CN114156535B - Electrolyte, lithium ion battery and power vehicle - Google Patents

Electrolyte, lithium ion battery and power vehicle Download PDF

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CN114156535B
CN114156535B CN202010928769.5A CN202010928769A CN114156535B CN 114156535 B CN114156535 B CN 114156535B CN 202010928769 A CN202010928769 A CN 202010928769A CN 114156535 B CN114156535 B CN 114156535B
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electrolyte
group
carbonate
lithium
battery
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CN114156535A (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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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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

The application provides an electrolyte, which comprises lithium salt, an organic solvent, a conventional film-forming additive and sulfonylurea additives shown as a formula (I):wherein R is 1 One selected from hydrogen atom, halogen atom, alkyl, alkoxy, amino, hydroxyl, ester group and acyl; r is R 2 Selected from the group consisting of hydrogen, alkyl, alkoxy, cycloalkyl, haloalkyl, haloalkoxy, halocycloalkyl, and cycloalkyl containing a ring heteroatom. The electrolyte can ensure that the battery has good normal temperature performance and low temperature performance, and also has excellent high temperature cycle performance and high temperature storage performance. The application also provides a lithium ion battery and a power vehicle containing the electrolyte.

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 is widely applied to the fields of portable electronic devices (mobile phones and the like), unmanned aerial vehicles, electric automobiles and the like due to the characteristics of high voltage, high specific capacity, no memory effect and the like, and along with the development of economy and science and technology, higher requirements are continuously put forward on the battery performance of the lithium ion battery, wherein the addition of a film forming additive into the electrolyte of the lithium ion battery becomes an effective means for improving the battery cycle energy.
Vinylene Carbonate (VC) is the most commonly used negative electrode film forming additive, is favorable for forming a stable and complete SEI film (solid electrolyte interface, solid electrolyte interface film) on the surface of a negative electrode material (such as graphite) in the charge and discharge process of a battery, can inhibit the damage of electrolyte to the structure of the negative electrode material and the falling off of the negative electrode material from a pole piece, and improves 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 is to have particularly excellent high temperature performance, the amount of VC is required to be large, the polarization potential of the battery under low temperature conditions is generally large, the resistance of the battery is greatly increased due to the high amount of VC, and the low temperature cycle performance (particularly the cycle performance under large current) of the battery is poor, and it is difficult to improve the high temperature performance and the low temperature performance of the battery at the same time by using other existing electrolyte systems. Therefore, it is necessary to develop an electrolyte system that can achieve a lithium ion battery having both normal temperature cycle performance, low temperature cycle performance and high temperature cycle performance.
Disclosure of Invention
In view of the above, the 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 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 application provides an electrolyte, which comprises lithium salt, an organic solvent and a conventional film-forming additive, and further comprises a sulfonylurea additive shown as a formula (I):
in the formula (I), R 1 One selected from hydrogen atom, halogen atom, alkyl, alkoxy, amino, hydroxyl, ester group and acyl; r is R 2 Selected from the group consisting of hydrogen, alkyl, alkoxy, cycloalkyl, haloalkyl, haloalkoxy, halocycloalkyl, or cycloalkyl 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 sulfonylurea additives on the basis of conventional film forming additives, the additives are physical adsorption type negative electrode additives, the physical adsorption type negative electrode additives have strong surface affinity with negative electrode materials (particularly graphite), when the negative electrode additives are adsorbed on the surface of a negative electrode, an adsorption film layer formed by the negative electrode additives can inhibit the reduction of electrolyte solvents (such as PC and the like) with more active properties, the stability of the electrolyte is maintained, the thickness of the adsorption film layer is thinner, the impedance is low, the lithium ion diffusion speed of an SEI film on the surface of the negative electrode plate is not obviously inhibited, and the normal temperature and low temperature cycle performance of a battery is not obviously reduced, particularly the low temperature cycle performance of the battery is not deteriorated. In addition, the stability of the sulfonylurea additive under high potential is higher, the sulfonylurea additive is not easy to oxidize at the positive electrode side, is not easy to reduce at the negative electrode side, does not shuttle back and forth between the positive electrode and the negative electrode of the battery, has low self-discharge rate of the battery, particularly when the battery is subjected to deep charge and discharge under high-temperature environment, even under larger polarization potential (such as charge and discharge under large current), the formed physical adsorption layer still has better electrochemical stability, and is favorable for keeping the SEI film stable; in addition, the sulfur-oxygen bond ((=o) S (=o)) in the sulfonylurea additive can keep better stability along with the change of temperature, and is not easy to decompose at high temperature, so that the battery can also have excellent high-temperature cycle performance and high-temperature storage performance.
