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CN114221034A - Electrochemical device and electronic device comprising same - Google Patents

Electrochemical device and electronic device comprising same Download PDF

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Publication number
CN114221034A
CN114221034A CN202111509418.1A CN202111509418A CN114221034A CN 114221034 A CN114221034 A CN 114221034A CN 202111509418 A CN202111509418 A CN 202111509418A CN 114221034 A CN114221034 A CN 114221034A
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compound
electrochemical device
mass
electrolyte
lithium
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CN114221034B (en
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陈辉
周邵云
林能镖
陈伟伟
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Dongguan Amperex Technology 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
    • H01M10/42—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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte

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Abstract

An electrolyte in an electrochemical device includes a sulfonate compound represented by a general formula (I) and a sulfate compound represented by a general formula (II). The sulfonic acid ester compound represented by the general formula (I) and the sulfuric acid ester compound represented by the general formula (II) are simultaneously arranged in the electrolyte, so that the sulfonic acid ester compound represented by the general formula (I) and the sulfuric acid ester compound represented by the general formula (II) are subjected to decomposition reduction reaction on the surfaces of a positive electrode and a negative electrode to form a good solid electrolyte interface film, the cycle performance of an electrochemical device is improved, and the impedance performance of the electrochemical device is improved.

Description

Electrochemical device and electronic device comprising same
Technical Field
The present disclosure relates to the field of electrochemical technologies, and more particularly, to an electrochemical device and an electronic device including the same.
Background
Electrochemical device, like lithium ion battery, because it has advantages such as operating voltage is high, energy density is high, environment friendly, circulation is stable, safety, by wide application in wearing equipment, smart mobile phone, unmanned aerial vehicle, fields such as notebook computer. With the development of modern information technology and the expansion of electrochemical device application, the requirements on the cycle performance and impedance performance of lithium ion batteries are higher and higher.
However, currently, when the cycle performance of a lithium ion battery is improved, the battery impedance performance of the lithium ion battery is often affected. Therefore, how to improve the impedance performance of the lithium ion battery while improving the cycle performance of the lithium ion battery becomes an urgent problem to be solved.
Disclosure of Invention
An object of the present invention is to provide an electrochemical device and an electronic device including the same, which can improve the cycle performance of a lithium ion battery and improve the impedance performance of the lithium ion battery. The specific technical scheme is as follows:
a first aspect of the present application provides an electrochemical device comprising an electrolyte; the electrolyte contains a sulfonate compound represented by general formula (I) and a sulfate compound represented by general formula (II);
Figure BDA0003405223960000011
wherein R is1、R2、R3、R4Each independently selected from substituted or unsubstituted C1To C6Alkyl, substituted or unsubstituted C2To C6Alkenyl, substituted or unsubstituted C2To C6Alkynyl or substituted or unsubstituted C1To C6When substituted, the substituent is fluorine or C3To C5A cycloalkyl group of (a).
Without being limited to any theory, the inventors of the present application have found that by controlling the electrolyte solution to contain the sulfonate compound represented by the general formula (I) and the sulfate compound represented by the general formula (II), the sulfate compound represented by the general formula (II) forms a dense and high-conductivity negative Solid Electrolyte Interface (SEI) film on the surface of the negative electrode, and the sulfonate compound represented by the general formula (I) can be decomposed and reduced on the positive and negative electrodes to form a good solid electrolyte interface film, thereby preventing the dissolution of transition metals in the positive electrode active material, reducing the generation of metal dendrites on the surface of the negative electrode, preventing the SEI film from being damaged by the transition metals, and reducing the impedance of the electrochemical device in the case of improving the cycle performance of the electrochemical device.
In some embodiments of the present application, the sulfonate compound is present in an amount W by mass based on the mass of the electrolyteI，0.01％≤WINot more than 0.5 percent and/or the mass percentage of the sulfate compound is WII，0.01％≤WIILess than or equal to 1 percent. By controlling the mass percentage of the sulfonate compound and/or the sulfate compound within the above range, the cycle performance of the electrochemical device can be improved and the impedance can be reduced.
In some embodiments of the present application, the sulfonate compound is present in an amount WIWith the mass percentage content W of the sulfate compoundIISatisfies the relationship: w is more than or equal to 0.04II/WI≤50。
In some embodiments of the present application, the sulfonate compound comprises at least one of a compound of formula (I-1) through a compound of formula (I-21):
Figure BDA0003405223960000021
Figure BDA0003405223960000031
in some embodiments herein, the sulfate compound comprises at least one of a compound of formula (II-1) through a compound of formula (II-17):
Figure BDA0003405223960000032
in some embodiments of the present application, the electrolyte further comprises a fluorophosphate ester compound represented by the general formula (III);
Figure BDA0003405223960000033
wherein R is5、R6Each independently selected from substituted or unsubstituted C1To C6Alkyl, substituted or unsubstituted C2To C6Alkenyl, substituted or unsubstituted C2To C6Alkynyl, substituted or unsubstituted C2To C6When substituted, the substituent is fluorine or C3To C5Cycloalkyl groups of (a); based on the mass of the electrolyte, the mass percentage of the fluorophosphate ester compound is WIII，0.01％≤WIIILess than or equal to 1 percent. By controlling the content of the fluorophosphate ester compound within the above-mentioned range, the high-temperature storage property of the electrochemical device can be improved.
