolyte and DFP accounting for 1 percent of the total weight of the electrolyte, and the additive X is SO accounting for 0.2 to 0.6 percent of the total weight of the electrolyte2The additive S is PS accounting for 1 percent of the total weight of the electrolyte and BTS accounting for 0.5 percent of the total weight of the electrolyte, or DTD accounting for 1 percent of the total weight of the electrolyte and PST accounting for 0.3 percent of the total weight of the electrolyte, and optionally TMSP accounting for 0.5 percent of the total weight of the electrolyte.
Further preferably, when the battery system is a high-voltage system and the positive electrode is 4.4V lithium cobaltate, the lithium salt is LiPF accounting for 10-20% of the total weight of the electrolyte6The non-aqueous organic solvent comprises EC, PC, DEC and PP, and the mass ratio of the EC to the PC to the DEC to the PP is 20: 15: 25: 60, adding a solvent to the mixture; wherein, the additive comprises the following components: the additive M is DFOB accounting for 0.5 percent of the total weight of the electrolyte, FSI accounting for 1 percent of the total weight of the electrolyte and DFP accounting for 0.5 percent of the total weight of the electrolyte; the additive X is SO accounting for 0.5-2% of the total weight of the electrolyte2CO accounting for 0.3-0.5% of the total weight of the electrolyte2Or NO accounting for 0.5 percent of the total weight of the electrolyte2(ii) a The additive S is PS accounting for 3% of the total weight of the electrolyte or PS accounting for 3% of the total weight of the electrolyte and a sulfone-based chain sulfur-containing additive with a structural formula N accounting for 0.2% of the total weight of the electrolyte, and further comprises FEC accounting for 7% of the total weight of the electrolyte, SN accounting for 2% of the total weight of the electrolyte and DENE accounting for 1% of the total weight of the electrolyte.
In order to realize the purpose of the invention, the invention also provides a lithium ion battery which comprises a positive pole piece, a negative pole piece, a diaphragm and the lithium ion batteryThe electrolyte comprises an anode pole piece and an anode diaphragm, wherein the anode pole piece comprises an anode current collector and an anode diaphragm on the surface of the anode current collector, the anode diaphragm comprises an anode active substance, a conductive agent and a binder, and the anode active substance is LiNi1-x-y-zCoxMnyAlzO2Wherein: 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, and x + y + z is more than or equal to 0 and less than or equal to 1, the working voltage of the lithium ion battery is more than or equal to 4.2V, the lithium ion battery can be applied to a ternary system, a lithium cobaltate high-voltage system and other anode systems, and the anode material is artificial graphite, composite graphite, natural graphite, a silicon-.
In the invention, the inorganic lithium salt type additive M can participate in the formation of an interface protective film on the interface of the pole piece; the non-metal oxide additive X can further react with lithium hexafluorophosphate and the inorganic lithium salt M to form a novel anion group in situ, and participates in the basic composition of inorganic components of the SEI film, so that the high and low temperature and cycle performance of the battery can be improved; the composite membrane formed by organically combining the three additives has the advantages of balanced proportion of each component, firmness, stability, good permeability, good characteristics of high temperature and low temperature non-shrinkage, high and low temperature and cycle characteristics, and can be widely applied to various battery systems.
Drawings
FIG. 1 is a dq/dv & V curve for comparative examples 1-7 of the present invention during cell formation;
FIG. 2 is a discharge curve of comparative examples 1 to 7 of the present invention at a low temperature of-20 ℃;
FIG. 3 is a discharge curve at low temperature-20 ℃ for comparative examples 10, 12 and some of the examples of the present invention.
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.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, 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 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.
Comparative example 1
In a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate and methyl ethyl carbonate are uniformly mixed according to the mass ratio of 30:20:50, and LiPF with the mass fraction of 12.5 percent is added into the mixed solution6And stirring until it was completely dissolved to obtain the electrolyte for lithium ion battery of comparative example 1.
