CN109755635B - Battery electrolyte additive giving consideration to high and low temperature performance, electrolyte and high-nickel ternary lithium ion battery - Google Patents
Battery electrolyte additive giving consideration to high and low temperature performance, electrolyte and high-nickel ternary lithium ion battery Download PDFInfo
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Abstract
The invention discloses a battery electrolyte additive giving consideration to high and low temperature performance, an electrolyte and a high-nickel ternary lithium ion battery. The additive comprises a fluorine-containing phenyl sulfonate compound additive A with a structure shown in a formula I, a cyclic sulfonate additive B with a structure shown in a formula II and a conventional negative electrode film-forming additive, and the battery electrolyte with high and low temperature performance comprises electrolyte lithium salt, a non-aqueous organic solvent and the additive. The electrolyte provided by the invention has the advantages that through the synergistic effect generated by the combined use of the three additives and the combination of the advantages of the electrolyte additives with different components, the electrolyte capable of effectively improving the performance of the high-nickel ternary lithium ion power battery is provided, and the electrolyte has good electrochemical properties such as cycle performance, rate capability, storage performance and safety performance under high-temperature and low-temperature conditions, so that the problem that the high-temperature and low-temperature performance of the existing battery cannot be considered at the same time is solved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a battery electrolyte additive giving consideration to high and low temperature performances, an electrolyte and a high-nickel ternary lithium ion battery.
Background
The new energy automobile industry in China is accompanied with the vigorous development of policy warm air, and the market space of power batteries is wide. However, the current power battery mainly uses lithium iron phosphate, and the specific energy thereof is limited, so that the requirement of the passenger vehicle on the endurance mileage will be difficult to meet in the future. Therefore, the performance index for pursuing high specific energy is an important development direction of the lithium ion power battery.
The high nickel material has been a research hotspot of material and energy science due to the high reversible specific capacity, low price and environmental friendliness, and is also a preferred material of future high-energy density power batteries, but some inherent disadvantages of the high nickel materialFor example, poor structural stability, poor high-temperature stability, poor storage performance, and poor high-low temperature performance in the circulation process greatly limit the wide application of the material in various fields. Therefore, it is urgent to find an electrolyte system which has both high and low temperature long cycle performance. Under the condition of low temperature, the lithium ion power battery of a conventional electrolyte system has the defects of increased electrolyte viscosity, reduced conductivity and increased electrode interface impedance, which often causes the phenomena of low battery charge and discharge capacity, lithium precipitation and the like, and further causes electrode reaction polarization, reduced discharge platform and energy attenuation of the lithium ion battery. While the battery is under high temperature condition, the battery is made of LiPF6The conventional electrolyte composed is easy to be oxidized and decomposed, and the generated HF can corrode a manganese-containing positive electrode material to cause partial metal ions to be dissolved out and deposited on a negative electrode, so that the composition and structure of a negative electrode solid electrolyte interface film are changed, the solid electrolyte interface is unstable, the impedance of an SEI film is increased, and further the battery is inflated, the performance is deteriorated, and even potential safety hazards are brought. Therefore, it is one of the research hotspots in the academia and industry to consider the development of electrolyte systems with high and low temperature long cycle performance. Through research, the use of the electrolyte solvent and the additive can effectively improve the high-low temperature cycle performance of the lithium ion battery. However, if the content of the solvent having a low melting point and a low viscosity is increased, the low-temperature performance of the battery is improved, but the normal-temperature performance and the high-temperature performance are deteriorated, and the three cannot be compatible.
In view of the above, it is necessary to provide an electrolyte additive and an electrolyte for a lithium ion battery with high and low temperature long cycle performance, so as to improve the electrochemical performance of a high-nickel ternary lithium ion power battery under high and low temperature conditions, further solve the problem that the high and low temperature performance of the battery in the prior art cannot be considered, and effectively expand the application range of the lithium ion battery.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provides a battery electrolyte additive with high and low temperature performance, an electrolyte and application thereof in a high-nickel ternary lithium ion battery. The electrolyte provided by the invention combines the advantages of electrolyte additives with different components, provides the electrolyte capable of effectively improving the performance of the high-nickel ternary lithium ion power battery, and has good electrochemical properties such as cycle performance, rate performance, storage performance and safety performance under high-temperature and low-temperature conditions, so that the problem that the high-low temperature performance of the existing battery cannot be considered at the same time is solved.