In some embodiments of the present application, said WIAnd said WIIISatisfies the relationship: w is more than or equal to 0.04III/WI≤10。
In some embodiments of the present application, the fluorophosphate compound comprises at least one of the compounds of formula (III-1) to formula (III-19):
Figure BDA0003405223960000041
in some embodiments herein, the electrolyte further comprises a nitrile compound including at least one of 1, 2-bis (cyanoethoxy) ethane, succinonitrile, adiponitrile, 1, 4-dicyano-2-butene, 1,3, 6-adiponitrile, or 1,2, 3-tris (2-cyanoethoxy) propane; the nitrile compound is contained in an amount of 0.5 to 3% by mass based on the mass of the electrolyte. By regulating the content of the nitrile compound within the above range, the overcharge performance of the electrochemical device can be improved.
In some embodiments of the present application, the electrolyte further comprises an additive a comprising at least one of lithium bis (oxalato) borate, lithium tetrafluoroborate, lithium difluoro (oxalato) borate, lithium difluorophosphate, lithium bis (fluorosulfonato) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium trifluoromethylsulfonate, lithium 4, 5-dicyano-2-trifluoromethylimidazole, or lithium tetraborate; the additive A is 0.5 to 3 mass percent based on the mass of the electrolyte. By regulating the content of the additive A within the range, the floating charge performance of the lithium ion battery can be improved.
In some embodiments of the present application, further comprising a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, the positive electrode active material layer comprising a positive electrode active material, the positive electrode active material comprising an element B, the element B comprising at least one of Al, Mg, or Ti; the content of the element B is 0.05 to 0.5% by mass based on the mass of the positive electrode active material. By regulating the content of the element B within the range, the cycle performance and the impedance performance of the lithium ion battery can be improved.
In a second aspect, an electronic device is provided that includes an electrochemical device provided in the first aspect of the present application.
The electrolyte solution contains the sulfonic acid ester compound represented by the general formula (I) and the sulfuric acid ester compound represented by the general formula (II) at the same time, so that the sulfonic acid ester compound represented by the general formula (I) and the sulfuric acid ester compound represented by the general formula (II) are subjected to decomposition reduction reaction on the surface of a negative electrode, a good solid electrolyte interface film is formed, the cycle performance of an electrochemical device is improved, and the impedance performance of the electrochemical device is improved. Of course, not all advantages described above need to be achieved at the same time in the practice of any one product or method of the present application.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the description herein are intended to be within the scope of the present disclosure.
In the summary of the present application, the present application is explained by taking a lithium ion battery as an example of an electrochemical device, but the electrochemical device of the present application is not limited to a lithium ion battery. It is to be understood by one skilled in the art that the following description is illustrative only and is not intended to limit the scope of the present application.
Hereinafter, embodiments of the present application will be described in more detail with reference to examples and comparative examples. Various tests and evaluations were carried out according to the following methods. Unless otherwise specified, "part" and "%" are based on mass.
A first aspect of the present application provides an electrochemical device comprising an electrolyte; the electrolyte contains a sulfonate compound represented by general formula (I) and a sulfate compound represented by general formula (II);
Figure BDA0003405223960000061
wherein R is1、R2、R3、R4Each independently selected from substituted or unsubstituted C1To C6Alkyl, substituted or unsubstituted C2To C6Alkenyl, substituted or unsubstituted C2To C6Alkynyl or substituted or unsubstituted C1To C6When substituted, the substituent is fluorine or C3To C5A cycloalkyl group of (a).
Without being limited to any theory, the inventors of the present application have found that by controlling the electrolyte solution to contain the sulfonate compound represented by the general formula (I) and the sulfate compound represented by the general formula (II), the sulfate compound represented by the general formula (II) forms a dense and high-conductivity negative Solid Electrolyte Interface (SEI) film on the surface of the negative electrode, and the sulfonate compound represented by the general formula (I) can be decomposed and reduced on the positive and negative electrodes to form a good solid electrolyte interface film, thereby preventing dissolution of transition metals in the positive electrode active material, reducing the generation of metal dendrites on the surface of the negative electrode, improving the cycle performance of the electrochemical device, and improving the impedance performance of the electrochemical device.
In some embodiments of the present application, the sulfonate compound is present in an amount W by mass based on the mass of the electrolyteI，0.01％≤WILess than or equal to 0.5 percent. For example, WIMay be 0.01%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5% or any range therebetween. By controlling the mass percentage of the sulfonate compound within the above range, the cycle performance of the electrochemical device can be better improved, and the impedance of the electrochemical device can be reduced.
In some embodiments of the present application, the sulfate compound is present in a mass percent W based on the mass of the electrolyteII，0.01％≤WIILess than or equal to 1 percent. For example, WIIMay be 0.01%, 0.1%, 0.3%, 0.5%, 0.7%, 0.9%, 1%, or any range therebetween. By controlling the mass percentage of the sulfate compound within the above range, the cycle performance of the electrochemical device can be improved and the impedance of the electrochemical device can be reduced.
In some embodiments of the present application, the sulfonate compound is present in an amount WIWith the mass percentage content W of the sulfate compoundIISatisfies the relationship: w is more than or equal to 0.04II/WILess than or equal to 50. For example, WII/WIAnd may be 0.04, 1, 10, 20, 30, 40, 50, or any range therebetween. Without being limited to any theory, the inventors of the present application have found that the stability of the SEI film can be effectively improved, the cycle performance of the electrochemical device can be improved, and the impedance of the electrochemical device can be reduced by synergistically controlling the mass percentage of the sulfonate compound and the sulfate compound.
