CN114156535A - Electrolyte, lithium ion battery and power vehicle - Google Patents

Electrolyte, lithium ion battery and power vehicle Download PDF

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CN114156535A
CN114156535A CN202010928769.5A CN202010928769A CN114156535A CN 114156535 A CN114156535 A CN 114156535A CN 202010928769 A CN202010928769 A CN 202010928769A CN 114156535 A CN114156535 A CN 114156535A
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electrolyte
lithium
carbonate
battery
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CN114156535B (en
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谭伟华
李继华
容亮斌
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BYD 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
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The application provides an electrolyte, which comprises a lithium salt, an organic solvent, a conventional film-forming additive and a sulfonylurea additive shown as a formula (I):
Figure DDA0002669409760000011
wherein R is1One selected from hydrogen atom, halogen atom, alkyl, alkoxy, amino, hydroxyl, ester group and acyl; r2Selected from hydrogen atoms, alkyl groups, alkoxy groups, cycloalkyl groups, haloalkyl groups, haloalkoxy groups, halocycloalkyl groups or cycloalkyl groups containing ring heteroatoms. The electrolyte can ensure that the battery has good normal temperature performance and low temperature performance and also has excellent high-temperature cycle performanceAnd high temperature storage properties. The application also provides a lithium ion battery containing the electrolyte and a power vehicle.

Description

Electrolyte, lithium ion battery and power vehicle
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to electrolyte, a lithium ion battery and a power vehicle.
Background
The lithium ion battery has the characteristics of high voltage, high specific capacity, no memory effect and the like, is widely applied to the fields of portable electronic devices (mobile phones and the like), unmanned aerial vehicles, electric automobiles and the like, continuously puts forward higher requirements on the battery performance of the lithium ion battery along with the development of economy and science and technology, and the addition of a film-forming additive into the electrolyte of the lithium ion battery becomes an effective means for improving the cycle energy of the battery.
Vinylene Carbonate (VC) is the most commonly used negative film-forming additive, and is helpful to form a stable and complete SEI film (solid electrolyte interface film) on the surface of a negative electrode material (such as graphite) in the charging and discharging processes of a battery, so as to inhibit the electrolyte from damaging the negative electrode material structure and falling off from a pole piece, and improve the cycle performance of the battery. However, although the cycle performance of the lithium battery using VC as a film-forming additive can be improved to a certain extent at normal temperature, if the battery has particularly excellent high-temperature performance, the usage amount of VC needs to be large, the polarization potential of the battery under low-temperature conditions is generally large, and the high usage amount of VC causes the impedance of the battery to be increased sharply, so that the low-temperature cycle performance of the battery (especially the cycle performance under large current) is not good, and it is difficult for other existing electrolyte systems to simultaneously improve the high-temperature performance and the low-temperature performance of the battery. Therefore, it is necessary to develop an electrolyte system that can satisfy the normal temperature cycle performance, the low temperature cycle performance, and the high temperature cycle performance of the lithium ion battery.
Disclosure of Invention
In view of the above, the present application provides an electrolyte for a lithium ion battery, which is added with a specific sulfonylurea additive on the basis of a conventional film forming additive, and the electrolyte can enable the lithium ion battery to have good normal temperature performance and low temperature performance, and also have excellent high temperature cycle performance and high temperature storage performance.
Specifically, the first aspect of the present application provides an electrolyte, which comprises a lithium salt, an organic solvent, a conventional film-forming additive, and a sulfonylurea additive represented by formula (i):
Figure BDA0002669409750000021
in the formula (I), R1Selected from hydrogen atom, halogen atom, alkyl and alkoxyOne of group, amido group, hydroxyl group, ester group and acyl group; r2Selected from a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a haloalkyl group, a haloalkoxy group, a halocycloalkyl group or a cycloalkyl group containing a ring heteroatom; the conventional film-forming additive is a film-forming additive that can prevent the electrode material from falling off.