In one aspect of the invention, the invention provides a battery electrolyte additive with high and low temperature performance, which comprises a fluorine-containing phenyl sulfonate compound additive A with a structure shown in formula I, a cyclic sulfonate compound additive B with a structure shown in formula II and a conventional negative electrode film-forming additive; wherein, the additive A containing fluorobenzene sulfonate is shown as a structural formula in a formula I:
wherein R is selected from alkyl, alkoxy, alkylene, acyl, cyano, benzyl, nitro, halogen atom, ester group containing 1-20 carbon atoms, sulfonyl group containing 1-20 carbon atoms, C substituted by halogen1-C20Any one of linear or branched alkyl; x1、X2、X3、X4And X5Each independently selected from any one of hydrogen atom, fluorine atom, alkyl, alkylene, alkoxy or aromatic group, and X1-X5At least one of which is substituted by a fluorine atom;
the cyclic sulfonate additive B is represented by the structural formula II:
wherein, Y1-Y5Each independently selected from hydrogen atom, fluorine atom, alkyl, alkenyl, cyano, alkoxy, C substituted by fluorine1-C12Any one of linear or branched alkyl groups.
Preferably, in some embodiments of the present invention, the fluorinated phenyl sulfonate compound additive a having the structure of formula i is selected from one or more of the following compounds:
preferably, in some embodiments of the present invention, the cyclic sulfonate additive B having the structure of formula ii is selected from one or more of the following compounds:
further, the conventional negative electrode film forming additive is selected from one or more of Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), vinyl sulfate (DTD), ethylene carbonate (VEC), 1, 2-difluoroethylene carbonate (DFEC), vinyl sulfite (ES), vinyl sulfite (VES), and tris (trimethylalkane) borate (TMSB).
Preferably, in some embodiments of the present invention, the content of the fluorine-containing phenyl sulfonate compound additive a having the structure of formula i is 0.1-3.0% of the total mass of the electrolyte; the content of the cyclic sulfonate additive B with the structure of the formula II accounts for 0.1-1.0% of the total mass of the electrolyte; the content of the conventional negative electrode film forming additive accounts for 0.5-5.0% of the total mass of the electrolyte.
Preferably, in some embodiments of the present invention, the conventional negative electrode film forming additive is fluoroethylene carbonate (FEC) and vinyl sulfate (DTD), and the content of fluoroethylene carbonate (FEC) and vinyl sulfate (DTD) is 1.0% and 0.5% of the total mass of the electrolyte, respectively.
In another aspect of the invention, the invention provides a battery electrolyte with high and low temperature performance, which comprises electrolyte lithium salt, a non-aqueous organic solvent and an additive, wherein the additive consists of the additive with the structures shown in formula I and formula II and a conventional negative electrode film-forming additive.
Further, the electrolyte lithium salt is selected from lithium hexafluorophosphate (LiPF)6) Lithium difluorobis (oxalato) phosphate (LiPF)2(C2O4)2) Lithium tetrafluoro oxalate phosphate (LiPF)4C2O4) Lithium difluorophosphate (LiPF)2O2) Lithium oxalate phosphate (LiPO)2C2O4) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiODFB), lithium tetrafluoroborate (LiBF)4) One or more of lithium bis (fluorosulfonyl) imide (LiTFSI) and lithium bis (fluorosulfonyl) imide (LiFSI).
Further, the lithium hexafluorophosphate (LiPF)6) The content of the lithium salt compound accounts for 12.5-15.0% of the total mass of the electrolyte, and the content of other lithium salt compounds accounts for 0.1-5.0% of the total mass of the electrolyte.