In some embodiments of the present application, the sulfonate compound comprises at least one of a compound of formula (I-1) through a compound of formula (I-21):
Figure BDA0003405223960000071
in some embodiments herein, the sulfate compound comprises at least one of a compound of formula (II-1) through a compound of formula (II-17):
Figure BDA0003405223960000072
Figure BDA0003405223960000081
in some embodiments of the present application, the electrolyte further comprises a fluorophosphate ester compound represented by the general formula (III);
Figure BDA0003405223960000082
wherein R is5、R6Each independently selected from substituted or unsubstituted C1To C6Alkyl, substituted or unsubstituted C2To C6Alkenyl, substituted or unsubstituted C2To C6Alkynyl, substituted or unsubstituted C2To C6When substituted, the substituent is fluorine or C3To C5Cycloalkyl groups of (a); based on the mass of the electrolyte, the mass percentage of the fluorophosphate ester compound is WIII，0.01％≤WIIILess than or equal to 1 percent. For example, WIIIMay be 0.01%, 0.1%, 0.3%, 0.5%, 0.7%, 0.9%, 1%, or any range therebetween. Without being bound to any theory, the inventors of the present application have found that a stable positive electrode electrolyte interface (CEI) film can be formed at the positive electrode by controlling the content of the fluorophosphate ester compound in the electrolyte within the above range, so that the contact of the positive electrode active material with the electrolyte is prevented at high temperature and high pressure, the positive electrode active material is protected, and the high temperature storage performance of the electrochemical device is improved.
In some embodiments of the present application, said WIAnd said WIIISatisfies the relationship:0.04≤WIII/WIless than or equal to 10. For example, WIII/WIMay be 0.04, 0.05, 1, 5, 10, or any range therebetween. Without being limited to any theory, the high-temperature storage performance of the battery cell can be further improved by synergistically controlling the mass percentage of the sulfonate compound and the fluorophosphate compound to satisfy the above-mentioned relational expression.
In some embodiments of the present application, the fluorophosphate compound comprises at least one of the compounds of formula (III-1) to formula (III-19):
Figure BDA0003405223960000083
Figure BDA0003405223960000091
in some embodiments of the present application, the electrolyte further comprises a nitrile compound including at least one of 1, 2-bis (cyanoethoxy) ethane, Succinonitrile (SN), Adiponitrile (AND), 1, 4-dicyano-2-butene (HEDN), 1,3, 6-Hexanetricarbonitrile (HTCN), or 1,2, 3-tris (2-cyanoethoxy) propane (TCEP); the nitrile compound is contained in an amount of 0.5 to 3% by mass based on the mass of the electrolyte. For example, the nitrile compound may be present in an amount of 0.5%, 1%, 1.5%, 2%, 2.5%, 3% by weight or any range therebetween. Without being limited to any theory, the inventor of the present application finds that by controlling the content of the nitrile compound within the above range, the transition metal of the positive electrode can be effectively passivated, the deposition of the transition metal on the surface of the negative electrode is reduced, the growth of lithium dendrite of the lithium ion battery is prevented, and the overcharge performance of the lithium ion battery is effectively improved.
In some embodiments of the present application, the electrolyte further comprises an additive a comprising lithium bis (oxalato) borate (LiBOB), lithium tetrafluoroborate (LiBF)4) Lithium difluorooxalato borate (LiDFOB), lithium difluorophosphate (LiPO)2F2) Lithium bis (fluorosulfonyl) imide (LiFSI) and lithium bis (trifluoromethylsulfonyl) imide(LiTFSI) and lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium 4, 5-dicyano-2-trifluoromethylimidazole (LITDI) or lithium tetraborate (Li2B4O7) At least one of; the additive A is 0.5 to 3 mass percent based on the mass of the electrolyte. For example, the additive a may be present in an amount of 0.5%, 1%, 1.5%, 2%, 2.5%, 3% by mass or any range therebetween. Without being limited to any theory, the inventors of the present application found that the additive a can form a stable CEI film at the positive electrode and a stable SEI film at the negative electrode, and that the CEI film and the SEI film can prevent direct contact between the electrode active material and the electrolyte, inhibit the electrolyte from being further oxidized, and improve the float charge performance of the lithium ion battery.
In some embodiments of the present application, the electrochemical device further comprises a positive electrode comprising a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, the positive electrode active material layer comprising a positive electrode active material, the positive electrode active material comprising an element B, the element B comprising at least one of Al, Mg, or Ti; the content of the element B is 0.05 to 0.5% by mass based on the mass of the positive electrode active material. For example, the element B may be present in an amount of 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5% by mass or any range therebetween. Without being limited to any theory, the inventors of the present application found that the cycle performance and the resistance performance of the electrochemical device can be improved by controlling the content of the element B in the positive electrode active material within the above range.
The electrolyte of the present application further includes a lithium salt. The kind of the lithium salt is not particularly limited as long as the object of the present invention can be achieved. For example, the lithium salt may comprise lithium hexafluorophosphate (LiPF)6) Lithium hexafluoroantimonate (LiSbF)6) Lithium hexafluoroarsenate (LiAsF)6) Lithium perfluorobutylsulfonate (LiC)4F9SO3) Lithium perchlorate (LiClO)4) Lithium aluminate (LiAlO)2) Lithium aluminum tetrachloride (LiAlCl)4) Lithium bis (sulfonimide) (LiN (C)xF2x+1SO2)(CyF2y+1SO2) Wherein x and y are natural numbers), lithium chloride (LiCl), or lithium fluoride (LiF). The lithium salt of the present application may further include at least one of fluorine, boron, or phosphorus. Preferably, the lithium salt may include LiPF6Because of LiPF6Can give high ionic conductivity and improve the cycle performance of the lithium ion battery.