Comparative example 2
In an argon-filled glove box (moisture < 10ppm, oxygen < 1ppm), ethylene carbonate,Uniformly mixing ethylene carbonate and methyl ethyl carbonate in a mass ratio of 30:20:50, and adding LiPF with the mass fraction of 12.5% into the mixed solution6And 1% of 1, 3% propane sultone, and stirred until it was completely dissolved to obtain the electrolyte for a lithium ion battery of comparative example 2.
Comparative example 3
Ethylene carbonate, ethylene carbonate and ethyl methyl carbonate were uniformly mixed in a glove box filled with argon gas (moisture < 10ppm, oxygen < 1ppm) at a mass ratio of 30:20:50, and LiPF6 of 12.5% by mass and ethylene sulfate of 1% by mass were added to the mixed solution and stirred until they were completely dissolved to obtain the electrolyte for a lithium ion battery of comparative example 3.
Comparative example 4
In a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate and methyl ethyl carbonate are uniformly mixed according to the mass ratio of 30:20:50, LiPF6 with the mass fraction of 12.5% is added into the mixed solution, then sulfur dioxide gas with the total weight of 0.5% of the electrolyte is introduced, and the solution is stirred until the solution is completely dissolved to obtain the electrolyte of the lithium ion battery of the comparative example 4.
Comparative example 5
In a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate and methyl ethyl carbonate are uniformly mixed according to the mass ratio of 30:20:50, LiPF6 with the mass fraction of 12.5% is added into the mixed solution, then sulfur dioxide gas with the weight of 1% of the total weight of the electrolyte is introduced, and the mixture is stirred until the sulfur dioxide gas is completely dissolved to obtain the electrolyte of the lithium ion battery of the comparative example 5.
Comparative example 6
In a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate and methyl ethyl carbonate are uniformly mixed according to the mass ratio of 30:20:50, LiPF6 with the mass fraction of 12.5% is added into the mixed solution, then sulfur dioxide gas with the weight of 1.5% of the total weight of the electrolyte is introduced, and the mixture is stirred until the sulfur dioxide gas is completely dissolved to obtain the electrolyte of the lithium ion battery of the comparative example 6.
Comparative example 7
Ethylene carbonate, ethylene carbonate and ethyl methyl carbonate were uniformly mixed in a glove box filled with argon gas (moisture < 10ppm, oxygen < 1ppm) at a mass ratio of 30:20:50, LiPF6 was added to the mixed solution at a mass fraction of 12.5%, then lithium difluorooxalato borate was introduced at a total weight of the electrolyte of 1.0%, and the solution was stirred until it was completely dissolved to obtain the lithium ion battery electrolyte of comparative example 7.
The preparation method of the lithium ion battery electrolyte of other comparative examples and examples is the same as that described above, and the addition ratio of the specific additives is shown in table 1.
Preparation of the Battery
Preparation of (one) ternary system 523/AG soft package battery
The preparation method of the NCM523/AG-4.2V battery in each comparison and example is as follows: LiNi as positive electrode active material0.8Co0.1Mn0.2O1(523) The conductive agent acetylene black, the carbon nano tube and the binder polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 95: 2.8: 0.2: 2, fully stirring and uniformly mixing the mixture in a N-methylpyrrolidone solvent system in a dry environment filled with nitrogen, coating the mixture on an Al foil, drying and cold-pressing the mixture to obtain the positive pole piece, wherein the compaction density of the positive pole piece is 3.45g/cm3。
The preparation method comprises the following steps of mixing a negative active material graphite, a conductive agent acetylene black, a carbon nano tube, a binder Styrene Butadiene Rubber (SBR), and a thickening agent sodium carboxymethyl cellulose (CMC) according to a mass ratio of 96: 1.8: 0.2: 1:1, fully stirring and uniformly mixing in a deionized water solvent system, coating the mixture on a Cu foil, drying and cold-pressing to obtain a negative pole piece, wherein the compacted density of the negative pole is 1.6g/cm3Polyethylene (PE) is used as a base film (14 μm), and a nano alumina coating (2 μm) is coated on the base film to be used as a diaphragm.
