阅读说明：本技术 一种电解液、电化学装置以及电子装置 (Electrolyte, electrochemical device and electronic device ) 是由 熊亚丽 管明明 王荣 郑建明 于 2020-11-12 设计创作，主要内容包括：本申请属于锂离子电池技术领域并提供了一种电解液以及包含该电解液的电化学装置和电子装置。本申请的电解液包括有机溶剂、锂盐和添加剂,其中,所述添加剂包括氟代碳酸乙烯酯和含P-N键的化合物,所述含P-N键的化合物包含式I所示的结构；以所述电解液的质量计,所述氟代碳酸乙烯酯在电解液中的质量百分数为a％,所述含P-N键的化合物在电解液中的质量百分数为b％,且满足0.1≤a/b≤200。本申请的电解液有效地改善电化学装置的高温循环、高温存储性能。(The application belongs to the technical field of lithium ion batteries and provides an electrolyte, an electrochemical device containing the electrolyte and an electronic device. The electrolyte comprises an organic solvent, a lithium salt and an additive, wherein the additive comprises fluoroethylene carbonate and a compound containing a P-N bond, and the compound containing the P-N bond comprises a structure shown in a formula I; the mass percent of the fluoroethylene carbonate in the electrolyte is a percent, and the mass percent of the compound containing the P-N bond in the electrolyte is b percent, based on the mass of the electrolyte, and the a/b is more than or equal to 0.1 and less than or equal to 200. The electrolyte effectively improves the high-temperature circulation and high-temperature storage performance of the electrochemical device.)

1. An electrolyte comprising fluoroethylene carbonate and a P-N bond containing compound, wherein the P-N bond containing compound comprises a compound having the structure of formula I:

wherein R is₀Represents an oxygen atom or is absent;

R₁、R₂、R₃、R₄、R₅、R₆each independently selected from C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₁-C₆An alkoxy group;

or R₁And R₂、R₃And R₄、R₅And R₆Each of which is linked to each other to form, together with the N atom, a cyclic group having 2 to 5 carbon atoms;

the mass percent of the fluoroethylene carbonate in the electrolyte is a percent, and the mass percent of the compound containing the P-N bond in the electrolyte is b percent, based on the mass of the electrolyte, and the a/b is more than or equal to 0.1 and less than or equal to 200.

2. The electrolyte of claim 1, wherein the compound of the structure of formula I comprises at least one of a compound of formula I-a or a compound of formula I-B:

wherein A is₁、A₂、A₃Each independently selected from a carbon atom, an oxygen atom or a single bond.

3. The electrolyte of claim 1, wherein the P-N bond-containing compound comprises at least one of the following compounds:

4. the electrolyte according to any one of claims 1 to 3, wherein the mass percentage of the P-N bond-containing compound in the electrolyte is 0.1% to 5%, and the mass percentage of the fluoroethylene carbonate in the electrolyte is 0.5% to 15%, based on the mass of the electrolyte.

5. The electrolyte of any one of claims 1 to 3, further comprising a sulfur-containing compound of formula II;

wherein R is₂₁And R₂₂Each independently selected from linear or branched substituted or unsubstituted C₁-C₆Alkyl, substituted or unsubstituted C₃-C₆Cycloalkyl, substituted or unsubstituted C₁-C₆Alkoxy radicalSubstituted or unsubstituted C₂-C₆Alkenyl, substituted or unsubstituted C₂-C₆Alkynyl, sulfone, silyl, cyano, R₂₃O-; wherein the substituent is a halogen atom; r₂₃Is C₁-C₆Alkyl, substituted or unsubstituted C₃-C₆Cycloalkyl, or substituted or unsubstituted C₃-C₆A heterocyclic group;

or R₂₁And R₂₂Are connected with each other to form a substituted or unsubstituted cyclic group with 3-4 carbon atoms together with the sulfone group; wherein the mass percent of the sulfur-containing compound in the electrolyte is 1-6% by mass of the electrolyte.