Preferably, in some embodiments of the invention, the electrolyte lithium salt is lithium hexafluorophosphate (LiPF)6) Lithium difluorophosphate (LiPF)2O2) And lithium bis (fluorosulfonyl) imide (LiFSI), and lithium hexafluorophosphate (LiPF)6) Lithium difluorophosphate (LiPF)2O2) The content of the lithium bis (fluorosulfonyl) imide and the content of the lithium bis (fluorosulfonyl) imide (LiFSI) respectively account for 12.5%, 0.5% and 2.5% of the total mass of the electrolyte.
Further, the non-aqueous organic solvent is selected from carbonate compounds and/or carboxylic ester compounds, wherein the carbonate compounds comprise cyclic carbonate and chain carbonate, and the cyclic carbonate is at least one of Ethylene Carbonate (EC) and Propylene Carbonate (PC); the chain carbonate comprises one or more of diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC) and Methyl Propyl Carbonate (MPC).
Preferably, the content of the cyclic carbonate is 25.0-45.0% of the total mass of the electrolyte; the content of the chain carbonate accounts for 40.0-70.0% of the total mass of the electrolyte.
More preferably, in some embodiments of the present invention, the non-aqueous organic solvent is Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC), and the mass ratio of Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) is 1: 1: 1.
in another aspect of the present invention, the present invention provides a high-nickel ternary lithium ion battery with high and low temperature performance, wherein the lithium ion battery comprises a cathode plate, an anode plate, a separation film arranged between the cathode plate and the anode plate, and the battery electrolyte with high and low temperature performance.
Further, the cathode plate comprises an aluminum foil current collector and a cathode diaphragm, and the anode plate comprises a copper foil current collector and an anode diaphragm; the cathode membrane comprises a cathode active substance, a conductive agent and a binder; the anode membrane includes an anode active material, a conductive agent, and a binder.
Further, the cathode active material is LiNi1-x-y-zCoxMnyAlzO2Wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5, and x + y + z is more than or equal to 0 and less than or equal to 1; the anode active substance is artificial graphite, natural graphite, lithium titanate or SiOwThe silicon-carbon composite material is compounded with graphite, wherein w is more than 1 and less than 2.
Compared with the prior art, the invention has the following advantages:
(1) one or more of the conventional negative electrode film forming additives can be reduced preferentially on the surface of the negative electrode and decomposed to form an SEI film with excellent performance, so that the decomposition process of an electrolyte is effectively prevented, and the reversible capacity performance, the cycle performance and the safety performance of the power battery are improved;
(2) the fluorine-containing phenyl sulfonate compound additive A with the structure shown in the formula I participates in the formation of an SEI film on the surface of a negative electrode in preference to a solvent, inhibits the reductive decomposition of an organic solvent, and reduces the interface impedance of the SEI film, so that the low-temperature cycle performance of a power battery is improved; meanwhile, the compound is preferentially oxidized by a solvent to form an excellent interface protective film on the surface of the anode, so that the reaction activity of an electrode material and an electrolyte is reduced, the dissolution of metal ions is inhibited, and the room-temperature cycle performance of the power battery is improved; in addition, benzene rings and sulfonic acid groups in the compound form a thinner SEI film by changing the composition of the SEI film, so that Li+At the electrode-electrolyte interfaceThe high-current density is used for rapid transmission and diffusion, the interface impedance of the electrode is further reduced, and the multiplying power performance of the power battery under the room temperature condition is improved; furthermore, the compound prevents LiPF by forming a passivation film on the surface of the electrode6HF generated by thermal decomposition and hydrolysis corrodes the anode material, so that the dissolution of metal ions in the anode and the deposition on the cathode are reduced, the direct contact between the electrolyte and the anode is reduced, and the power battery has good cycle performance and capacity recovery rate at high temperature;