And stacking the positive pole piece, the diaphragm and the negative pole piece in sequence to enable the diaphragm to be positioned between the positive pole piece and the negative pole piece to play an isolating role, and winding to obtain the bare cell. And placing the bare cell in an outer package, injecting the electrolyte prepared in the comparative examples 1-7, and performing the procedures of packaging, laying aside, formation, aging, secondary packaging, capacity grading and the like to obtain the high-nickel NCM523/AG-4.2V ternary positive electrode material soft package lithium ion battery.
Preparation of (di) ternary system 811/AG soft package battery
Each proportional ratioAnd the preparation method of the NCM811/AG-4.2V battery in the example is as follows: LiNi as positive electrode active material0.8Co0.1Mn0.2O1(811) The conductive agent acetylene black, the carbon nano tube and the binder polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 95: 2.8: 0.2: 2, fully stirring and uniformly mixing the mixture in a N-methylpyrrolidone solvent system in a dry environment filled with nitrogen, coating the mixture on an Al foil, drying and cold-pressing the mixture to obtain the positive pole piece, wherein the compaction density of the positive pole piece is 3.45g/cm3。
The preparation method comprises the following steps of mixing a negative active material graphite, a conductive agent acetylene black, a carbon nano tube, a binder Styrene Butadiene Rubber (SBR), and a thickening agent sodium carboxymethyl cellulose (CMC) according to a mass ratio of 96: 1.8: 0.2: 1:1, fully stirring and uniformly mixing in a deionized water solvent system, coating the mixture on a Cu foil, drying and cold-pressing to obtain a negative pole piece, wherein the compacted density of the negative pole is 1.6g/cm3Polyethylene (PE) is used as a base film (14 μm), and a nano alumina coating (2 μm) is coated on the base film to be used as a diaphragm.
And stacking the positive pole piece, the diaphragm and the negative pole piece in sequence to enable the diaphragm to be positioned between the positive pole piece and the negative pole piece to play an isolating role, and winding to obtain the bare cell. And placing the bare cell in an outer package, injecting the electrolyte prepared in the comparative examples 8-14 and the examples 1-15, and carrying out the procedures of packaging, laying aside, forming, aging, secondary packaging, capacity grading and the like to obtain the high-nickel NCM811/AG-4.2V ternary positive electrode material soft package lithium ion battery.
(III) preparation of high-voltage 4.4V system soft package lithium ion battery
Fully stirring and uniformly mixing a positive active material lithium cobaltate 9000C, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) in an N-methylpyrrolidone solvent system according to a mass ratio of 96:2:2, coating the mixture on an aluminum foil, drying and cold-pressing the mixture to obtain a positive plate, wherein the compaction density is 4.15g/cm3。
Fully stirring and uniformly mixing the negative active material artificial graphite, the conductive agent acetylene black, the binder Styrene Butadiene Rubber (SBR) and the thickening agent carboxymethylcellulose sodium (CMC) in a deionized water solvent system according to the mass ratio of 96:2:1:1, coating the mixture on a copper foil, drying and cold pressing to obtain a negative plate, wherein the compaction density is 1.72g/cm3。
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 film and the negative plate, winding the laminated positive plate, the isolating film and the negative plate along the same direction to obtain a bare cell, packaging the bare cell by adopting an aluminum plastic film, and carrying out processes of packaging, laying aside, forming, aging, secondary packaging, capacity grading and the like on the battery injected with the electrolyte prepared in the comparative examples 15-17 and the examples 16-24 to obtain the high-voltage lithium cobalt oxide 4.4V lithium ion battery.