The electrolyte provided by the first aspect of the application is further added with a sulfonylurea additive on the basis of a conventional film-forming additive, the additive is a physical adsorption type negative electrode additive, the surface affinity of the additive with a negative electrode material (particularly graphite) is strong, when the additive is adsorbed on the surface of a negative electrode, an adsorption film layer formed by the additive can inhibit the reduction of an electrolyte solvent (such as PC and the like) with active properties, the stability of the electrolyte is maintained, the thickness of the adsorption film layer is thin, the impedance is low, the diffusion speed of lithium ions of an SEI film on the surface of a negative electrode sheet cannot be obviously inhibited, the normal-temperature and low-temperature cycle performance of a battery cannot be obviously reduced, and particularly the low-temperature cycle performance of the battery cannot be degraded. In addition, the sulfonylurea additive has high stability under high potential, is not easy to oxidize on the positive electrode side, is not easy to reduce on the negative electrode side, and cannot shuttle back and forth between the positive electrode and the negative electrode of the battery, the self-discharge rate of the battery is low, and particularly, when the battery is deeply charged and discharged under a high-temperature environment, a physical adsorption layer formed by the sulfonylurea additive still has good electrochemical stability even under a large polarization potential (such as charging and discharging under large current), and is beneficial to keeping the stability of an SEI film; in addition, the sulfur-oxygen bond ((═ O) S (═ O)) in the sulfonylurea additive can maintain good stability with temperature change, and is not easy to decompose at high temperature, so that the battery can have excellent high-temperature cycle performance and high-temperature storage performance.
The electrolyte containing the sulfonylurea additive can ensure that the battery can obtain a physical adsorption film layer with excellent performance in a wide temperature range of low temperature-normal temperature-high temperature, can form an ion channel of lithium ions on the surface of a negative electrode together with an SEI film formed by a conventional film forming additive, and is beneficial to improving the stability of the SEI film, thereby ensuring that the battery keeps good normal-temperature cycle performance and normal-temperature storage performance, and good low-temperature cycle performance, and simultaneously, the high-temperature cycle performance and high-temperature storage performance of the battery are obviously improved, and the self-discharge rate of the battery is reduced.
In this application, R1Can be selected from one of hydrogen atom, halogen atom, alkyl, alkoxy, amino, hydroxyl, ester (-COOR), acyl (-COR). Wherein the halogen atom comprises chlorine atom (Cl), bromine atom (Br) and iodine atom (I). The amine group may include a primary amino group (-NH)2) Secondary amino (or alkylamino, -NHR), tertiary amino (or dialkylamino, -NRR'). Alternatively, the number of carbon atoms of the alkyl group and the alkoxy group can be 1 to 10.
In this application, R2May be selected from a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a haloalkyl group, a haloalkoxy group, a halocycloalkyl group or a cycloalkyl group containing a ring hetero atom. Wherein cycloalkyl containing a ring heteroatom means that one or more carbon atoms of the 'cycloalkyl' is substituted with at least one heteroatom selected from N, S and O. The number of carbon atoms in the alkyl group, the haloalkyl group, the alkoxy group, and the haloalkoxy group may be 1 to 10, for example, 1 to 6. The number of carbon atoms in the cycloalkyl group, the halocycloalkyl group, the cycloalkyl group containing a ring hetero atom may be 2 to 10, preferably 3 to 10.
In some embodiments of the present application, R is1Can be hydrogen atom, chlorine atom, bromine atom, iodine atom, amino group, methyl group, ethyl group, methoxy group, ethoxy group (CH)3CH2O-), acetyl (CH)3CO-), methyl formate (CH)3OCO-) or a formate group (CH)3CH2OCO-). Preferably a hydrogen atom, a chlorine atom, a methyl group or an amino group.
In some embodiments of the present application, R is2It may be a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, azepanyl group or the like.
Specifically, in the embodiment of the present application, the specific structural formula of the sulfonylurea additive may be as shown in the following (J) to (T):
Figure BDA0002669409750000031
Figure BDA0002669409750000041
wherein the additive shown in the formula (J) is concretely p-tolbutamide. The additive shown in the formula (K) is specifically ammonia sulphonylurea. The additive shown in the formula (L) is concretely chlorpheniramine. The additive shown in the formula (M) is specifically p- (N, N-dimethyl) phensulbutea. The additive shown in the formula (N) is p-toluenesulfonyl urea. The additive shown in the formula (O) is 4-chlorobenzenesulfonyl urea. The additive shown in the formula (P) is specifically sulfonylurea. The additive shown in the formula (Q) is specifically tolfenuron. The additive shown in the formula (R) is specifically acetylbenzenesulfonylcyclohexaneurea. The additive shown in the formula (S) is specifically the ditosylsulfonamide. The additive shown in the formula (T) is specifically tolazamide. Wherein when R is1Is methyl, R2When the additive is hydrogen atom, the sulfonylurea additive can be not only p-toluenesulfonyl urea shown in formula (N), but also 2-methylbenzenesulfonyl urea and 3-methylbenzenesulfonyl urea.