(3) the cyclic sulfonate compound additive B with the structure of formula II can be used for reducing other components in the electrolyte to form a film on the surfaces of the anode and the cathode of the battery preferentially in the first charging and discharging, and the formed SEI film has good thermal stability, can inhibit the co-intercalation and reductive decomposition of solvent molecules in the cathode, remarkably improves the discharge platform of the lithium ion battery, reduces the gas generation of the battery in a high-temperature environment, and effectively improves the high-temperature storage and high-temperature cycle performance of the power battery;
(4) compared with the single use of LiPF6The invention adds a novel conductive lithium salt lithium difluorophosphate (LiPO) with good film forming property2F2) Or the lithium bis (fluorosulfonyl) imide (LiFSI) adopts a combination of various novel film-forming lithium salts, which is beneficial to improving the high-low temperature performance, rate capability, long cycle performance and safety performance of the lithium ion power battery; the introduction of lithium salt additives such as phosphate and the like can enable the positive and negative electrode films of the battery to be more compact and stable, reduce the interface impedance of the positive and negative electrodes and enable the power battery to have better cycle performance;
(5) the four substances in the electrolyte of the invention act together and influence each other, and compared with only using one or two or three of the substances, the electrolyte can improve the performance of the electrolyte and has the function of 1+1+1+1 > 4.
In conclusion, the electrolyte additive for the high-nickel ternary lithium ion power battery and the electrolyte containing the same, which have both high and low temperature long cycle performance, provided by the invention, have excellent film-forming performance on the surface of an electrode through the synergistic effect of the fluorine-containing benzene sulfonate compound additive, the cyclic sulfonate compound additive, the novel nitrogen-containing lithium salt additive and the conventional negative film-forming additive, so that the electrochemical performance of the high-nickel ternary lithium ion power battery at low temperature and high temperature is effectively improved, the problem that the high and low temperature performance of the battery in the prior art cannot be considered is well solved, and the application range of the battery is effectively expanded.
Drawings
FIG. 1 is a diagram of the molecular structures and HOMO/LUMO orbitals of various solvents and additives;
FIG. 2 is an EIS curve of a Li | AG battery in electrolytes containing different additives;
FIG. 3 shows the capacity retention and capacity recovery of NCM 622/graphite batteries containing different electrolyte compositions after storage at 60 ℃;
figure 4 is a-20 ℃ low temperature discharge curve for NCM 622/graphite cells containing different electrolyte compositions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and 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.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
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.
Furthermore, the description below of the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily for the same embodiment or example.
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 electrolyte: in a glove box filled with argon, ethylene carbonate, dimethyl carbonate and propylene carbonate are mixed according to the mass ratio of EC: DMC: EMC 1: 1: 1, and then 12.5 wt% of lithium hexafluorophosphate (LiPF) based on the total weight of the electrolyte was slowly added to the mixed solution6) 0.5 wt% lithium difluorophosphate (LiPO) based on the total weight of the electrolyte2F2) And 2.5 wt% of lithium bis (fluorosulfonyl) imide (LiFSI) based on the total weight of the electrolyte, and finally 1.0 wt% of compound a having a structure represented by formula i, 0.5 wt% of compound B having a structure represented by formula ii (see table 1 for specific selection of compound A, B), 1.0 wt% of fluoroethylene carbonate (FEC), and 2.0 wt% of vinyl sulfate (DTD) based on the total weight of the electrolyte were added and stirred uniformly to obtain the lithium ion battery electrolyte of example 1.
Preparing a soft package battery: stacking the prepared positive plate, the diaphragm and the negative plate in sequence, enabling the diaphragm to be positioned between the positive plate and the negative plate, and winding to obtain a bare cell; and (3) placing the bare cell into an outer package, injecting the prepared electrolyte into the dried battery, packaging, standing, forming, shaping and grading to finish the preparation of the lithium ion soft package battery (the full battery material is a high nickel system of NCM 622/graphite 4.2V).