Performance testing and results
In order to fully illustrate the characteristics of the additive introduced by the invention, the charging and discharging curves of the batteries of different additive groups 1-7 in the comparative examples in the formation process are analyzed, the reaction condition of the additive in the formation process at the negative electrode interface is analyzed, and the attached figure 1 is the comparison of dq/dv & V curves of the batteries of the comparative examples 1-7. From fig. 1, it can be seen that the blank group (comparative example 1) shows weak reduction around 3.1V, which means that the ethylene carbonate participates in the formation of SEI film on the surface of the negative electrode, while the reduction potential of 1,3 propane sultone in comparative example 2 is 3.0V on the negative electrode in full electricity, and the reduction potential of the ethylene sulfate in comparative example 3 is around 2.8V, which indicates that the reduction potential of the above conventional sulfur-based additive is prior to the ethylene carbonate, thereby forming a better solid electrolyte film, and after the lithium difluorooxalato borate is introduced in comparative example 7, the characteristic reduction peak of the additive is found to be around 2.0V in the full cell, and the oxalate additive is found to participate in the formation of passivation film on the negative electrode interface prior to the above two sulfur-based additives. Further comparing the curves of the sulfur dioxide, which is a non-metal oxide additive, of the present invention, it can be seen that when the amount of the sulfur dioxide is 0.5%, the sulfur dioxide participates in the formation of the SEI film around 1.25V, when the amount of the sulfur dioxide is increased to 1%, in addition to the reduction at 1.25V, the reduction reaction further occurs around 2.5V, which indicates that the additive repairs the interface film with the increase of the voltage, comparative example 6, which further increases the amount of the sulfur dioxide added to 1.5%, shows distinct reaction characteristics, and the chemical reaction characteristic peaks around 1.25V and 2.7V are further enhanced, and in addition to the enhancement, new chemical reaction characteristic peaks around 1.6 and 2.0V are further occurred. By introducing the non-metal oxide additives with different contents into an electrolyte system, different chemical reaction processes are presented, which shows that the amount of the additives has different influences on the formation process and the performance of the battery.
It can be seen from the NCM523/AG soft-package battery low-temperature discharge curves of comparative examples 1 to 7 in fig. 2 that the comparative example 2 low-temperature discharge platform of 1,3 propane sultone introduced into the system is lower than that of the blank group, and the discharge capacity is also reduced, the low-impedance additive vinyl sulfate in the comparative example 3 has no improvement effect on the battery low-temperature discharge platform, and only improves the discharge capacity to a certain extent, showing that the two sulfur-containing compounds have no obvious help on low-temperature performance, and it is found that the low-temperature discharge platform of the battery is improved to a small extent, the discharge capacity is also improved, and the surface lithium salt type additive has a certain effect on low-temperature improvement. After the sulfur dioxide which is the non-metallic oxide additive is introduced, the low-temperature discharge platform of the battery is obviously improved, and further comparison shows that the addition amount of different contents still has difference to the low-temperature improvement, the highest low-temperature discharge voltage of comparative example 4 with the addition amount of 0.5 percent is increased from 3.5V to 3.7V, and the discharge capacity is obviously improved. When the addition amount of sulfur dioxide is further increased to 1.0% and 1.5%, the highest low-temperature discharge voltage of the battery is increased to 3.8V, which shows that the discharge platform is further improved by the increase of the addition amount of the additive, and the low-temperature discharge capacity is not obviously improved after the addition amount of the additive is increased, and is reduced on the contrary after excessive addition, but the additive mainly has a remarkable improvement effect on the low-temperature discharge platform.
The invention further researches the low-temperature discharge effect of the electrolyte in high nickel, and the comparison of the discharge curves in the attached figure 3 shows that the low-temperature discharge platform of the comparative example 10 only added with the additive S is the lowest and the discharge capacity is less; after the lithium salt additive M is introduced on the basis, the discharge platform and the discharge capacity of the lithium salt additive M are improved, but the lithium salt additive M still does not reach the best state, and after the non-metal oxide X provided by the invention is further added into an electrolyte system containing the additives S and M, the low-temperature discharge platform voltage of the battery is further improved, which is shown in the above examples 1 and 6 that the additives have better low-temperature effects. Further comparing the low-temperature discharge performance of the batteries of examples 12 and 15, it was found that the low-temperature discharge plateau and the discharge capacity were reduced to some extent after the high-resistance additive was added to the electrolyte system of the present invention; while example 3, in which the non-metal oxide was excessively added, the low-temperature discharge capacity was significantly decreased although the low-temperature discharge plateau remained at a high level. The additive is supposed to excessively participate in the reaction after being excessively added, so that the diffusion of lithium ions is not facilitated, the amount of the additive needs to be controlled so as to enable the comprehensive performance of the battery to be better, and researches show that the battery has relatively better comprehensive performance when the addition amount is within 1.5%.