Wherein the content of the sulfonylurea additive in the electrolyte may be 0.1-5.0 parts by weight based on 100 parts by weight of the organic solvent. Preferably 0.2 to 2.0 parts by weight.
In the present application, the conventional film-forming additive is a film-forming additive that can inhibit the battery electrode material from falling off (or "peeling") from the current collector. In particular, conventional film-forming additives can preferably suppress exfoliation of graphite, which is an anode material. Specifically, the conventional film forming additive may include at least one of Vinylene Carbonate (VC), Vinyl Ethylene Carbonate (VEC), phenyl ethylene carbonate (PhEC), styrene ethylene carbonate (PhVC), fluoroethylene carbonate (FEC), Catechol Carbonate (CC), Alkenylphenyl Methyl Carbonate (AMC), vitamin a (va), and 2-hydro furan (CN-F).
Alternatively, the content of the conventional film forming additive in the electrolyte is 0.5 to 5 parts by weight, preferably 1.0 to 5.0 parts by weight, and more preferably 1.0 to 3.5 parts by weight, based on 100 parts by weight of the organic solvent. If the dosage of the conventional film forming additive is too much, the low-temperature impedance of the battery is greatly increased, and the low-temperature performance of the battery is reduced. In the presence of the sulfonylurea additives, a small amount of conventional film forming additives (such as VC, VEC and the like) can generate a thin and compact SEI film which has smaller low-temperature resistance, so that the battery can be ensured to have better normal-temperature and low-temperature cycle performance, and the SEI film formed by the sulfonylurea additives is stable and not easy to break at high temperature and has small resistance, so that the battery has more excellent high-temperature cycle performance and high-temperature storage performance.
In the electrolyte of the present application, the lithium salt may include lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium hexafluoroantimonate (LiSbF)6) Lithium perchlorate (LiClO)4) Lithium bis (oxalato) borate (LiBOB), lithium bis (oxalato) borate (LiDFOB), lithium trifluoro (LiCF)3SO3) Lithium perfluorobutylsulfonate (LiC)4F9SO3) Lithium bis (trifluoromethylsulfonyl) imide (Li (CF)3SO2)2N), lithium bis (perfluoroethylsulfonyl) imide (Li (C)2F5SO2)2N) is selected. The content of the lithium salt in the electrolyte is not particularly limited, and may be determined by the conventional amount in the art. For example, the concentration of the lithium salt in the electrolyte may be 0.1 to 2.0mol/L, preferably 0.7 to 1.6 mol/L.
In the electrolyte of the present application, the organic solvent may include one or more of gamma-butyrolactone (GBL), Ethylene Carbonate (EC), Propylene Carbonate (PC), butylene carbonate, dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), Methyl Propyl Carbonate (MPC), ethyl propyl carbonate, N-methylpyrrolidone, N-dimethylformamide, N-methylformamide, N-methylacetamide, acetonitrile, sulfolane, dimethyl sulfoxide, dimethyl sulfite, and other cyclic organic esters containing fluorine, sulfur, or unsaturated bonds, etc., but is not limited thereto. Preferably, the organic solvent is one or more, more preferably two or more, of GBL, EC, PC, EMC, DEC and DMC.
The electrolyte provided by the first aspect of the application contains a conventional film forming additive and the sulfonylurea additive, can enable a battery to obtain a thin, compact and complete SEI film and a low-impedance and thin physical adsorption film layer in a negative electrode shape when the battery works in a wide temperature range from low temperature to normal temperature to high temperature, and can also enable the SEI film to keep stable by the physical adsorption film, so that the electrolyte can ensure that the battery has good normal-temperature cycle performance and normal-temperature storage performance, and the high-temperature cycle performance and high-temperature storage performance of the battery are obviously improved while the good low-temperature cycle performance is kept, and the self-discharge rate of the battery is reduced.
The preparation method of the electrolyte provided by the application is simple, and comprises the following steps: adding lithium salt, conventional film-forming additive and the sulfonylurea additive into an organic solvent, and stirring to fully dissolve and uniformly disperse the components to obtain the electrolyte. The addition sequence of the lithium salt, the conventional film-forming additive and the sulfonylurea additive is not required, and the lithium salt, the conventional film-forming additive and the sulfonylurea additive can be added in batches or simultaneously.
In a second aspect, the present application provides a lithium ion battery, wherein the electrolyte according to the first aspect of the present application is embedded in the lithium ion battery. The battery containing the electrolyte has good normal-temperature cycle performance and normal-temperature storage performance, good low-temperature cycle performance, excellent high-temperature cycle performance and high-temperature storage performance, and low self-discharge rate.