6. The electrolyte of claim 5, wherein the sulfur-containing compound comprises one or more of the following compounds:

7. the electrolyte of any one of claims 1 to 3, further comprising a phosphoric cyclic anhydride compound comprising a compound represented by formula III:

wherein R is₃₁、R₃₂、R₃₃Each independently selected from H, substituted or unsubstituted C₁-C₅Saturated alkyl, substituted or unsubstituted C₂-C₁₀Unsaturated alkyl of C₆-C₁₈An aromatic ring of (2).

8. The electrolyte of claim 7, wherein the phosphoric cyclic anhydride compound comprises one or more of the following compounds:

9. the electrolyte of claim 7, wherein the mass percent of the phosphoric cyclic anhydride compound in the electrolyte is 0.1-3% by mass of the electrolyte.

10. The electrolyte of claim 1, wherein the electrolyte further comprises a trinitrile compound, wherein the trinitrile compound comprises at least one of 1,3, 5-pentanitrile, 1,3, 6-hexanetricarbonitrile, 1,2, 6-hexanetricarbonitrile, or 1,2, 3-tris (2-cyanoethoxy) propane, and the mass percentage of the trinitrile compound in the electrolyte is 0.1-6% by mass based on the mass of the electrolyte.

11. An electrochemical device, comprising:

a positive electrode;

a negative electrode;

a separator provided between the positive electrode and the negative electrode; and

the electrolyte of any one of claims 1 to 10.

12. The electrochemical device according to claim 11, characterized in that the required content of the compound of formula I per Ah capacity, W, in g/Ah, is the ratio of the values W to K: k is 0.12 to 1.15;

wherein K represents m²A value of specific surface area per unit mass of the negative electrode active material in terms of/g, and K is not less than 1.0 and not more than 2.0.

13. An electronic device comprising the electrochemical device.

[ technical field ] A method for producing a semiconductor device

The present disclosure relates to the field of electrochemical technologies, and in particular, to an electrolyte, and an electrochemical device and an electronic device using the electrolyte.

[ background of the invention ]

Lithium Cobaltate (LCO) is superior to other ternary cathode materials such as lithium manganate, lithium iron phosphate and the like in the aspects of compaction density, high voltage, high capacity, high temperature resistance and the like, and is always the first choice of cathode materials of batteries of consumer electronic products (3C electronics for short) such as mobile phones, notebook computers, digital cameras and the like. With the development of 3C electronic products and the advent of the 5G era, high energy density has become a necessary trend; researchers improve the specific capacity of lithium cobaltate by increasing the charge cut-off voltage of LCO and enabling more ions to participate in charge and discharge.

As is well known, LCO having a layered structure is a skeleton in which Li ions and cobalt (Co) ions are alternately arranged in a framework composed of oxygen anions. Under the condition of no lithium intercalation, the inside of the crystal structure maintains the rule of positive and negative ions which are alternately arranged, and the material structure is stable. However, when charging is started, the following reaction process occurs. Firstly, the anode material starts to remove lithium, oxygen atoms of a Li layer lose negative ion barrier after lithium ions are removed to generate repulsion, and the surface structure becomes unstable; lithium ions are continuously removed, the oxygen activity of crystal lattices at the surface is improved to a certain degree, gas overflow is generated, the stability of Co atoms on the surface is poor, the Co atoms are dissolved, electrolyte is oxidized, the high-temperature storage performance of the lithium ion battery is poor, the expansion thickness of the battery is increased, and the use safety problem is generated; particularly, as the lithium removal amount increases with the increase of the charging cut-off voltage, the activity of oxygen atoms and Co elements increases, and the high-temperature performance is further deteriorated.

[ summary of the invention ]

In order to solve the problems in the prior art, the application provides an electrolyte.

One aspect of the present application provides an electrolyte comprising fluoroethylene carbonate and a P-N bond-containing compound comprising a compound represented by formula I:

wherein R is₀Represents an oxygen atom or is absent;

R₁、R₂、R₃、R₄、R₅、R₆each independently selected from C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₁-C₆An alkoxy group;

or R₁And R₂、R₃And R₄、R₅And R₆Each of which is linked to each other to form, together with the N atom, a cyclic group having 2 to 5 carbon atoms;

the mass percent of the fluoroethylene carbonate in the electrolyte is a percent, and the mass percent of the compound containing the P-N bond in the electrolyte is b percent, based on the mass of the electrolyte, and the a/b is more than or equal to 0.1 and less than or equal to 200. In one embodiment of the present application, the compound of the structure shown in formula I comprises at least one of a compound shown in formula I-A or a compound shown in formula I-B:

wherein A is₁、A₂、A₃Each independently selected from a carbon atom, an oxygen atom or a single bond.