TABLE 1 comparative examples and the component ratios of the lithium-ion battery electrolytes of the examples
And injecting the electrolyte obtained in the comparative example and the implementation into the lithium ion battery to obtain the lithium ion battery corresponding to the electrolyte.
The batteries of comparative examples 1 to 17 and examples 1 to 24 were subjected to normal temperature cycle, high temperature cycle of 45 c, low temperature-20 c and high temperature storage property tests. The test items and the test results are shown in Table 2.
TABLE 2 ternary and lithium cobaltate systems lithium ion batteries
The conditions of the change of the thickness, the internal resistance and the capacity of the battery in each system after normal-temperature circulation, high-temperature circulation at 45 ℃ and high-temperature storage are further compared. From the data in the table above, it can be seen that the normal temperature cycle performance of the steam in the battery pack containing only the additive S (comparative example 10) cannot be guaranteed, and the normal temperature cycle performance of the battery is improved by introducing the inorganic lithium salt type additive M provided by the present invention into the system (comparative example 12); the inorganic salt additive M alone (comparative example 8) had a gas generation condition in high-temperature storage, a large change rate of the internal resistance of the battery, and poor capacity retention and recovery ability. After the non-metallic oxide additive is introduced into the system, the normal-temperature cycle performance and the high-temperature cycle performance of the battery are both improved, the change rate of the internal resistance of the battery in the aspect of high-temperature storage is smaller overall, and after the additive S is used alone, the normal-temperature cycle performance and the high-temperature cycle performance of the battery in a system with a positive electrode material of 523 are both kept better, but the long cycle performance cannot be realized in a high-nickel 811 system. After the additive M, the additive S and the non-metal oxide X are organically combined, the normal temperature, the high temperature and the storage performance of the battery are further improved, and in order to enable the comprehensive performance of the battery to be optimal, a small amount of sulfone-based compound is further introduced, as shown in examples 11 and 15, as can be seen from performance comparison data, the high temperature cycle performance of the high-nickel battery can be further improved by further adding the sulfone-based compound, and the storage performance of the high-nickel battery can be further improved. Comparing the data, it can be seen that when the additive X is added in too much amount, the storage performance and the cycle performance of the battery are rather reduced, and similar to the low-temperature performance of the battery, the internal resistance of the battery is probably greatly influenced by the excessive addition of the additive, and the comprehensive performance of the battery is reduced. The situation of each group of batteries of the lithium cobaltate system is compared, and the batteries can have good high and low temperature and good cycling stability and show good application prospect by introducing the three additives into the high-voltage lithium cobaltate system.
Through the conditions of the comparative example and the embodiment, the analysis is as follows, in the invention, the inorganic lithium salt type additive M can participate in the formation of an interface protective film on a pole piece interface, and the problems of quick gas generation and quick internal resistance change exist in a high-nickel system; the non-metal oxide additive X can further react with lithium hexafluorophosphate and the inorganic lithium salt M to form a novel anion group in situ, and participates in the basic composition of inorganic components of the SEI film, so that the high and low temperature and cycle performance of the battery are improved, the excessive introduction has opposite effects on the low temperature and storage performance of the battery, and the addition amount of the additive X needs to be controlled; the sulfuryl-containing compound can further improve the high-temperature storage and high-temperature cycle performance of the battery; the sulfur compound S can form a multi-dimensional SEI film composition with an organic structure, provides a framework and a support for inorganic components, and improves the storage performance of the battery. The composite membrane formed by organically combining the three additives has the advantages of balanced proportion of each component, firmness, stability, good permeability, good characteristics of difficult dissolution at high temperature and no shrinkage at low temperature, high and low temperature and cycle characteristics, and can be widely applied to various battery systems.
It will be understood by those skilled in the art that the foregoing is merely exemplary of the present invention, and is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The electrolyte for the high-temperature and low-temperature lithium ion battery comprises a non-aqueous organic solvent, lithium salt and an additive, and is characterized in that the additive comprises an inorganic lithium salt additive M, a non-metal oxide additive X and a sulfur organic additive S.