Specifically, the lithium ion battery comprises a battery shell, and a battery core and an electrolyte, which are accommodated in the battery shell, wherein the battery core comprises a positive plate, a negative plate and a diaphragm located between the positive plate and the negative plate, and the electrolyte is as described in the first aspect of the present application.
The preparation method of the lithium ion battery comprises the following steps: and sequentially stacking the positive plate, the diaphragm and the negative plate to form a battery core, accommodating the battery core in a battery shell, injecting the electrolyte, and sealing the battery shell to obtain the lithium ion battery.
The negative plate, the positive plate and the diaphragm are all conventional choices in the battery field. For example, the positive electrode sheet includes a current collector and a positive electrode material layer disposed on the current collector, wherein the positive electrode material layer includes a positive electrode active material, a positive electrode binder, and optionally a conductive agent. The negative electrode sheet includes a current collector and a negative electrode material layer disposed on the current collector, wherein the negative electrode material layer may include a negative electrode active material, a negative electrode binder, and optionally a conductive agent. The diaphragm comprises modified polyethylene felt, modified polypropylene felt, superfine glass fiber felt, vinylon felt, or a composite film formed by welding or bonding nylon felt and a wettable polyolefin microporous film.
In a third aspect, the present application provides a powered vehicle comprising a lithium ion battery as described in the second aspect of the present application.
Advantages of embodiments of the present application 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 embodiments of the present application.
Detailed Description
The examples of the present application are further illustrated below in various examples.
Example 1
A method of making a lithium ion battery, comprising:
a) preparing an electrolyte by the following steps: in a glove box, mixing organic solvents of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and Propylene Carbonate (PC) according to the proportion in table 1 to obtain a mixed solvent; LiPF is added to 100 parts by weight of the mixed solvent6As electrolyte, the concentration is 1.0mol/L, and the following additives are added: 2.0 parts by weight of Vinylene Carbonate (VC) (commercially available from Shandong Shishenghua chemical group), and X parts by weight of p-toluenesulfonamide (purity 99.7%) (commercially available from Shokuguano chemical Co., Ltd.) were stirred until all solid substances were dissolved to obtain a desired electrolyte, wherein the contents of the respective components are shown in Table 1.
b) Preparing a positive plate: the anode active material LiFePO is added4(Hunan Tan electrochemical technology Co., Ltd.) together with conductive carbon black and polyvinylidene fluoride in a ratio of 97.5: 1.5: 1.0, dissolving in N-methyl pyrrolidone, stirring uniformly to obtain anode slurry with solid content of 50 wt%, coating the anode slurry on two sides of an aluminum foil with thickness of 13 mu m, baking at 110 +/-5 ℃, rolling, and drying in vacuum to form an anode material layer with thickness of 155 mu m +/-2 mu m, thus obtaining the anode sheet.
c) Preparing a negative plate: mixing a negative electrode active material-artificial graphite subjected to secondary granulation (commercially available from Shenzhen fibrate Rui GmbH, and the trademark is S360) with conductive carbon black, styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) according to a ratio of 96.2: 1.0: 1.3: dispersing the mixture in deionized water according to the weight ratio of 1.5, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on two sides of a copper foil with the thickness of 6 microns, baking at the temperature of 110 +/-5 ℃, rolling, and drying in vacuum to form a negative electrode material layer with the thickness of 110 +/-2 microns, thereby obtaining the negative electrode plate.
d) Assembling the battery: in a glove box, the above positive electrode sheet, 14 μm thick polypropylene separator and negative electrode sheet were stacked in this order, wound into a square bare cell, the bare cell was put into a battery case and welded, and then the above electrolyte was injected into the battery case, which was sealed to make a LP053450ARU type lithium ion battery, and the battery obtained in example 1 was denoted as S1.
Batteries of examples 2-7 were prepared according to the battery preparation method provided in example 1 and the formulation shown in table 1, and were designated as S2-S7, respectively.
Example 8
Battery S8 was prepared with reference to the battery preparation method provided in example 1, which differs from example 1 in that: when preparing the electrolyte, the p-chlorobenzenesulfenuron is adopted to replace the p-toluenesulfonylurea.
Example 9
Battery S9 was prepared with reference to the battery preparation method provided in example 1, which differs from example 1 in that: when preparing the electrolyte, the albuterol is used to replace the tolbutamide.