In some embodiments of the present application, the P-N bond-containing compound comprises at least one of the compounds shown below:

in some embodiments of the present application, the mass percentage of the P — N bond-containing compound in the electrolyte is 0.1% to 5% by mass based on the mass of the electrolyte.

In some embodiments of the present application, the electrolyte further comprises a sulfur-containing compound represented by formula ii;

wherein R is₂₁And R₂₂Each independently selected from linear or branched substituted or unsubstituted C₁-C₆Alkyl, substituted or unsubstituted C₃-C₆Cycloalkyl, substituted or unsubstituted C₁-C₆Alkoxy, substituted or unsubstituted C₂-C₆Alkenyl, substituted or unsubstituted C₂-C₆Alkynyl, sulfone, silyl, cyano, R₂₃O-; wherein the substituent is a halogen atom; r₂₃Is C₁-C₆Alkyl, substituted or unsubstituted C₃-C₆Cycloalkyl, or substituted or unsubstituted C₃-C₆A heterocyclic group;

or R₂₁And R₂₂Are connected with each other to form a substituted or unsubstituted cyclic group having 3 to 4 carbon atoms together with the sulfone group.

In some embodiments of the present application, the sulfur-containing compound comprises one or more of the following compounds:

in some embodiments of the present application, the sulfur-containing compound of formula ii is present in the electrolyte in an amount of 1% to 6% by weight.

In some embodiments of the present application, the electrolyte further comprises a phosphoric cyclic anhydride compound having a compound represented by formula iii:

wherein R is₃₁、R₃₂、R₃₃Each independently selected from H, substituted or unsubstituted C₁-C₅Saturated alkyl, substituted or unsubstituted C₂-C₁₀Unsaturated alkyl of C₆-C₁₈An aromatic ring of (2). For example, substituted or unsubstituted C₁-C₅C of (A)₁-C₅The saturated alkyl group of (a) includes, but is not limited to, methyl, methylene, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and the like. Substituted or unsubstituted C₂-C₁₀The unsaturated alkyl group of (a) includes, but is not limited to, ethenyl, propenyl, cyclopropenyl, 1-butenyl, 3-pentenyl, propynyl, and the like.

In some embodiments of the present application, the phosphoric cyclic anhydride compound comprises one or more of the following compounds:

in some embodiments of the present application, the mass percentage of the phosphoric cyclic anhydride compound in the electrolyte is 0.01% to 3% by mass of the electrolyte, for example, the content of the phosphoric cyclic anhydride compound may be 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.3%, 1.5%, 2.0%, 3.0% or a range between any two of the above values.

Next, a lithium ion battery according to a second aspect of the present application will be described.

Another aspect of the present application provides an electrochemical device, which includes a positive electrode sheet, a negative electrode sheet, a separator disposed between the positive electrode sheet and the negative electrode sheet at an interval, an electrolyte, and a packaging foil; the positive plate comprises a positive current collector and a positive active material layer coated on the positive current collector, the positive active material layer comprises a positive active material, the negative plate comprises a negative current collector and a negative active material layer coated on the negative current collector, and the negative active material layer comprises a negative active material; the electrolyte is the electrolyte described in the application.

In some embodiments of the present application, the ratio W of the content of said compound of formula I, W to K, in g/Ah, required per Ah capacity: k is 0.12 to 1.15;

wherein K represents m²A value of specific surface area per unit mass of the negative electrode active material in terms of/g, and K is not less than 1.0 and not more than 2.0.

The present application also provides an electronic device comprising an electrochemical device as described above.

The technical scheme provided by the application can achieve the following beneficial effects:

the electrolyte comprises the compound containing the P-N bond in the formula I, and the stability of the electrolyte on the surface of the positive active material can be improved. Meanwhile, the compound can also absorb oxygen released by the anode, inhibit the decomposition of electrolyte, reduce gas generation and effectively improve the high-temperature cycle and high-temperature storage performance of the lithium ion battery.