The electrolyte containing the sulfonylurea additive can ensure that a battery can obtain a physical adsorption film layer with excellent performance in a wide temperature range from low temperature to normal temperature to 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, so that the battery is ensured to maintain good normal temperature cycle performance and normal temperature storage performance and good low temperature cycle performance, and meanwhile, the high temperature cycle performance and high temperature storage performance of the battery are also obviously improved, and the self discharge rate of the battery is reduced.
In the present application, R 1 Can be selected from one of hydrogen atom, halogen atom, alkyl group, alkoxy group, amino group, hydroxyl group, ester group (-COOR), and acyl group (-COR). Wherein the halogen atom comprises chlorine atom (Cl), bromine atom (Br) and iodine atom (I). The amine groups may include primary amine groups (-NH) 2 ) Secondary amine groups (or called alkylamino, -NHR), tertiary amine groups (or called dialkylamino, -NRR'). Alternatively, the alkyl group and the alkoxy group may have 1 to 10 carbon atoms.
In the present application, R 2 May be selected from hydrogen atoms, alkyl groups, alkoxy groups, cycloalkyl groups, haloalkyl groups, haloalkoxy groups, halocycloalkyl groups, or cycloalkyl groups containing ring heteroatoms. Wherein cycloalkyl containing a ring heteroatom means that one or more carbon atoms of the 'cycloalkyl' group are replaced by at least one heteroatom selected from N, S and O. Wherein the number of carbon atoms in the alkyl, haloalkyl, alkoxy, haloalkoxy groups may be from 1 to 10, for example from 1 to 6. The number of carbon atoms in the cycloalkyl, halocycloalkyl, cycloalkyl containing a ring heteroatom may be from 2 to 10, preferably from 3 to 10.
In some embodiments of the application, the R 1 Can be hydrogen atom, chlorine atom, bromine atom, iodine atom, amino group, methyl group, ethyl group, methoxy group, ethoxy group (CH) 3 CH 2 O-), acetyl (CH) 3 CO-), methyl formate group (CH) 3 OCO-) or ethyl formate radical (CH 3 CH 2 OCO-). Preferably a hydrogen atom, a chlorine atom, a methyl group or an amino group.
In some embodiments of the application, the R 2 Can be a hydrogen atom, methyl, ethyl, propyl, butyl, cyclopentyl, cyclohexyl, cycloheptyl, azepanyl, or the like.
Specifically, in the embodiment of the present application, the specific structural formula of the sulfonylurea additive may be shown as (J) - (T) below:
wherein the additive shown in the formula (J) is specifically p-toluenesulfonylurea. The additive represented by the formula (K) is specifically amisulbutamide. The additive represented by the formula (L) is specifically p-chlorobenzenesulfonyl urea. The additive represented by the formula (M) is specifically p- (N, N-dimethyl) phenylsulfobutylurea. The additive represented by the formula (N) is specifically p-toluenesulfonyl urea. The additive represented by the formula (O) is specifically 4-chlorobenzenesulfonyl urea. The additive shown in the formula (P) is specifically sulfaurea. The additive represented by formula (Q) is specifically tolfenuron. The additive represented by the formula (R) is specifically acetylbenzenesulfonylcyclohexylurea. The additive represented by the formula (S) is specifically a sea tolfenuron. The additive represented by formula (T) is tola sulfonylurea. Wherein when R is 1 Is methyl, R 2 In the case of hydrogen atoms, the sulfo groupThe ureide additive may be 2-methylbenzenesulfonyl urea or 3-methylbenzenesulfonyl urea in addition to p-toluenesulfonyl urea represented by the formula (N).
Wherein the sulfonylurea additive may be contained in the electrolyte in an amount of 0.1 to 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, the conventional film-forming additive can well inhibit the peeling of graphite as a negative electrode material. In particular, the conventional film-forming additive may include at least one of Vinylene Carbonate (VC), vinyl carbonate (VEC), phenyl ethylene carbonate (PhEC), styrene carbonate (PhVC), fluoroethylene carbonate (FEC), catechol Carbonate (CC), alkenylphenyl Methyl Carbonate (AMC), vitamin A (VA), and 2-hydrofuran (CN-F).