2. The high and low temperature compatible lithium ion battery electrolyte according to claim 1, wherein the inorganic lithium salt additive M is selected from one or more of a phosphorus-containing lithium salt additive, a boron-containing lithium salt additive and a nitrogen-containing lithium salt additive; preferably, the phosphorus-containing lithium salt in the inorganic lithium salt additive M comprises lithium difluorophosphate, lithium difluorobis (oxalato) phosphate, lithium tetrafluoro (oxalato) phosphate and lithium tris (oxalato) phosphate; the boron-containing lithium salt additive comprises lithium difluoro oxalate borate, lithium tetrafluoroborate and lithium bis oxalate borate; the nitrogen-containing lithium salt comprises lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethyl) sulfonyl imide; further preferably, the addition amount of the inorganic lithium salt additive M is 0.3 to 20% by weight of the total weight of the electrolyte.
3. The electrolyte for the lithium ion battery compatible with high and low temperature according to claim 1, wherein the non-metal oxide additive X is one or more selected from phosphorus oxytrifluoride, sulfur dioxide, sulfur trioxide, carbon dioxide, nitrogen monoxide, nitrogen dioxide, dinitrogen trioxide, phosphorus pentoxide, phosphorus trioxide, and phosphorus oxychloride; preferably, the addition amount of the non-metal oxide additive X accounts for 0.1-5% of the total weight of the electrolyte; more preferably, the purity of the non-metal oxide is 99.9% or more, and the non-metal oxide is introduced into the electrolyte system after being mixed and diluted with nitrogen gas.
4. The electrolyte solution for the high and low temperature lithium ion battery according to claim 1, wherein the sulfur-based organic additive S is one or more of a cyclic sulfur-containing compound and a chain sulfur-containing compound; preferably, the cyclic sulfur-containing compound comprises one or more of 1, 3-Propane Sultone (PS), 1, 4-butane sultone, 1, 3-propene sultone, vinyl sulfate, ethyl sulfite, methylene methanedisulfonate, sultone, 3a,6 a-dihydro- [1,3,2] dioxolo [4,5-d ] [1,3,2] dioxathiol-2, 2,5, 5-tetraoxy, 4-methyl vinyl sulfate, 4-butyl vinyl sulfate, DTD, 4-fluoro-1, 3-propane sultone.
5. The electrolyte solution for the high and low temperature lithium ion battery as claimed in claim 1, wherein the chain sulfur compound comprises p-methylphenyl isocyanate, trifluoromethanesulfonic anhydride, lithium ethylsulfate, lithium methylsulfate, lithium trifluoromethanesulfonate, lithium allylsulfate, bis (trimethylsilyl) sulfate (BTS), tert-butyldimethylsilyltrifluoromethanesulfonate, trimethylsilyl trifluoromethanesulfonate and a sulfone-based chain sulfur additive having a structural formula N:
wherein R is1、R2Each independently selected from alkyl, fluorine-containing alkyl, phenyl substituent, alkenyl, alkynyl, nitrile group and trimethylsilyl.
6. The electrolyte for the high and low temperature lithium ion battery as claimed in claim 5, wherein the sulfuryl chain sulfur-containing additive with the structural formula N is selected from one or more of the following compounds:
7. the electrolyte for the lithium ion battery compatible with high and low temperatures according to claim 1, wherein the additive further comprises one or more of tris (trimethylsilyl) phosphate (TMSP), Succinonitrile (SN), vinylene carbonate, fluoroethylene carbonate (FEC), 1, 2-difluoroethylene carbonate, 4-trifluoromethyl ethylene carbonate, vinyl ethylene carbonate, ethylene glycol bis (propionitrile) ether (done), citraconic anhydride and succinic anhydride, and the addition amount of the additive is 0.1-20% of the total weight of the electrolyte.