[ description of the drawings ]

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive labor.

FIG. 1 is a schematic diagram of the structure of a compound containing a P-N bond provided herein.

[ detailed description ] embodiments

To make the purpose, technical solutions and advantages of the present application clearer, the technical solutions of the present application will be clearly and completely described below with reference to the embodiments, and it is obvious that the described embodiments are a part of the embodiments of the present application, and not all of the embodiments. The embodiments described herein are illustrative and are provided to provide a basic understanding of the present application. The embodiments of the present application should not be construed as limiting the present application. All other embodiments obtained by those skilled in the art without any creative effort based on the technical solutions and the given embodiments provided in the present application belong to the protection scope of the present application.

In the detailed description and claims, a list of items connected by the terms "one of," "one of," or other similar terms may mean any one of the listed items. For example, if items a and B are listed, the phrase "one of a and B" means a alone or B alone. In another example, if items A, B and C are listed, the phrase "one of A, B and C" means only a; only B; or only C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements. In the detailed description and claims, a list of items linked by the term "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means a only; only B; or A and B. In another example, if an item is listed

Targets A, B and C, then the phrase "at least one of A, B and C" means a only; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements.

The following definitions are used in this application (unless explicitly stated otherwise):

for simplicity, a "Cn-Cm" group refers to a group having from "n" to "m" carbon atoms,

wherein "n" and "m" are integers. For example, "C1-C10" alkyl is an alkyl group having 1 to 10 carbon atoms.

As used herein, the term "halogen" may be F, Cl, Br or I.

As used herein, the term "cyano" encompasses organic species containing an organic group-CN.

In order to solve the problems in the prior art, the application provides an electrolyte.

First, electrolyte

One aspect of the present application provides an electrolyte, which includes fluoroethylene carbonate (FEC) and a P-N bond-containing compound, where fig. 1 is a schematic structural diagram of a P-N bond-containing compound provided herein, and the P-N bond-containing compound has a compound represented by formula I as shown in fig. 1:

wherein R is₀Represents an oxygen atom or is absent;

R₁、R₂、R₃、R₄、R₅、R₆each independently selected from C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₁-C₆An alkoxy group;

or R₁And R₂、R₃And R₄、R₅And R₆Each of which is linked to each other, forms a cyclic group having 2 to 5 carbon atoms together with the N atom, the fluoroethylene carbonate accounts for a% by mass of the electrolyte and the P-N bond-containing compound accounts for b% by mass of the electrolyte, and satisfies a/b of 0.1. ltoreq. a/b.ltoreq.200.

When R is₀In the absence, its corresponding double bond is also absent.

In one embodiment of the present application, 0.1 ≦ a/b ≦ 150 is satisfied. When a/b is not less than 0.1 and not more than 150, more excellent high-temperature performance can be obtained.

In one embodiment of the present application, the compound of the structure shown in formula I comprises at least one of a compound shown in formula I-A or a compound shown in formula I-B:

wherein A is₁、A₂、A₃Each independently selected from a carbon atom, an oxygen atom or a single bond. The groups or single bonds do not contain active hydrogen atoms, so that the gas generation of the battery is avoided, and the performance of the battery is deteriorated.

In some embodiments of the present application, the P-N bond-containing compound comprises at least one of the compounds shown below:

in some embodiments of the present application, the mass percentage of the P — N bond-containing compound in the electrolyte is 0.1% to 5% by mass based on the mass of the electrolyte. When the content of the phosphorus-containing additive is less than 0.1%, the formed protective film is insufficient, and the influence on the performance of the battery is small; when the content is more than 5%, the resistance of the formed film is large, which affects the battery performance.

In some embodiments of the present application, the P — N bond-containing compound may be present in the electrolyte in an amount of 0.1% to 3% by mass based on the mass of the electrolyte, for example, the P — N bond-containing compound may be present in an amount of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, or a range between any two of the above values.