Alternatively, the content of the conventional film-forming additive in the electrolytic solution is 0.5 to 5 parts by weight, preferably 1.0 to 5.0 parts by weight, further 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 large, the low-temperature resistance of the battery can be greatly increased, and the low-temperature performance of the battery can be reduced. In the presence of the sulfonylurea additive, a small amount of conventional film forming additives (such as VC, VEC and the like) can generate a thin and compact SEI film, and the film has small low-temperature resistance, so that the battery can be ensured to have good normal-temperature and low-temperature cycle performance, and the SEI film formed by assistance of the sulfonylurea additive 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 dioxaborate (LiBOB), lithium difluorooxalato borate (LiDFOB), lithium trifluoromethane sulfonate (LiCF) 3 SO 3 ) Lithium perfluorobutyl sulfonate (LiC) 4 F 9 SO 3 ) Lithium bis (trifluoromethylsulfonyl) imide (Li (CF) 3 SO 2 ) 2 N), lithium bis (perfluoroethylsulfonyl) imide (Li (C) 2 F 5 SO 2 ) 2 N) one or more of the following. There is no particular requirement for the lithium salt content in the electrolyte, and it may be referred to the conventional amounts 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 1.6mol/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), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate, N-methylpyrrolidone, N-dimethylformamide, N-methylformamide, N-methylacetamide, acetonitrile, sulfolane, dimethylsulfoxide, dimethyl sulfite, and other cyclic organic esters containing fluorine, sulfur or an unsaturated bond, etc., but is not limited thereto. Preferably, the organic solvent is one or more of GBL, EC, PC, EMC, DEC and DMC, more preferably two or more thereof.
The electrolyte provided by the first aspect of the application contains the conventional film forming additive and the sulfonylurea additive, so that the electrolyte can ensure that a thin, compact and complete SEI film and a low-impedance and thin physical adsorption film layer can be obtained on a negative electrode when the battery works in a wide temperature range of low temperature, normal temperature and high temperature, and the physical adsorption film can keep the SEI film stable, thereby ensuring that the battery has good normal temperature cycle performance and normal temperature storage performance, good low temperature cycle performance, obviously improving the high temperature cycle performance and high temperature storage performance of the battery, and reducing the self discharge rate of the battery.
The preparation method of the electrolyte provided by the application is simpler, 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 having the electrolyte according to the first aspect of the present application built therein. 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 an electric core and electrolyte which are accommodated in the battery shell, wherein the electric core comprises a positive plate, a negative plate and a diaphragm positioned between the positive plate and the negative plate, and the electrolyte is as described in the first aspect of the 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.
Wherein, the negative plate, the positive plate and the diaphragm are all conventional choices in the field of batteries. 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 a modified polyethylene felt, a modified polypropylene felt, an ultrafine glass fiber felt, a vinylon felt, a composite film formed by welding or bonding a nylon felt and a wettable polyolefin microporous film, and the like.
In a third aspect, the present application provides a powered vehicle comprising a lithium ion battery according to the second aspect of the application.
Advantages of embodiments of the 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 application.
Detailed Description
The following examples are provided to further illustrate embodiments of the application.
Example 1
A method of preparing a lithium ion battery comprising:
a) The preparation method of the electrolyte comprises the following steps: in a glove box, mixing organic solvents of Ethylene Carbonate (EC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), propylene Carbonate (PC) according to the ratio of table 1 to obtain a mixed solvent; liPF is added to 100 parts by weight of the mixed solvent 6 As 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 Shi Dashenghua chemical Co., ltd.) and X parts by weight of p-toluenesulfonylurea (purity: 99.7%) (commercially available from Shouguang chemical Co., ltd.) were stirred until all solid matters were completely dissolved to obtain the desired electrolyte, wherein the contents of the respective components were as shown in Table 1.
b) Preparing a positive plate: liFePO as positive electrode active material 4 (commercially available from Xiangtan electrochemical technologies Co., ltd.) with conductive carbon black and polyvinylidene fluoride at 97.5:1.5:1.0, dissolving in N-methyl pyrrolidone, stirring uniformly to obtain positive electrode slurry with the solid content of 50wt%, coating the positive electrode slurry on two sides of an aluminum foil with the thickness of 13 mu m, baking at 110+/-5 ℃, calendaring, and vacuum drying to form a positive electrode material layer with the thickness of 155 mu m+/-2 mu m, thereby obtaining the positive electrode plate.