The electrolyte of the present application further includes a non-aqueous solvent. The nonaqueous solvent is not particularly limited in the present application as long as the object of the present application can be achieved. For example, the nonaqueous solvent may contain at least one of a carbonate compound, a carboxylate compound, an ether compound, or other organic solvent. The carbonate compound may be a chain carbonate compound. Examples of the above chain carbonate compound are at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), Methyl Propyl Carbonate (MPC), Ethyl Propyl Carbonate (EPC), or methyl ethyl carbonate (EMC). Examples of the above carboxylic acid ester compound are at least one of ethyl acetate, n-propyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, or propyl propionate. Examples of the above ether compounds are at least one of dibutyl ether, tetraglyme, diglyme, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, 1-ethoxy-1-methoxyethane, 2-methyltetrahydrofuran or tetrahydrofuran. Examples of the above-mentioned other organic solvent are at least one of dimethyl sulfoxide, 1, 2-dioxolane, sulfolane, methylsulfolane, 1, 3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, or a phosphate ester. The content of the nonaqueous solvent is not particularly limited as long as the object of the present application can be achieved.
In the present application, the electrolyte may further include other additives, and the other additives are not particularly limited as long as the object of the present application can be achieved, and for example, may include, but are not limited to, at least one of vinyl sulfate (DTD), Vinylene Carbonate (VC), or vinyl sulfite (PS).
The positive electrode current collector of the present application is not particularly limited, and may be any positive electrode current collector known in the art, such as a copper foil, an aluminum alloy foil, a composite current collector, and the like.
In the present application, the thicknesses of the positive electrode current collector and the positive electrode active material layer are not particularly limited as long as the object of the present application can be achieved. For example, the thickness of the positive electrode current collector is 8 to 12 μm, and the thickness of the positive electrode active material layer is 30 to 120 μm.
In the present application, the positive electrode active material layer may further include a conductive agent, and the conductive agent is not particularly limited as long as the object of the present application can be achieved, and may include, for example, but not limited to, at least one of conductive carbon black, carbon nanotubes, carbon fibers, flake graphite, ketjen black, graphene, a metal material, or a conductive polymer. The carbon nanotubes may include, but are not limited to, single-walled carbon nanotubes and/or multi-walled carbon nanotubes. The carbon fibers may include, but are not limited to, vapor grown carbon fibers and/or nano carbon fibers. The metal material may include, but is not limited to, metal powder and/or metal fiber, and specifically, the metal may include, but is not limited to, at least one of copper, nickel, aluminum, or silver. The above-mentioned conductive polymer may include, but is not limited to, at least one of polyphenylene derivatives, polyaniline, polythiophene, polyacetylene, or polypyrrole.
In the present application, a binder may be further included in the positive electrode active material layer, and the present application is not particularly limited as long as the object of the present application can be achieved, and for example, polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymer, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, and the like may be included, but not limited thereto.
Optionally, the positive electrode may further include a conductive layer between the positive electrode current collector and the positive electrode active material layer. The composition of the conductive layer is not particularly limited in the present application, and may be a conductive layer commonly used in the art.
The negative electrode sheet in the present application is not particularly limited as long as the object of the present application can be achieved, and for example, the negative electrode sheet generally includes a negative electrode current collector and a negative electrode active material layer. In the present application, the negative electrode active material layer may be provided on one surface in the thickness direction of the negative electrode current collector, and may also be provided on both surfaces in the thickness direction of the negative electrode current collector. The "surface" herein may be the entire region of the negative electrode current collector or a partial region of the negative electrode current collector, and the present application is not particularly limited as long as the object of the present application can be achieved.
In the present application, the negative active material layer includes a negative active material, wherein the negative active material is not particularly limited as long as the object of the present application can be achieved, and may include, for example, but not limited to, natural graphite, artificial graphite, mesophase micro carbon spheres, hard carbon, soft carbon, silicon-carbon composite, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO2Spinel-structured lithiated TiO2-Li4Ti5O12Or a Li-Al alloy.
The negative electrode collector in the present application is not particularly limited as long as the object of the present application can be achieved, and a material such as a metal foil or a porous metal plate, for example, a foil or a porous plate of a metal such as copper, nickel, titanium, or iron, or an alloy thereof, such as a copper foil, may be used. In the present application, the thickness of the negative electrode current collector is not particularly limited as long as the object of the present application can be achieved, and is, for example, 4 to 12 μm.
In the present application, a conductive agent may be further included in the anode active material layer, and the present application has no particular limitation on the conductive agent as long as the object of the present application can be achieved.
In the present application, a binder may be further included in the anode active material layer, and the present application does not particularly limit the binder as long as the object of the present application can be achieved, and for example, at least one of styrene-butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl butyral, aqueous acrylic resin, or carboxymethyl cellulose may be included, but not limited thereto.
In the present application, a thickener may be further included in the negative electrode active material layer, and the thickener is not particularly limited as long as the object of the present application can be achieved, and for example, the thickener may be sodium carboxymethyl cellulose.
Optionally, the negative electrode may further include a conductive layer between the negative electrode current collector and the negative electrode active material layer. The composition of the conductive layer is not particularly limited in the present application, and may be a conductive layer commonly used in the art.