In some embodiments of the present application, the electrolyte further comprises a sulfur-containing compound represented by formula ii;

wherein R is₂₁And R₂₂Each independently selected from linear or branched substituted or unsubstituted C₁-C₆Alkyl, substituted or unsubstituted C₃-C₆Cycloalkyl, substituted or unsubstituted C₁-C₆Alkoxy, substituted or unsubstituted C₂-C₆Alkenyl, substituted or unsubstituted C₂-C₆Alkynyl, sulfone, silyl, cyano, R₂₃O-; wherein the substituent is a halogen atom; r₂₃Is C₁-C₆Alkyl, substituted or unsubstituted C₃-C₆Cycloalkyl, or substituted or unsubstituted C₃-C₆A heterocyclic group;

or R₂₁And R₂₂Are connected with each other to form a C3-C4 cyclic group with substituted or unsubstituted carbon atoms together with the sulfone group.

In some embodiments of the present application, the sulfur-containing compound comprises one or more of the following compounds:

in some embodiments of the present disclosure, the sulfur-containing compound of formula ii may be present in the electrolyte in an amount of 1% to 6% by weight, for example, the sulfur-containing compound of formula ii may be present in an amount of 1%, 1.5%, 1.8%, 2.0%, 2.2%, 2.4%, 2.5%, 3%, 3.2%, 3.5%, 3.7%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, or a range between any two of the foregoing values.

The positive and negative film-forming potentials of the sulfur-containing compound are high, the formed interfacial film is excellent in thermal stability and rich in lithium ion conduction groups, and the sulfur-containing compound and the phosphorus-containing compound in the formula I have a synergistic effect, so that the stability of the surface interface of the positive electrode can be greatly improved, the positive electrode interface is protected, the consumption of electrolyte is inhibited, and the high-temperature cycle and high-temperature storage performance of the battery is improved.

In some embodiments of the present application, the electrolyte further comprises a phosphoric cyclic anhydride based compound comprising a compound represented by formula iii:

wherein R is₃₁、R₃₂、R₃₃Each independently selected from H, substituted or unsubstituted C₁-C₅Saturated alkyl, substituted or unsubstituted C₂-C₁₀Unsaturated alkyl of C₆-C₁₈An aromatic ring of (2). For example, substituted or unsubstituted C₁-C₅C of (A)₁-C₅The saturated alkyl group of (a) includes, but is not limited to, methyl, methylene, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and the like. Substituted or unsubstituted C₂-C₁₀The unsaturated alkyl group of (a) includes, but is not limited to, ethenyl, propenyl, cyclopropenyl, 1-butenyl, 3-pentenyl, propynyl, and the like.

In some embodiments of the present application, the phosphoric cyclic anhydride compound comprises one or more of the following compounds:

in some embodiments of the present application, the mass percentage of the phosphoric cyclic anhydride compound in the electrolyte is 0.01% to 3% by mass of the electrolyte, for example, the content of the phosphoric cyclic anhydride compound may be 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.3%, 1.5%, 2.0%, 3.0% or a range between any two of the above values.

The phosphoric cyclic anhydride compound can perform complex reaction with components in an SEI film formed on a negative electrode interface, is beneficial to forming a more stable SEI film on the interface film, can remarkably reduce the impedance of the negative electrode interface film, and has good high-temperature cycle and high-temperature storage performance and lower impedance by the synergistic effect with the additive.

In some embodiments herein, the lithium salt is selected from inorganic lithium salts and/or organic lithium salts.

Preferably, the lithium salt is selected from lithium hexafluorophosphate (LiPF)₆) Lithium tetrafluoroborate (LiBF)₄) One or more of lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (oxalato) borate (LiBOB), and lithium bis (oxalato) borate (lidob).

In some embodiments of the present application, the concentration of the lithium salt in the electrolyte is 0.6mol/L to 2 mol/L.

Two, electrochemical device

The present application also provides an electrochemical device comprising an electrolyte according to the present application.

Next, a lithium ion battery according to a second aspect of the present application will be described.

Another aspect of the present application provides an electrochemical device, which includes a positive electrode sheet, a negative electrode sheet, a separator disposed between the positive electrode sheet and the negative electrode sheet at an interval, an electrolyte, and a packaging foil; the positive plate comprises a positive current collector and a positive active material layer coated on the positive current collector, the positive active material layer comprises a positive active material, the negative plate comprises a negative current collector and a negative active material layer coated on the negative current collector, and the negative active material layer comprises a negative active material; the electrolyte is the electrolyte described in the application.