Preparing a button cell: in a glove box filled with argon, a positive electrode shell is placed on an insulating table, 1-2 drops of electrolyte are dripped, a pole piece, a diaphragm, a lithium piece, a gasket, an elastic piece and a negative electrode shell are sequentially placed, and the positive electrode shell is lightly placed on a manual electric sealing machine for sealing. And after the assembly is finished, taking out the assembled battery pack, standing for 12h, and testing (the half battery material is AG/Li).
Examples 2 to 9 and comparative examples 1 to 5
Examples 2 to 9 and comparative examples 1 to 5 were the same as example 1 except that the electrolyte composition was changed to additives shown in Table 1.
TABLE 1 composition ratios of the components of the electrolytes of examples 1-9 and comparative examples 1-5
Performance testing
The full cells obtained in examples 1 to 9 and comparative examples 1 to 5 were subjected to performance tests:
(1) and (3) testing the normal-temperature cycle performance: at 25 ℃, the battery after capacity grading is charged to 4.2V at constant current and constant voltage according to 1C, the current is cut off at 0.05C, then the battery is discharged to 3.0V at constant current according to 1C, and the capacity retention rate of the 1000 th cycle is calculated after 1000 cycles of charge/discharge according to the cycle, and 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 thickness expansion and capacity residual recovery rate at high temperature of 60 ℃: firstly, the battery is placed at normal temperature and is circularly charged and discharged for 1 time (4.2V-3.0V) at 0.5C, and the discharge capacity C before the battery is stored is recorded0Then charging the battery to 4.2V full-voltage state with constant current and constant voltage, and using vernier caliper to test the thickness d of the battery before high-temperature storage1(the two diagonals of the battery are respectively connected through a straight line, and the intersection point of the two diagonals is a battery thickness test point), then the battery is placed in a 60 ℃ incubator for storage for 7 days, and after the storage is finished, the battery is taken out and the thermal thickness d of the stored battery is tested2Calculating the expansion rate of the thickness of the battery after the battery is stored for 7 days at a constant temperature of 60 ℃; after the battery is cooled for 24 hours at room temperature, the battery is discharged to 3.0V at a constant current of 0.5C, then charged to 4.2V at a constant current and a constant voltage of 0.5C, and the discharge capacity C after the battery is stored is recorded1And a charging capacity C2And calculating the capacity residual rate and the capacity recovery rate after the battery is stored for 7 days at the constant temperature of 60 ℃, wherein the calculation formula is as follows:
thickness expansion rate of battery after 7 days of storage at 60 ═ d2-d1)/d1*100％；
Capacity residue rate C after 7 days of high temperature storage at 60 DEG C1/C0*100％；
Capacity recovery rate C after 7 days of high-temperature storage at 60 DEG C2/C0*100％。
(3) And (3) testing the low-temperature cycle performance: under the condition of low temperature of minus 20 ℃, the battery after capacity grading is charged to 4.2V at constant current and constant voltage of 0.3C, the current is cut off at 0.05C, then the battery is discharged to 3.0V at constant current of 0.5C, and according to the cycle, the cycle capacity retention rate of 50 weeks is calculated after 50 cycles of charging/discharging. The calculation formula is as follows:
the 50 th cycle capacity retention ratio (%) (50 th cycle discharge capacity/first cycle discharge capacity) × 100%.
The results of the above performance tests are shown in table 2.
Table 2 lithium ion battery electrical performance test results
As can be seen from a comparison of the test results of comparative example 4 and examples 1-7 in Table 2: the fluorine-containing phenyl sulfonate compound additive A with the structure of the formula I is used, so that the normal temperature, low temperature and high temperature cycle performance of the high-nickel ternary lithium ion power battery can be effectively improved, the excellent electrochemical performance is realized in a wider temperature range, the problem that the high and low temperature performance of the battery in the prior art cannot be considered is well solved, and the application range of the high-nickel ternary lithium ion power battery is effectively expanded.