Example 10
Battery S10 was prepared with reference to the battery preparation method provided in example 1, which differs from example 1 in that: in the preparation of the electrolyte, p- (N, N-dimethyl) phensulbutea is used instead of tolbutamide.
TABLE 1 composition of electrolyte in batteries of examples
Figure BDA0002669409750000081
Figure BDA0002669409750000091
To highlight the advantageous effects of the examples of the present application, the following comparative examples 1 to 4 are provided.
Comparative examples 1 to 4
Preparing an electrolyte: in a glove box, mixing organic solvents EC, EMC, DEC, DMC and PC according to the proportion shown in Table 2 to obtain an organic mixed solvent; adding LiPF to 100 parts by weight of an organic mixed solvent6As an electrolyte, the concentration of the electrolyte is 1.0mol/L, and the following additives are selectively added: VC, Propylene Sulfite (PS), Methylene Methyldisulfonate (MMDS), vinyl sulfate (DTD); stirring until all solid substances are dissolved completely to obtain the required electrolyte, and the content of each raw material is shown in table 2.
Preparing a battery: the electrolytes of comparative examples 1 to 4 were prepared into batteries according to the battery preparation method described in example 1, and the prepared batteries were sequentially referred to as D1, D2, D3, and D4.
TABLE 2 comparative batteries and electrolyte compositions thereof
Figure BDA0002669409750000092
Performance testing
The lithium ion batteries manufactured according to the above examples 1 to 9 and comparative examples 1 to 4 were respectively subjected to the following tests:
normal temperature cycle performance (normal temperature cycle capacity retention): putting each battery into a thermostat at 25 ℃, connecting a battery performance tester BS-9300 through an outgoing line, charging at a constant current of 0.5C until the cut-off voltage is 3.8V, standing for 30min, discharging at a constant current of 0.5C until the voltage is 2.0V, standing for 30min, and performing 200 cycles under the condition, wherein the ratio of the 200 th discharge capacity to the 1 st discharge capacity is the capacity retention rate of the battery after circulating for 200 times at normal temperature.
Normal temperature storage performance (normal temperature storage capacity remaining rate): charging each battery at a constant current of 0.5C at the room temperature of 25 +/-2 ℃ until the cut-off voltage is 3.80V, and recording the charging capacity; and then, storing the battery in a constant temperature box at 25 ℃ for 28 days, then, placing the battery at the normal temperature of 25 +/-2 ℃, then, discharging at a constant current of 0.5 ℃ until the cut-off voltage is 2.0V, recording the discharge capacity, and determining the ratio of the discharge capacity to the charge capacity of each battery as the capacity residual rate of the battery stored at the normal temperature so as to evaluate the quality of the normal-temperature storage performance of the battery.
High temperature cycle performance (high temperature cycle capacity retention): the battery is placed in a thermostat at the temperature of 60 ℃, is connected with a battery performance tester BS-9300 through an outgoing line, is charged at a constant current of 0.5C until the voltage is 3.8V, is placed for 30min, is discharged at a constant current of 0.5C until the voltage is 2.0V, is placed for 30min, is subjected to 200 cycles under the condition, and the ratio of the 200 th discharge capacity to the 1 st discharge capacity is the cycle capacity retention rate of the battery after being subjected to high-temperature cycle for 200 times at the temperature of 60 ℃.
High-temperature storage performance (capacity remaining rate of high-temperature storage): charging each battery at a constant current of 0.5C at the room temperature of 25 +/-2 ℃ until the cut-off voltage is 3.80V, and recording the charging capacity; then the battery is placed in a thermostat at 60 ℃ for 28 days, then the battery is placed at the normal temperature of 25 +/-2 ℃ for more than 24 hours, then the battery is discharged at a constant current of 0.5 ℃ until the voltage is 2.0V, and the discharge capacity is recorded; the ratio of the discharge capacity to the charge capacity of each battery is the capacity residual rate of the battery stored at high temperature of 60 ℃, so that the high-temperature storage performance of the battery is evaluated.
Low temperature cycle performance (low temperature cycle capacity retention): the battery is placed in a thermostat at the temperature of minus 20 ℃, is connected with a battery performance tester BS-9300 through an outgoing line, is charged at a constant current of 0.2C until the voltage is 3.6V, is placed for 30min, is discharged at a constant current of 0.2C until the voltage is 2.0V, is placed for 30min, is subjected to 150 cycles under the condition, and the ratio of the 150-th discharge capacity to the 1-th discharge capacity is the cycle capacity retention rate of the battery after being subjected to low-temperature cycle 200 times at the temperature of minus 20 ℃, so that the quality of the low-temperature cycle performance of the battery is evaluated.