The separator in the present application is not particularly limited as long as the object of the present application can be achieved. The separator may include a substrate layer and a surface treatment layer, and the substrate layer is not particularly limited in the present application, and may include, for example, but not limited to, at least one of Polyethylene (PE), polypropylene (PP), a Polyolefin (PO) based separator mainly based on polytetrafluoroethylene, a polyester film such as a polyethylene terephthalate (PET) film, a cellulose film, a polyimide film (PI), a polyamide film (PA), spandex, an aramid film, a woven film, a non-woven film (non-woven fabric), a microporous film, a composite film, a separator paper, a roll-pressed film, or a spun film, preferably PP. The separation membrane of the present application may have a porous structure, and the size of the pore diameter is not particularly limited as long as the object of the present application can be achieved, and for example, the size of the pore diameter may be 0.01 μm to 1 μm. In the present application, the thickness of the separator is not particularly limited as long as the object of the present application can be achieved, and for example, the thickness may be 5 μm to 500 μm.
In the present application, a surface treatment layer may be further provided on at least one surface of the base material layer, and the surface treatment layer is not particularly limited in the present application, and may be a polymer layer or an inorganic layer, or may be a layer formed by mixing a polymer and an inorganic substance. The inorganic layer may include, but is not limited to, inorganic particles and an inorganic layer binder, and the inorganic particles are not particularly limited in the present application, and for example, may include, but are not limited to, at least one of alumina, silica, magnesia, titania, hafnia, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconia, yttria, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, or barium sulfate. The inorganic layer binder is not particularly limited herein, and may include, for example, but not limited to, at least one of polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, or polyhexafluoropropylene. The polymer layer comprises a polymer, and the material of the polymer may include, but is not limited to, at least one of polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride, or poly (vinylidene fluoride-hexafluoropropylene).
The electrochemical device of the present application is not particularly limited, and may include any device in which electrochemical reactions occur. In some embodiments, the electrochemical device may include, but is not limited to, a lithium ion battery.
The preparation process of the electrochemical device is well known to those skilled in the art, and the present application is not particularly limited, and for example, may include, but is not limited to, the following steps: stacking the positive pole piece, the isolating membrane and the negative pole piece in sequence, winding and folding the positive pole piece, the isolating membrane and the negative pole piece according to needs to obtain an electrode assembly with a winding structure, putting the electrode assembly into a packaging bag, injecting electrolyte into the packaging bag and sealing the packaging bag to obtain the electrochemical device; or, stacking the positive electrode, the separator and the negative electrode in sequence, fixing four corners of the whole lamination structure with an adhesive tape to obtain an electrode assembly of the lamination structure, placing the electrode assembly in a packaging bag, injecting electrolyte into the packaging bag and sealing the packaging bag to obtain the electrochemical device. In addition, an overcurrent prevention element, a guide plate, or the like may be placed in the packaging bag as necessary to prevent a pressure rise or overcharge/discharge inside the electrochemical device.
In a second aspect, the present application provides an electronic device comprising an electrochemical device according to any one of the previous embodiments of the present application. The electrochemical device provided by the application has good cycle performance and impedance performance, so that the electronic device provided by the application has good cycle performance and impedance performance.
The electronic device of the present application is not particularly limited, and may be any electronic device known in the art. For example, the display device includes, but is not limited to, a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a portable phone, a portable facsimile, a portable copier, a portable printer, a headphone, a video recorder, a liquid crystal television, a handy cleaner, a portable CD player, a mini disc, a transceiver, an electronic organizer, a calculator, a memory card, a portable recorder, a radio, a backup power source, a motor, an automobile, a motorcycle, a power-assisted bicycle, a lighting fixture, a toy, a game machine, a clock, an electric tool, a flashlight, a camera, a large-sized household battery, a lithium ion capacitor, and the like.
The test method and the test equipment are as follows:
and (3) testing high-temperature cycle performance:
the battery is placed in a constant temperature box at 45 ℃, the battery is charged to 4.35V at a constant current of 1C, the battery is charged to 0.05C at a constant voltage of 4.35V, and then the battery is discharged to 2.8V at a constant current of 1.0C, the process is a charge-discharge cycle process, 800 cycles of charge-discharge tests are carried out according to the above mode, and the capacity retention ratio is monitored, wherein the 45 ℃ cycle capacity retention ratio is (the 800 th cycle discharge capacity/the initial discharge capacity) multiplied by 100%.
And (3) testing the floating charge performance:
and (3) placing the lithium ion battery in a constant temperature box at 25 ℃, and standing for 30 minutes to keep the temperature of the lithium ion battery constant. Discharging with 0.5C constant current until the voltage is 2.8V, charging with 1C constant current until the voltage is 4.35V, charging with constant voltage until the current is 0.05C, testing and recording the initial thickness d of the battery with a micrometer0. And transferring the tested lithium ion battery to a 45 ℃ constant temperature box, continuously charging for 50 days at a voltage of 4.35V, transferring the lithium ion battery to a 25 ℃ constant temperature box after the charging is finished, and testing and recording the thickness d of the lithium ion battery. Thickness expansion rate (%) of lithium ion battery float charge (d-d)0)/d0X 100%, and stopping the test when the thickness expansion rate is more than 50%.