8. The electrolyte for the lithium ion battery compatible with high and low temperature according to claim 1, wherein when the battery is a high nickel system, positive electrode 811 type, the lithium salt is LiPF accounting for 10-20% of the total weight of the electrolyte6The non-aqueous organic solvent comprises ethylene carbonate, ethylene carbonate and methyl ethyl carbonate which are uniformly mixed according to the mass ratio of 30:20: 50; wherein, the additive comprises the following components:
the additive M is DFOB accounting for 0.2-1% of the total weight of the electrolyte and DFP accounting for 0.3-1% of the total weight of the electrolyte, and the additive X is SO accounting for 0.1-1% of the total weight of the electrolyte2CO accounting for 0.5 percent of the total weight of the electrolyte2POF accounting for 0.5 percent of the total weight of the electrolyte3Or NO accounting for 0.5 percent of the total weight of the electrolyte2The additive S is PS accounting for 0.5 percent of the total weight of the electrolyte and DTD accounting for 0.5 percent of the total weight of the electrolyte;
or the additive M is FSI accounting for 2% of the total weight of the electrolyte and DFP accounting for 1% of the total weight of the electrolyte, and the additive X is CO accounting for 0.1-0.6% of the total weight of the electrolyte2The additive S is PS accounting for 0.5 percent of the total weight of the electrolyte and DTD accounting for 0.5 percent of the total weight of the electrolyte, or DTD accounting for 1 percent of the total weight of the electrolyte and a sulfuryl chain-shaped sulfur-containing additive with a structural formula N accounting for 0.5 percent of the total weight of the electrolyte;
or the additive M is DFOB/BOB accounting for 0.5 percent of the total weight of the electrolyte and DFP accounting for 1 percent of the total weight of the electrolyte, and the additive X is SO accounting for 0.2 to 0.6 percent of the total weight of the electrolyte2The additive S is PS accounting for 1 percent of the total weight of the electrolyte and BTS accounting for 0.5 percent of the total weight of the electrolyte, or DTD accounting for 1 percent of the total weight of the electrolyte and PST accounting for 0.3 percent of the total weight of the electrolyte, and optionally TMSP accounting for 0.5 percent of the total weight of the electrolyte.
9. The electrolyte for the lithium ion battery compatible with high and low temperature according to claim 1, wherein when the battery is a high voltage system and the positive electrode is 4.4V lithium cobalt oxide, the lithium salt is LiPF accounting for 10-20% of the total weight of the electrolyte6The non-aqueous organic solvent comprises EC, PC, DEC and PP, and the mass ratio of the EC to the PC to the DEC to the PP is 20: 15: 25: 60, adding a solvent to the mixture; wherein, the additive comprises the following components: the additive M is DFOB accounting for 0.5 percent of the total weight of the electrolyte, FSI accounting for 1 percent of the total weight of the electrolyte and DFP accounting for 0.5 percent of the total weight of the electrolyte; the additive X is SO accounting for 0.5-2% of the total weight of the electrolyte2CO accounting for 0.3-0.5% of the total weight of the electrolyte2Or NO accounting for 0.5 percent of the total weight of the electrolyte2(ii) a The additive S is PS accounting for 3 percent of the total weight of the electrolyte or PS accounting for 3 percent of the total weight of the electrolyte and a sulfuryl chain-shaped sulfur-containing additive with a structural formula N accounting for 0.2 percent of the total weight of the electrolyte, and also comprises7% of FEC accounting for the total weight of the electrolyte, 2% of SN accounting for the total weight of the electrolyte and 1% of DENE accounting for the total weight of the electrolyte.
10. A lithium ion battery is characterized by comprising a positive pole piece, a negative pole piece, a diaphragm and the electrolyte of any one of claims 1 to 9, wherein the positive pole piece comprises a positive current collector and a positive membrane on the surface of the positive current collector, the positive membrane comprises a positive active substance, a conductive agent and a binder, and the positive active substance is LiNi1-x-y- zCoxMnyAlzO2Wherein: 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, and x + y + z is more than or equal to 0 and less than or equal to 1, the working voltage of the lithium ion battery is more than or equal to 4.2V, the lithium ion battery can be applied to a ternary system, a lithium cobaltate high-voltage system and other anode systems, and the anode material is artificial graphite, composite graphite, natural graphite, a silicon-.
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