The results of the performance test of each cell are shown in table 3 below.
Table 3 performance test results of each battery
Figure BDA0002669409750000111
As can be seen from the data in table 3, the batteries S1-S10 (except S7) prepared in examples 1-10 of the present application have better low-temperature cycle capacity retention rate and significantly improved high-temperature cycle capacity retention rate and high-temperature storage capacity retention rate under the condition of good normal-temperature cycle capacity retention rate and normal-temperature storage capacity retention rate, compared with the batteries D1-D4 prepared in the comparative example. Furthermore, the battery S7 exhibited a decrease in low-temperature cycle performance due to the higher amount of VC (higher than that of comparative batteries D2-D4, up to the upper limit defined in the present application) as a conventional film-forming additive, but its high-temperature cycle and high-temperature storage performance were still higher than those of batteries D2-D4, and the low-temperature cycle performance of battery S7 was still particularly excellent as compared with that of battery D1, which was the same as that of the VC additive.
Therefore, the electrolyte for the lithium battery provided by the application can enable the prepared lithium ion battery to have good normal-temperature performance and simultaneously have good low-temperature performance and excellent high-temperature performance.
The foregoing is illustrative of the present application and it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the application and are intended to be within the scope of the application.

Claims (10)

1. An electrolyte, characterized in that the electrolyte comprises a lithium salt, an organic solvent, a conventional film-forming additive, and a sulfonylurea additive represented by formula (I):
Figure FDA0002669409740000011
in the formula (I), R1One selected from hydrogen atom, halogen atom, alkyl, alkoxy, amino, hydroxyl, ester group and acyl; r2Selected from a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a haloalkyl group, a haloalkoxy group, a halocycloalkyl group or a cycloalkyl group containing a ring heteroatom; wherein the conventional film forming additive is a film forming additive capable of preventing the electrode material from falling off.
2. The electrolyte according to claim 1, wherein the number of carbon atoms in the alkyl group, alkoxy group, haloalkyl group, haloalkoxy group is 1 to 10, and the number of carbon atoms in the cycloalkyl group, halocycloalkyl group, and cycloalkyl group containing a ring hetero atom is 2 to 10.
3. The electrolyte of claim 2, wherein R is1Selected from hydrogen atom, chlorine atom, bromine atom, iodine atom, amino group, methyl group, ethyl group, acetyl group, methoxy group, ethoxy group, methyl formate group or ethyl formate group.
4. The electrolyte of claim 2, wherein R is2Selected from hydrogen atom, methyl, ethyl, propyl, butyl, cyclopentyl, cyclohexyl, cycloheptyl or nitrogen heterocyclic heptyl.
5. The electrolyte according to any one of claims 1 to 4, wherein the content of the sulfonylurea additive in the electrolyte is 0.1 to 5.0 parts by weight based on 100 parts by weight of the organic solvent.
6. The electrolyte of claim 1, wherein the conventional film forming additive comprises at least one of vinylene carbonate, vinyl ethylene carbonate, phenyl ethylene carbonate, styrene ethylene carbonate, fluoroethylene carbonate, catechol carbonate, enphenyl methyl carbonate, vitamin a, and 2-hydro furan.
7. The electrolyte of claim 6, wherein the conventional film forming additive is present in the electrolyte in an amount of 0.5 to 5.0 parts by weight based on 100 parts by weight of the organic solvent.
8. The electrolyte of claim 1, wherein the lithium salt comprises one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluoroantimonate, lithium perchlorate, lithium dioxalate borate, lithium difluorooxalate borate, lithium trifluoromethylsulfonate, lithium perfluorobutylsulfonate, lithium bis (trifluoromethylsulfonyl) imide, and lithium bis (perfluoroethylsulfonyl) imide;
the organic solvent comprises one or more of gamma-butyrolactone, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, N-methylpyrrolidone, N-dimethylformamide, N-methylformamide, N-methylacetamide, acetonitrile, sulfolane, dimethyl sulfoxide, dimethyl sulfite, and other cyclic organic esters containing fluorine, sulfur or unsaturated bonds.
9. A lithium ion battery having the electrolyte as claimed in any one of claims 1 to 8 incorporated therein.
10. A powered vehicle, characterized in that it contains a lithium ion battery according to claim 9.
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