And (3) testing the high-temperature storage performance at 60 ℃:
and (3) placing the lithium ion battery in a constant temperature box at 25 ℃, and standing for 30 minutes to keep the temperature of the lithium ion battery constant. Charging to 4.45V at constant current of 0.5C, then charging at constant voltage to current of 0.05C, testing the thickness of the lithium ion battery and recording as d0, and dischargingAnd (5) placing the lithium ion battery in a constant temperature oven at 60 ℃ for 60 days, transferring the lithium ion battery to a constant temperature oven at 25 ℃ after the completion of the operation, and testing and recording the thickness d of the lithium ion battery. Thickness expansion rate (%) after 60 days of high-temperature storage of lithium ion battery (d-d)0)/d0×100％。
High-temperature storage performance test at 85 ℃:
and (3) placing the lithium ion battery in a constant temperature box at 25 ℃, and standing for 30 minutes to keep the temperature of the lithium ion battery constant. Charging to 4.35V at constant current of 0.5C, then charging at constant voltage to current of 0.05C, testing the thickness of the lithium ion battery and recording as d0And placing the lithium ion battery in an oven with the temperature of 85 ℃ for 24 hours, transferring the lithium ion battery into an oven with the temperature of 25 ℃ after the completion of the 24 hours, and testing and recording the thickness d of the lithium ion battery. Thickness expansion rate (%) after 24-hour high-temperature storage of lithium ion battery (d-d)0)/d0X 100%. And stopping the test when the thickness expansion rate is more than 50%.
50% SOC impedance test:
and (3) placing the lithium ion battery in a constant temperature box at 25 ℃, discharging at a constant current of 0.5 ℃ until the voltage is 2.8V, standing for 5min, then charging at a constant current of 0.5C until the voltage is 4.35V, and charging at a constant voltage until the current is 0.025C. Standing for 5min, discharging to 2.8V at constant current of 0.1C, and recording the discharge capacity at this time as C1. Charging to 4.35V at constant current of 0.5C1, constant voltage to current of 0.025C1, standing for 5min, discharging at constant current of 0.1C1 for 5 hr, and recording the voltage V1. Subsequently, the discharge was performed for 1s with a constant current of 1C, and the voltage V2 at this time was recorded. The battery 50% remaining charge (SOC) corresponds to an impedance of: (V1-V2)/(1C-0.1C 1).
And (3) overcharging test:
the lithium ion battery is discharged to 2.8V at the temperature of 25 ℃ at the temperature of 0.5C, is charged to 10V at the constant current of 2C (wherein the voltage of the battery is 4.35V at 100 percent SOC), is charged for 3h at constant voltage, the surface temperature change of the lithium ion battery is monitored, if the lithium ion battery is not ignited and smokes, the lithium ion battery passes, and the number of the passing batteries is counted.
Examples 1 to 1
(1) Preparation of positive pole piece
Mixing positive electrode active material, conductive agent acetylene black, adhesive polyvinylidene fluoride (PVDF) at weight ratio of 96: 2 in N-methylpyrrolidone (NMP)Fully stirring and mixing the mixture in the solvent to form uniform positive electrode slurry with the solid content of 72 wt%; uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil with the thickness of 12 mu m; and drying the aluminum foil at 85 ℃, cold-pressing to obtain a positive pole piece with the thickness of the positive active material layer being 100 mu m, and repeating the steps on the other surface of the positive pole piece to obtain the positive pole piece with the positive active material layer coated on the two surfaces. Cutting the positive pole piece into the specification of 74mm multiplied by 867mm, and welding the pole lugs for later use. Wherein the positive electrode active material layer has a compacted density of 3.40g/cm3The positive active material includes NCM811 (LiNi)0.8Mn0.1Co0.1O2) And element Ti, wherein the mass percentage of the element Ti is 0.09 percent based on the mass of the positive electrode active material, and the balance is NCM 811.
(2) Preparation of negative pole piece
The negative electrode active material graphite, the binder Styrene Butadiene Rubber (SBR) and the thickener sodium carboxymethyl cellulose (CMC) are fully stirred and mixed in a proper amount of deionized water solvent according to the weight ratio of 97.4: 1.4: 1.2, so that uniform negative electrode slurry with the solid content of 54 wt% is formed. And uniformly coating the negative electrode slurry on one surface of a copper foil with the thickness of 8 mu m, drying at 110 ℃, cold-pressing to obtain a negative electrode plate with a 150 mu m negative electrode active material layer and a single-surface negative electrode active material layer, and repeating the coating steps on the other surface of the negative electrode plate to obtain the negative electrode plate with the double-surface negative electrode active material layer. Cutting the negative pole piece into the specification of (74mm multiplied by 867mm) and welding a pole ear for later use.
(3) Preparation of the electrolyte
At water content<In a 10ppm argon atmosphere glove box, uniformly mixing Ethylene Carbonate (EC), Propylene Carbonate (PC) and diethyl carbonate (DEC) according to the mass ratio of 3: 4 to obtain a basic solvent, and then fully drying lithium salt LiPF6Dissolving in the basic solvent to obtain an electrolyte, wherein lithium salt LiPF6The mass percentage content is 12.5 percent. Adding an additive sulfonic acid ester compound and an additive sulfuric acid ester compound into the electrolyte, wherein the mass percent of the sulfonic acid ester compound is based on the mass of the electrolyteThe content is 0.01 percent, and the mass percentage content of the sulfate compound is 0.05 percent.
(4) Isolation film
A PE porous polymer film is used as a separation film. The thickness of the isolating film is 5 microns, the porosity is 39 percent, and the inorganic coating is Al2O3The organic particles are polyvinylidene fluoride.