As can be seen from a comparison of the results of the electrical property tests of comparative example 4 and examples 1-3 in Table 2: in the embodiment, the additive A of the fluorine-containing phenyl sulfonate compound with the structure shown in the formula I participates in and changes the formation of an SEI film on the surface of a negative electrode, so that the reductive decomposition of an organic solvent is inhibited, the interfacial resistance of the SEI film is reduced, and the low-temperature cycle performance of a power battery is improved; meanwhile, benzene ring and sulfonic acid group in the compound form an excellent interface protective film on the surface of the positive electrode, so that the reaction activity of an electrode material and an electrolyte is reduced, the dissolution of metal ions is inhibited, and Li is improved+The transmission rate at the electrode-electrolyte interface further reduces the electrode interface impedance and improves the room-temperature cycle performance and the rate performance of the power battery; in addition, the compound prevents LiPF by forming a passivation film on the surface of the electrode6HF generated by thermal decomposition and hydrolysis corrodes the anode material, thereby reducing gold in the anodeThe dissolution of the metal ions and the deposition on the negative electrode, and the direct contact between the electrolyte and the positive electrode are reduced, so that the power battery has good cycle performance and capacity recovery rate at high temperature.
Further, compared with a comparative example 5 without the additive B with the structure shown in the formula II, the cyclic sulfonate compound additive is used in each embodiment of the invention, other components in the electrolyte can be preferentially reduced to form a stable film on the surfaces of the anode and the cathode of the battery during first charging and discharging, so that the co-intercalation and reductive decomposition of solvent molecules on the cathode are inhibited, the discharge platform of the lithium ion battery is remarkably improved, the gas generation of the battery in a high-temperature environment is reduced, and the high-temperature storage and high-temperature cycle performance of the power battery are effectively improved.
Furthermore, compared with comparative examples 4-5 using the fluorinated phenyl sulfonate additive with the structure of formula I or the cyclic sulfonate additive B with the structure of formula II alone and comparative example 3 not adding the additive A with the structure of formula I or the additive B with the structure of formula II, the electrolyte of each embodiment of the invention is jointly used in the electrolyte through the synergistic effect of the fluorinated phenyl sulfonate additive, the cyclic sulfonate additive, the novel nitrogen-containing lithium salt additive and the conventional negative electrode film-forming additive, so that the electrolyte has excellent film-forming performance on the surface of an electrode, and the electrochemical performance of the electrolyte is improved.
Further, in each example of the present invention, a novel conductive lithium salt lithium difluorophosphate (LiPO) having good film-forming characteristics was added as compared with comparative example 2 in which no nitrogen-containing lithium salt was added2F2) Or/and lithium bis (fluorosulfonyl) imide (LiFSI) compared to LiPF alone6The combination of various novel film-forming lithium salts is beneficial to improving the high-low temperature performance, the rate capability, the long cycle performance and the safety performance of the lithium ion battery; the introduction of lithium salt additives such as phosphate and the like can enable the positive and negative electrodes of the battery to form more compact and stable films, reduce the interface impedance of the positive and negative electrodes and enable the power battery to have better cycle performance.
Those skilled in the art to which the invention pertains will readily appreciate that variations and modifications of the above-described embodiments are possible in light of the above teachings and teachings. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (14)
1. The battery electrolyte additive giving consideration to high and low temperature performance is characterized by comprising a fluorine-containing phenyl sulfonate compound additive A with a structure shown in a formula I, a cyclic sulfonate additive B with a structure shown in a formula II, a conventional negative electrode film-forming additive, lithium difluorophosphate and lithium difluorosulfimide; wherein, the additive A containing fluorobenzene sulfonate is shown as formula A1The structural formula is shown as follows:
the cyclic sulfonate additive B is represented by the structural formula II:
wherein, Y1-Y5Each independently selected from hydrogen atom, fluorine atom, alkyl, alkenyl, cyano, alkoxy, C substituted by fluorine1-C12Any one of linear or branched alkyl;
the conventional negative film forming additive is fluoroethylene carbonate and ethylene sulfate.