c) Preparing a negative plate: the negative electrode active material, secondary granulated artificial graphite (commercially available from Shenzhen Bei Terui Co., ltd., trade mark S360), was mixed with conductive carbon black, styrene-butadiene rubber (SBR), and carboxymethyl cellulose (CMC) in a ratio of 96.2:1.0:1.3: dispersing 1.5 weight ratio in deionized water, stirring uniformly to obtain negative electrode slurry, coating the negative electrode slurry on two sides of copper foil with the thickness of 6 mu m, baking at 110+/-5 ℃, calendaring, and vacuum drying to form a negative electrode material layer with the thickness of 110 mu m+/-2 mu m, thus obtaining the negative electrode plate.
d) Assembling a battery: in a glove box, the positive electrode sheet, a 14 μm thick polypropylene separator and the negative electrode sheet were sequentially stacked, wound into a square bare cell, the bare cell was put into a battery case and welded, then the above electrolyte was injected into the battery case, the battery case was sealed, and an LP053450ARU type lithium ion battery was produced, and the battery produced in example 1 was designated as S1.
According to the battery manufacturing method provided in example 1, batteries of examples 2 to 7 were manufactured in accordance with the proportions shown in Table 1, and are denoted as S2 to 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: in preparing the electrolyte, p-chlorobenzenesulfonyl urea is used instead of p-toluenesulfonyl urea.
Example 9
Battery S9 was prepared with reference to the battery preparation method provided in example 1, which differs from example 1 in that: in preparing the electrolyte, sulfamuron is used instead of p-toluenesulfonylurea.
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 preparing the electrolyte, p- (N, N-dimethyl) phenylsulfobutylurea was used instead of p-tolylsulfuron.
Table 1 composition of electrolyte in the battery of each example
To highlight the beneficial effects of the examples of the present application, the following comparative examples 1 to 4 are specifically provided.
Comparative examples 1 to 4
Preparation of electrolyte: mixing the organic solvents EC, EMC, DEC, DMC, PC in a glove box according to the proportion shown in table 2 to obtain an organic mixed solvent; relative to100 parts by weight of an organic mixed solvent, liPF is added 6 As an electrolyte, the concentration of the electrolyte is 1.0mol/L, and the following additives are selectively added: VC, propylene Sulfite (PS), methylene Methylsulfonate (MMDS), vinyl sulfate (DTD); stirring until all the solid materials were dissolved to obtain the desired electrolyte, the contents of the respective raw materials being shown in table 2.
Preparation of the battery: according to the battery preparation method described in example 1, the electrolytes of comparative examples 1 to 4 were prepared into batteries, and the prepared batteries were sequentially designated as D1, D2, D3, and D4.
Table 2 batteries of each comparative example and electrolyte compositions thereof
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 rate): placing each battery in an incubator at 25 ℃, connecting a battery performance tester BS-9300 through an outgoing line, charging at 0.5C constant current until the cut-off voltage is 3.8V, placing for 30min, discharging at 0.5C constant current, placing for 2.0V, placing 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 in the cycle of 200 times at normal temperature.
Normal temperature storage performance (normal temperature storage capacity remaining rate): charging each battery at 0.5C constant current under the condition of room temperature of 25+/-2 ℃ until the cut-off voltage is 3.80V, and recording the charging capacity; then the battery is stored in an incubator at 25 ℃ for 28 days, then the battery is placed at the normal temperature of 25+/-2 ℃, then the constant current discharge is carried out at 0.5 ℃ until the cut-off voltage is 2.0V, the discharge capacity is recorded, and the ratio of the discharge capacity to the charge capacity of each battery is the capacity remaining rate of the battery stored at the normal temperature, so that the quality of the battery stored at the normal temperature is evaluated.
High temperature cycle performance (high temperature cycle capacity retention rate): the battery is placed in an incubator at the temperature of 60 ℃, is connected with a battery performance tester BS-9300 through an outgoing line, is charged with 0.5C constant current until the voltage is 3.8V, is placed aside for 30min, is discharged with 0.5C constant current, is placed to 2.0V, is placed aside for 30min, and is cycled for 200 times under the condition, and the ratio of the discharge capacity of the 200 th time to the discharge capacity of the 1 st time is the cycle capacity retention rate of the battery at the high temperature of 60 ℃ for 200 times.