(5) Preparation of lithium ion battery
Stacking the positive pole piece, the isolating film and the negative pole piece in sequence to enable the isolating film to be positioned between the positive pole piece and the negative pole piece to play an isolating role, and then winding to obtain the bare cell; and (3) placing the bare cell in an outer packaging foil, injecting the prepared electrolyte into the dried cell, and performing vacuum packaging, standing, formation, shaping and other processes to complete the preparation of the lithium ion battery.
Examples 1-2 to examples 1-24
The examples were the same as example 1-1 except that the relevant parameters were changed as shown in Table 1.
Comparative examples 1-1 to 1-5
The examples were the same as example 1-1 except that the relevant parameters were changed as shown in Table 1.
Example 2-1 to example 2-14
Except that the kind and mass percentage of the sulfonate compound, the kind and mass percentage of the sulfate compound, the kind and mass percentage of the fluorophosphate compound, and the ratio W of the mass percentage of the fluorophosphate compound to the mass percentage of the sulfonate compound were adjusted as shown in Table 2III/WIOtherwise, the procedure was as in example 1-1.
Example 3-1 to example 3-9
The procedure of example 1-1 was repeated, except that the type and mass% of the sulfonate compound, the type and mass% of the sulfate compound, the type and mass% of the fluorophosphate compound, and the type and mass% of the nitrile compound were adjusted as shown in Table 3.
Example 4-1 to example 4-7
The procedure was repeated as in example 3-1, except that the type and the content by mass of additive A were adjusted as shown in Table 4.
Example 5-1
(1) Preparation of positive pole piece
LiCoO as positive electrode active material2(LCO), conductive carbon black, carbon nano tubes and adhesive polyvinylidene fluoride are fully stirred and mixed in a proper amount of N-methyl pyrrolidone (NMP) solvent according to the weight ratio of 97.9: 0.4: 0.5: 1.2 to form uniform anode slurry with the solid content of 72 wt%; uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil with the thickness of 12 mu m; and drying the aluminum foil at 85 ℃, cold-pressing to obtain a positive pole piece with the thickness of the positive active material layer being 100 mu m, and repeating the steps on the other surface of the positive pole piece to obtain the positive pole piece with the positive active material layer coated on the two surfaces. Cutting the positive pole piece into the specification of 74mm multiplied by 867mm, and welding the pole lugs for later use. Wherein the positive electrode active material layer has a compacted density of 4.15g/cm3。
(2) Preparation of the electrolyte
Uniformly mixing Ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC), Ethyl Propionate (EP) and Propyl Propionate (PP) according to the mass ratio of 1: 1 to obtain a basic solvent, and then fully drying lithium salt LiPF6Dissolving in the basic solvent to obtain an electrolyte, wherein lithium salt LiPF6The mass percentage content is 12.5 percent. And adding additives of a sulfonic acid ester compound, a sulfuric acid ester compound and a fluorophosphoric acid ester compound into the electrolyte, wherein the mass percent of the sulfonic acid ester compound is 0.01%, the mass percent of the sulfuric acid ester compound is 0.05% and the mass percent of the fluorophosphoric acid ester compound is 0.10% based on the mass of the electrolyte.
< preparation of negative electrode sheet >, < preparation of separator > and < preparation of lithium ion battery > were the same as in example 1-1.
Example 5-2 to example 5-14
The procedure was as in example 5-1, except that the relevant parameters were changed as shown in Table 5.
Comparative examples 5-1 to 5-4
The procedure was as in example 5-1, except that the relevant parameters were changed as shown in Table 5.
TABLE 1
Figure BDA0003405223960000171
Note: "/" indicates the absence of corresponding preparation parameters.
TABLE 2
Figure BDA0003405223960000181
Note: "/" indicates the absence of corresponding preparation parameters.
TABLE 3
Figure BDA0003405223960000182
Note: "/" indicates the absence of corresponding preparation parameters.
TABLE 4
Figure BDA0003405223960000191
Note: "/" indicates the absence of corresponding preparation parameters.
TABLE 5
Figure BDA0003405223960000192
Note: "/" indicates the absence of corresponding preparation parameters.
It can be seen from examples 1-1 to 1-5, 1-16 to 1-18, 1-1, 1-3 and 1-4 that as the percentage of the sulfonate compound increases, the cycle performance of the electrochemical device increases and the dc resistance of the electrochemical device decreases. However, when the sulfonate compound is contained in a relatively high amount by mass, the cycle performance and the impedance performance of the electrochemical device are affected.
It can be seen from examples 1-6 to examples 1-15, comparative examples 1-1 and comparative examples 1-2 that as the amount of the sulfate compound increases in percentage by mass, the cycle performance of the electrochemical device increases and the dc resistance of the electrochemical device decreases. However, when the content of the sulfate compound is high, the cycle performance and the impedance performance of the electrochemical device are affected.
It can be seen from examples 1 to 19 to examples 1 to 22 that the cycle performance and the dc resistance performance of the electrochemical device are improved as the mass percentage of the element Ti is increased, and the cycle performance and the dc resistance performance of the electrochemical device are affected when the mass percentage of the element Ti is excessively high.
As can be seen from examples 1-1 to examples 1-24 and comparative examples 1-5, when W isII/WIWhen the value of (b) is within the range of the present application, the cycle performance of the electrochemical device is improved and the dc resistance of the electrochemical device is lowered.
As can be seen from examples 1-1 to examples 1-25, comparative examples 1-1 and comparative examples 1-5, the electrochemical device has more excellent cycle performance and reduced direct current resistance by containing both the sulfonate compound and the sulfate compound in the electrolyte.