2. The battery electrolyte additive with both high and low temperature performance as claimed in claim 1, wherein the cyclic sulfonate additive B with the structure of formula II is selected from one or more of the following compounds:
3. the battery electrolyte additive for both high and low temperature performance of claim 1 wherein the additive has formula a1The content of the fluorine-containing phenyl sulfonate compound additive A in the structure accounts for 0.1-3.0% of the total mass of the electrolyte; the content of the cyclic sulfonate additive B with the structure of the formula II accounts for 0.1-1.0% of the total mass of the electrolyte; the content of the conventional negative electrode film forming additive accounts for 0.5-5.0% of the total mass of the electrolyte.
4. The battery electrolyte additive for achieving both high and low temperature performance as claimed in claim 3, wherein the content of fluoroethylene carbonate and ethylene sulfate is 1.0% and 0.5% of the total mass of the electrolyte respectively.
5. A battery electrolyte with high and low temperature performance, which is characterized by comprising an electrolyte lithium salt, a non-aqueous organic solvent and an additive, wherein the additive is the battery electrolyte additive with high and low temperature performance as claimed in any one of claims 1 to 4.
6. The battery electrolyte having both high and low temperature performance as claimed in claim 5, wherein the electrolyte lithium salt is lithium hexafluorophosphate.
7. The battery electrolyte with both high and low temperature performance as claimed in claim 6, wherein the content of lithium hexafluorophosphate is 12.5-15.0% of the total mass of the electrolyte, and the content of lithium difluorophosphate and lithium bis-fluorosulfonylimide in the additive is 0.1-5.0% of the total mass of the electrolyte.
8. The battery electrolyte with both high and low temperature performance according to claim 7, wherein the contents of lithium hexafluorophosphate, lithium difluorophosphate and lithium bis-fluorosulfonylimide respectively account for 12.5%, 0.5% and 2.5% of the total mass of the electrolyte.
9. The battery electrolyte solution compatible with high and low temperature performance according to claim 5, wherein the non-aqueous organic solvent is selected from carbonate compounds and/or carboxylic ester compounds, wherein the carbonate compounds comprise cyclic carbonate and chain carbonate, and the cyclic carbonate is at least one of ethylene carbonate and propylene carbonate; the chain carbonate comprises one or more of diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate and methyl propyl carbonate.
10. The battery electrolyte with both high and low temperature performance according to claim 9, wherein the content of the cyclic carbonate is 25.0-45.0% of the total mass of the electrolyte; the content of the chain carbonate accounts for 40.0-70.0% of the total mass of the electrolyte.
11. The battery electrolyte solution compatible with high and low temperature performance according to claim 9, wherein the non-aqueous organic solvent is 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 1: 1: 1.
12. a high-nickel ternary lithium ion battery with high and low temperature performance is characterized by comprising a cathode pole piece, an anode pole piece, a separation film arranged between the cathode pole piece and the anode pole piece and the battery electrolyte with high and low temperature performance according to any one of claims 5 to 11.
13. The high-nickel ternary lithium ion battery with both high and low temperature performance of claim 12, wherein the cathode plate comprises an aluminum foil current collector and a cathode membrane, and the anode plate comprises a copper foil current collector and an anode membrane; the cathode membrane comprises a cathode active substance, a conductive agent and a binder; the anode membrane includes an anode active material, a conductive agent, and a binder.
14. The lithium ion battery as claimed in claim 13, wherein the cathode active material is LiNi1-x-y-zCoxMnyAlzO2Wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5, and x + y + z is more than or equal to 0 and less than or equal to 1; the anode active substance is artificial graphite, natural graphite, lithium titanate or SiOwThe silicon-carbon composite material is compounded with graphite, wherein w is more than 1 and less than 2.
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| CN110212235B (en) * | 2019-06-12 | 2022-04-08 | 广州天赐高新材料股份有限公司 | Lithium secondary battery electrolyte capable of reducing battery impedance and lithium secondary battery thereof |
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