In some embodiments of the present application, the ratio W of the content of said compound of formula I, W to K, in g/Ah, required per Ah capacity: k is 0.12 to 1.15;

wherein K represents m²A value of specific surface area per unit mass of the negative electrode active material in terms of/g, and K is not less than 1.0 and not more than 2.0.

The specific surface area of the anode active material can be achieved by controlling the selection of the anode active material.

The present application also provides an electronic device comprising an electrochemical device as described above.

The technical scheme provided by the application can achieve the following beneficial effects:

the electrolyte comprises the compound containing the P-N bond in the formula I, and the stability of the electrolyte on the surface of the positive active material can be improved. Meanwhile, the compound can also absorb oxygen released by the anode, inhibit the decomposition of electrolyte, reduce gas generation and effectively improve the high-temperature cycle and high-temperature storage performance of the lithium ion battery.

Examples

The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.

Preparing an electrolyte: in an argon atmosphere glove box with the water content of less than 10ppm, Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are mixed according to the mass ratio of EC to EMC to DEC of 30 to 50 to 20, then fully dried lithium salt LiPF6 is dissolved in the non-aqueous solvent, the content of LiPF6 is 1mol/L, and finally a certain mass of additives are added to prepare the electrolyte in the embodiment.

As shown in table 1, a compound containing formula I or other additive was added to the base electrolyte.

Preparing an electrolyte: in an argon atmosphere glove box with the water content of less than 10ppm, Ethylene Carbonate (EC), diethyl carbonate (DEC) and Propylene Carbonate (PC) are uniformly mixed according to the mass ratio of 3:4:3, fully dried lithium salt LiPF6 is dissolved in the non-aqueous solvent, and finally a certain mass of additives are added to prepare the electrolyte in the embodiment.

As shown in table 1, a phosphorus-containing additive, a linear or cyclic sulfur-containing compound, and a cyclic phosphate additive were added to the base electrolyte.

1. Battery preparation

(1) Preparation of positive plate

Mixing lithium cobaltate, a conductive agent SuperP and polyvinylidene fluoride according to a mass ratio of 96:2:2, adding N-methyl pyrrolidone, and stirring under the action of a vacuum stirrer until a system is uniform to obtain anode slurry, wherein the solid content of the anode slurry is 75 wt%; uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil; drying the aluminum foil at 85 ℃, then carrying out cold pressing, cutting into pieces, slitting, and drying for 4 hours at 85 ℃ under 15 ℃ of vacuum to obtain the positive plate.

(2) Preparation of negative plate

Mixing artificial graphite, sodium carboxymethylcellulose (abbreviated as CMC) and styrene butadiene rubber (abbreviated as SBR) according to a mass ratio of 97:1:2, adding deionized water, and obtaining negative electrode slurry under the action of a vacuum stirrer, wherein the solid content of the negative electrode slurry is 54 wt%; uniformly coating the negative electrode slurry on a copper foil of a negative electrode current collector; and drying the copper foil at 85 ℃, then carrying out cold pressing, cutting and slitting, and drying for 12h at 120 ℃ under a vacuum condition to obtain the negative plate.

(3) Preparation of electrolyte

Mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and Propylene Carbonate (PC) in a dry argon atmosphere glove box according to a mass ratio of 3:4:3, adding an additive, dissolving and fully stirring, and adding lithium salt LiPF₆And mixing uniformly to obtain the electrolyte. Wherein, LiPF₆The concentration of (2) is 1.15 mol/L. Specific kinds and contents of the additives used in the electrolyte are shown in tables 1,2, and 3. The content of the additive is a mass percentage calculated based on the mass of the electrolyte.

(4) Preparation of the separator

A Polyethylene (PE) separator film with a thickness of 7 μm was used.

(5) Preparation of lithium ion battery

Stacking the positive plate, the isolating film and the negative plate in sequence to enable the isolating film to be positioned between the positive plate and the negative plate to play an isolating role, and then winding to obtain a bare cell; and (3) after welding a tab, placing the bare cell in an outer packaging foil aluminum-plastic film, injecting the prepared electrolyte into the dried bare cell, and performing vacuum packaging, standing, formation (charging to 3.3V at a constant current of 0.02C and then charging to 3.6V at a constant current of 0.1C), shaping, capacity testing and other processes to obtain the soft package lithium ion battery (with the thickness of 3.3mm, the width of 39mm and the length of 96 mm).