It can be seen from examples 2-1 to 2-14 and 1-7 that the stability of the CEI film can be improved with the addition of the fluorophosphate compound, so that the contact of the positive active material and the electrolyte can be prevented at high temperature and high pressure, the positive active material can be further protected, and the high-temperature storage performance of the electrochemical device can be improved. When W isIII/WIWhen the value of (A) is within the range of the present application, the high-temperature storage property of the electrochemical device is improved, and when W isIII/WIWhen the value of (A) is too low, the improvement of high-temperature storage property of the electrochemical device is weak, and when W is too lowIII/WIWhen the value of (b) is too high, the high-temperature storage performance of the electrochemical device is affected.
It is seen from examples 3-1 to 3-9 that, with the addition of the nitrile compound, the transition metal of the positive electrode can be effectively passivated, the dissolution of the transition metal is suppressed, and the overcharge performance of the electrochemical device is improved.
It can be seen from examples 3-1, 4-1 to 4-7 that, with the addition of the additive a, a thicker and more stable SEI film and CEI film can be formed, which can prevent direct contact between the electrode active material and the electrolyte, inhibit the electrolyte from being further oxidized, and improve the float charge performance of the electrochemical device.
It can be seen from examples 5-1 to 5-14 and comparative examples 5-1 to 5-4 that the cycle performance of the electrochemical device can be improved and the high-temperature storage performance of the electrochemical device can be improved by adding a sulfonate compound, a sulfate compound and a fluorophosphate compound to the electrolyte in the lithium cobaltate system. With WII/WIAnd WIII/WIThe increase in the value of (A) improves the high-temperature storage performance of the electrochemical device, but WII/WIAnd WIII/WIWhen the value of (b) is too high, the high-temperature storage performance of the electrochemical device is affected.
The above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.

Claims (12)

1. An electrochemical device comprising an electrolyte;
the electrolyte contains a sulfonate compound represented by general formula (I) and a sulfate compound represented by general formula (II);
Figure FDA0003405223950000011
wherein R is1、R2、R3、R4Each independently selected from substituted or unsubstituted C1To C6Alkyl, substituted or unsubstituted C2To C6Alkenyl, substituted or unsubstituted C2To C6Alkynyl or substituted or unsubstituted C1To C6Alkyl group containing ether bond of (1)When substituted, the substituents are fluorine or C3To C5A cycloalkyl group of (a).
2. The electrochemical device according to claim 1, wherein the sulfonate compound is contained in an amount of W by mass based on the mass of the electrolyteI，0.01％≤WINot more than 0.5 percent and/or the mass percentage of the sulfate compound is WII，0.01％≤WII≤1％。
3. The electrochemical device according to claim 2, wherein the sulfonate compound is present in an amount W by massIWith the mass percentage content W of the sulfate compoundIISatisfies the relationship: w is more than or equal to 0.04II/WI≤50。
4. The electrochemical device of claim 1, wherein the sulfonate compound comprises at least one of a compound of formula (I-1) to a compound of formula (I-21):
Figure FDA0003405223950000012
Figure FDA0003405223950000021
5. the electrochemical device of claim 1, wherein the sulfate compound comprises at least one of a compound of formula (II-1) to a compound of formula (II-17):
Figure FDA0003405223950000022
6. the electrochemical device according to claim 1, wherein the electrolyte further comprises a fluorophosphate ester compound represented by the general formula (III);
Figure FDA0003405223950000031
wherein R is5、R6Each independently selected from substituted or unsubstituted C1To C6Alkyl, substituted or unsubstituted C2To C6Alkenyl, substituted or unsubstituted C2To C6Alkynyl, substituted or unsubstituted C2To C6When substituted, the substituent is fluorine or C3To C5Cycloalkyl groups of (a);
based on the mass of the electrolyte, the mass percentage of the fluorophosphate ester compound is WIII，0.01％≤WIII≤1％。
7. The electrochemical device of claim 6, wherein W isIAnd said WIIISatisfies the relationship: w is more than or equal to 0.04III/WI≤10。
8. The electrochemical device of claim 6, wherein the fluorophosphate compound comprises at least one of a compound of formula (III-1) to a compound of formula (III-19):
Figure FDA0003405223950000032
Figure FDA0003405223950000041
9. the electrochemical device according to claim 1, wherein the electrolyte further contains a nitrile compound including at least one of 1, 2-bis (cyanoethoxy) ethane, succinonitrile, adiponitrile, 1, 4-dicyano-2-butene, 1,3, 6-adiponitrile, or 1,2, 3-tris (2-cyanoethoxy) propane;
the nitrile compound is contained in an amount of 0.5 to 3% by mass based on the mass of the electrolyte.
10. The electrochemical device according to claim 1, wherein the electrolyte further comprises an additive a comprising at least one of lithium bis (oxalato) borate, lithium tetrafluoroborate, lithium difluoro (oxalato) borate, lithium difluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium trifluoromethylsulfonate, lithium 4, 5-dicyano-2-trifluoromethylimidazole, or lithium tetraborate;
the additive A is 0.5 to 3 mass percent based on the mass of the electrolyte.
11. The electrochemical device of claim 1, further comprising a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, the positive electrode active material layer comprising a positive electrode active material comprising an element B comprising at least one of Al, Mg, or Ti;
the mass percentage content W of the element B based on the mass of the positive electrode active materialB0.05% to 0.5%.
12. An electronic device comprising the electrochemical device of any one of claims 1 to 11.
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