High temperature storage performance (capacity remaining rate of high temperature storage): charging each battery at 0.5C constant current under the condition of room temperature of 25+/-2 ℃ until the cut-off voltage is 3.80V, and recording the charging capacity; then placing the battery in an incubator at 60 ℃ for 28 days, placing the battery at normal temperature of 25+/-2 ℃ for more than 24 hours, discharging at a constant current of 0.5 ℃ until the voltage is 2.0V, and recording the discharge capacity; the ratio of the discharge capacity to the charge capacity of each battery is the capacity remaining rate of the battery stored at a 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 rate): the battery is placed in an incubator at the temperature of minus 20 ℃, is connected with a battery performance tester BS-9300 through an outgoing line, is charged with constant current of 0.2C, is charged to 3.6V, is placed for 30min, is discharged with constant current of 0.2C, is placed to 2.0V, is placed for 30min, is subjected to 150 cycles under the condition, and the ratio of the discharge capacity of 150 times to the discharge capacity of 1 st time is the cycle capacity retention rate of 200 times of the battery in low-temperature cycle at the temperature of minus 20 ℃, so that the quality of the battery in low-temperature cycle performance is evaluated.
The performance test results of each cell are shown in table 3 below.
Table 3 results of performance test of each battery
As can be seen from the data in table 3, the batteries S1 to S10 (except S7) prepared in examples 1 to 10 of the present application can still have a better low-temperature cycle capacity retention rate and also have significantly improved high-temperature cycle capacity retention rate and high-temperature storage capacity retention rate in the case of having a good normal-temperature cycle capacity retention rate and normal-temperature storage capacity retention rate, as compared to the batteries D1 to D4 prepared in comparative examples. In addition, since the amount of the conventional film-forming additive VC added to the battery S7 is high (higher than that of the comparative batteries D2 to D4, reaching the upper limit defined in the present application), the low-temperature cycle performance thereof is lowered, but the high-temperature cycle and high-temperature storage performance thereof is still higher than that of the batteries D2 to D4, and the low-temperature cycle performance of the battery S7 is particularly excellent as compared with the battery D1 having the same VC added thereto.
Therefore, the electrolyte for the lithium battery provided by the application can ensure that the lithium ion battery prepared from the electrolyte has good normal temperature performance and also has good low temperature performance and excellent high temperature performance.
While the foregoing is directed to exemplary embodiments of the present application, it will be appreciated by those skilled in the art that various modifications and adaptations can be made thereto without departing from the principles of the present application, and such modifications and adaptations are intended to be comprehended within the scope of the present application.

Claims (10)

1. An electrolyte is characterized by comprising lithium salt, an organic solvent, a conventional film-forming additive and sulfonylurea additives shown in a formula (I):
in the formula (I), R 1 One selected from hydrogen atom, halogen atom, alkyl, alkoxy, amino, hydroxyl, ester group and acyl; r is R 2 Selected from the group consisting of hydrogen, alkyl, alkoxy, cycloalkyl, haloalkyl, haloalkoxy, halocycloalkyl, or cycloalkyl 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, the alkoxy group, the haloalkyl group, the haloalkoxy group is 1 to 10, and the number of carbon atoms in the cycloalkyl group, the halocycloalkyl group, and the cycloalkyl group containing a ring hetero atom is 2 to 10.
3. The electrolyte of claim 2 wherein R is 1 Selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, an amino group, a methyl group, an ethyl group, an acetyl group, a methoxy group, an ethoxy group, a methyl formate group, and an ethyl formate group.
4. The electrolyte of claim 2 wherein R is 2 Selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, cyclopentyl, cyclohexyl, cycloheptyl, and azepanyl.
5. The electrolyte according to any one of claims 1 to 4, wherein the sulfonylurea additive is contained in the electrolyte in an amount of 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 carbonate, fluoroethylene carbonate, catechol carbonate, alkenylphenyl methyl carbonate, vitamin a, and 2-hydrofuran.
7. The electrolyte of claim 6 wherein said conventional film-forming additive is present in said electrolyte in an amount of 0.5 to 5.0 parts by weight based on 100 parts by weight of said 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 dioxaborate, lithium difluorooxalato borate, lithium trifluoromethane sulfonate, lithium perfluorobutyl sulfonate, lithium bis (trifluoromethane sulfonyl) imide, and lithium bis (perfluoroethyl sulfonyl) imide;
the organic solvent comprises one or more of gamma-butyrolactone, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl 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 defined in any one of claims 1 to 8 built therein.
10. A powered vehicle comprising a lithium-ion battery according to claim 9.
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