2. Test method

Testing one: high-temperature storage performance test of lithium ion battery

Discharging the battery to 3.0V at 25 ℃ at 0.5C, then charging to 4.45V at a constant current of 0.7C, charging to a current of 0.05C at a constant voltage of 4.45V, testing by a micrometer, and recording the thickness of the battery as H11; fully charging and storing for 24 hours at 85 ℃, testing and recording the thickness of the battery by using a micrometer after 24 hours, and recording as H₁₂

Thickness expansion ratio ═ H₁₂-H₁₁)/H₁₁×100％

And (2) testing: and (3) placing the lithium ion battery in a constant temperature box with the temperature of 45 ℃ for standing for 30 minutes to keep the temperature of the lithium ion battery constant. Discharging the lithium ion battery reaching the constant temperature to 3.0V at the constant current of 0.2C at the temperature of 45 ℃, and standing for 3 minutes; charging to 4.45V at constant current of 0.7C, charging to 0.025C at constant voltage of 4.45V, and standing for 5 min; then discharging with a constant current of 0.2C until the voltage is 3.0V, and standing for 3 minutes; this is one charge-discharge cycle. Thus, the capacity retention rate after 500 cycles of the battery was calculated.

Capacity retention (%) after 500 cycles of the lithium ion battery was equal to 500-cycle discharge capacity/1-cycle discharge capacity × 100%

Test III, direct current impedance DCR (0 ℃) test of lithium ion battery

Standing the lithium ion battery in a high-low temperature box at 0 ℃ for 4 hours to keep the temperature of the lithium ion battery constant; charging to 4.45V at a constant current of 0.1C and charging at a constant voltage until the current is 0.05C, and standing for 10 minutes; then discharging to 3.4V at constant current of 0.1C, standing for 5 minutes, and taking the capacity of the step as a reference. Charging the battery to 4.45V at a constant current of 0.1C and constant voltage to a current of 0.05C at 0 ℃, and standing for 10 minutes; discharging at constant current of 0.1C for 8h (calculated by actual capacity obtained in the previous step), and recording the voltage at the moment as 30V 1; then, the battery was discharged at a constant current of 1C for 1s (the capacity was calculated as the battery mark capacity), the voltage at that time was recorded as V2, and the dc impedance corresponding to the 20% SOC state of the battery was calculated.

20% SOC dc impedance (V2-V1)/(1C-0.1C)

3. Test results

(1) Influence of P-N additive and fluoroethylene carbonate additive on battery performance.

TABLE 1 electrolyte parameters and Electrical Performance data for examples 1-16 and comparative examples 1-4

Comparing comparative example 1 with comparative example 2, it can be seen that the addition of the compound having a P — N bond has a good effect of improving high-temperature cycle and high-temperature storage. The reason is that the compound containing the P-N bond can improve the stability of the electrolyte on the surface of the active material, can absorb oxygen released by the anode, inhibit the decomposition of the electrolyte, reduce the gas generation, and can effectively improve the high-temperature cycle and high-temperature storage performance of the lithium ion battery. As can be seen from comparison of examples 1 to 9, respectively, when a P-N bond-containing compound (content: b%) is used in combination with FEC (content: a%) while satisfying 0.1. ltoreq. a/b. ltoreq.200, the high-temperature storage and cycle properties are further improved.

It can be seen from comparing examples 1 to 16 with comparative examples 3 to 4 that when a/b is less than 0.1, the improvement of high-temperature cycle is not significant because the LiF content in the negative electrode is low, the formed SEI film has poor mechanical stability, and is not beneficial to the improvement of cycle; when a/b is more than 200, the high-temperature cycle improvement is remarkable, but the high-temperature storage deterioration is more remarkable. This is because if the FEC content is too high, it is easily decomposed by oxidation to generate gas, and the high-temperature storage performance is deteriorated.

(2) Influence of P-N-containing additives and S-containing additives on battery performance.

TABLE 2 electrolyte parameters and Electrical Performance data for examples 17-29 and comparative example 5

It can be seen from the comparison of examples 17-22 with example 6 and comparative example 5 that the addition of the compound of formula II has a better effect of improving the high temperature cycle and the high temperature storage. The reason is that the introduction of the compound shown in the formula II can further improve the stability of an SEI interface film, further improve the stability of the electrolyte on the surface of an active material, inhibit the decomposition of the electrolyte, reduce the gas generation, and effectively improve the high-temperature cycle and high-temperature storage performance of the lithium ion battery.

As can be seen from comparative examples 23 to 26, similar effects can be achieved by the synergistic action of different compounds of the formula I with compounds of the formula II; however, when the amount of the compound of formula ii is too high, the high temperature storage performance is affected mainly because the resistance increases due to the excessive thickness of the protective film formed on the positive and negative electrodes, which affects the electrical properties.

It can be seen from comparative examples 27 to 29 that similar improvements can be achieved by using different compounds of formula II in combination.

(3) Influence of synergistic effect of P-N-containing additives, S-containing additives and phosphoric cyclic anhydride on battery performance.

Table 3 shows the parameters of the electrolyte and the electrical properties of the electrolyte of example 4, examples 23, 24-29 and comparative example 6, and examples 30-40 are based on example 4 and added with the materials shown in Table 3.

TABLE 3

By comparing the test results of example 23 with examples 30 to 41 and example 4, it can be seen that the formula i, the formula ii and the formula iii cooperate to enable the lithium ion battery to have a higher high-temperature cycle capacity retention rate and a lower high-temperature storage volume expansion rate, and the lithium ion battery also has a lower normal-temperature dc impedance, that is, when the three cooperate, the compound of the formula i can improve the high-temperature performance of the lithium ion battery, and can prevent the compound of the formula i from damaging the SEI film; it can be seen from the test results of examples 32 to 36 that the low-temperature dc resistance gradually decreases when the content of the compound of formula iii is within a suitable range, but that the high-temperature cycle capacity retention ratio and the high-temperature storage volume expansion ratio of the battery are affected when the content is too high.

The test results of the comparative example 6 and the examples 30 to 41 show that the lithium ion battery has poor high-temperature cycle capacity retention rate and high-temperature storage volume expansion rate performance due to the fact that the positive electrode is not protected by the positive electrode film-forming additive, so that the electrolyte is easy to react with the positive electrode, and the performance of the lithium ion battery is poor due to the fact that the additive of the formula III is only added into the electrolyte.

(4) Table 4 shows the effect of the content of the compound of formula i in the electrolyte on the high temperature storage volume expansion rate and capacity retention rate of the lithium ion battery. The examples shown in table 4 are modifications of example 4.

TABLE 4 influence of the content of the compound of formula I on the high-temperature storage volume expansion and capacity retention of lithium ion batteries

By comparing the test results of example 4 and examples 42-45, it can be seen that when W/K is constant, the formula i, the formula ii, and the formula iii act synergistically, so that the lithium ion battery has a high-temperature cycle capacity retention rate and a low high-temperature storage volume expansion rate, and the lithium ion battery also has a low normal-temperature dc impedance.

As shown in example 51, when W: K is more than 1.15, the capacity retention ratio of the lithium ion battery is low.

As shown in example 52, when W: K is less than 0.12, the high-temperature storage volume expansion ratio of the lithium ion battery is large. As shown in examples 46 to 50, as W: K is gradually increased in the range of 0.12 to 1.14, the high-temperature storage volume expansion rate of the lithium ion battery is gradually decreased, but the capacity retention rate is increased first and then decreased. The reason is that as the content of the compound of formula I increases, the interface of the positive electrode is improved, so that the stability of the electrolyte is improved, and meanwhile, the P-N bond of the compound of formula I can perform a complex reaction with lithium salt, so that the lithium salt is stabilized, the decomposition reaction of the lithium salt at high temperature is improved, and the volume expansion rate of the lithium salt at high-temperature storage is reduced. However, the positive electrode of the compound of formula I has a low film-forming potential and is easy to form a film on the surface of the positive electrode, but the film-forming resistance is larger along with the increase of the content, so that the capacity retention rate is reduced.

Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.