CN114450834B - Electrochemical device and electronic device - Google Patents
Electrochemical device and electronic device Download PDFInfo
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- CN114450834B CN114450834B CN202180005430.0A CN202180005430A CN114450834B CN 114450834 B CN114450834 B CN 114450834B CN 202180005430 A CN202180005430 A CN 202180005430A CN 114450834 B CN114450834 B CN 114450834B
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- H—ELECTRICITY
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- 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
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Abstract
本申请提供了一种电化学装置和电子装置，该电化学装置包含正极、负极、隔离膜和电解液，该电解液包含三氟氧化磷和多氰基化合物，该多氰基化合物包含至少两个氰基。该电解液能够在正极表面形成致密稳定的保护膜，抑制电解液在高电压下的分解反应。包含该电解液的电化学装置具有良好的高温安全性能和循环性能。The present application provides an electrochemical device and an electronic device, wherein the electrochemical device comprises a positive electrode, a negative electrode, a separator and an electrolyte, wherein the electrolyte comprises phosphorus oxyfluoride and a polycyano compound, wherein the polycyano compound comprises at least two cyano groups. The electrolyte can form a dense and stable protective film on the surface of the positive electrode, inhibiting the decomposition reaction of the electrolyte under high voltage. The electrochemical device comprising the electrolyte has good high temperature safety performance and cycle performance.
Description
Technical Field
The present application relates to the field of electrochemistry, and in particular, to an electrochemical device and an electronic device.
Background
The lithium ion battery has the advantages of high energy storage density, high open circuit voltage, low self-discharge rate, long cycle life, good safety and the like, and is widely applied to electronic products such as cameras, mobile phones, unmanned aerial vehicles, notebook computers, intelligent watches and the like as a power supply. At present, the charge cut-off voltage of the lithium ion battery is raised to increase the lithium removal amount of the positive electrode material, and the method is an effective means for increasing the energy density of the lithium ion battery.
However, the increase of the charge cut-off voltage of the lithium ion battery easily causes the problems of gas expansion, rapid decay of the cycle capacity at high temperature and occurrence of thermal runaway at high temperature of the lithium ion battery. The positive electrode surface of the lithium ion battery has strong electrochemical oxidation activity under high voltage, and once the electrochemical window of the electrolyte is exceeded, the electrolyte is subjected to oxidative decomposition, so that the phenomena of capacity attenuation, gas production, heat release and the like are caused. In view of this, developing a suitable lithium ion battery is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The present application is directed to an electrochemical device and an electronic device to improve high temperature safety and cycle performance of the electrochemical device.
In a first aspect, the present application provides an electrochemical device 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, a negative electrode, a separator, and an electrolyte comprising phosphorus oxytrifluoride and a polycyano compound comprising at least two cyano groups.
According to some embodiments of the application, the phosphorus oxytrifluoride is present in an amount of 0.001% to 5% by mass, based on the total mass of the electrolyte.
According to some embodiments of the application, the phosphorus oxytrifluoride is present in an amount of 0.001% to 3% by mass, based on the total mass of the electrolyte.
According to some embodiments of the application, the polycyano compound is present in an amount of 0.1% to 10% by mass B based on the total mass of the electrolyte.
According to some embodiments of the application, the polycyano compound is present in an amount of 2 to 8% by mass, based on the total mass of the electrolyte.
According to some embodiments of the application, the phosphorus oxytrifluoride is present in an amount of A and the polycyano compound is present in an amount of B that is 0.15% to 11% based on the total mass of the electrolyte.
According to some embodiments of the application, the polycyano compound includes at least one of the compounds of structural formula (I):
Wherein R is selected from C 1 -C 15 alkyl, C 1 -C 15 alkenyl or C 1 -C 15 alkynyl, a and C are each independently 0 or positive integer, a and C are not simultaneously 0, 2-a+c-7, 0-b-6, and the number b of alkylene groups connected by each cyano group can be the same or different.
According to some embodiments of the application, the polycyano compound includes any one of the following formulas (1) to (62):
according to some embodiments of the application, the electrolyte further comprises at least one of a fluoroester compound, a cyclic sulfonate, or a cyclic carbonate containing an unsaturated bond.
According to some embodiments of the application, the mass percentage content C of the fluoroester compound is 0.1% to 15% based on the total mass of the electrolyte.
According to some embodiments of the application, the cyclic sulfonate is present in an amount of 0.1% to 5% by mass, based on the total mass of the electrolyte.
According to some embodiments of the application, the unsaturated bond-containing cyclic carbonate content E is 0.01% to 2% by mass based on the total mass of the electrolyte.
According to some embodiments of the application, the content of the trifluoro-phosphorus oxide A and the content of the cyclic sulfonate D are 0.1% to 20% by mass.
According to some embodiments of the present application, the fluoroester compound comprises fluoroethylene carbonate, difluoroethylene carbonate, fluoroethylmethyl carbonate dimethyl fluorocarbonate, diethyl fluorocarbonate, ethyl fluoropropionate, propyl fluoropropionate at least one of methyl fluoropropionate, ethyl fluoroacetate, methyl fluoroacetate, propyl fluoroacetate, vinyl difluorocarbonate, and vinyl trifluoromethylcarbonate.
According to some embodiments of the application, the cyclic sulfonate comprises at least one of 1, 3-propane sultone or 1, 4-butane sultone.
According to some embodiments of the application, the unsaturated bond-containing cyclic carbonate comprises at least one of vinylene carbonate or vinyl ethylene carbonate.
According to some embodiments of the application, the electrolyte comprises a fluoroester compound and a cyclic sulfonate.
According to some embodiments of the application, the electrolyte comprises a fluoroester compound, a cyclic sulfonate, or a cyclic carbonate containing an unsaturated bond.
According to some embodiments of the present application, the metal element other than lithium in the positive electrode active material satisfies 600> F/A >10 between the mass percentage F of the metal element in the positive electrode active material and the mass percentage A of the phosphorus oxytrifluoride in the electrolyte.
According to some embodiments of the application, the metal element other than lithium comprises at least one of Fe, co, ni, mn, ti, mg, al, zr, la, Y, V, cr, ge, ru, sn, ti, nb, mo.
In a second aspect, the present application provides an electronic device comprising an electrochemical device according to the first aspect of the application.
Detailed Description
The present application will be described in further detail with reference to the following examples, in order to make the objects, technical solutions, and advantages of the present application more apparent. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other technical solutions obtained by a person skilled in the art based on the embodiments of the present application fall within the scope of protection of the present application.
In the context of the present application, the present application is explained using 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. The specific technical scheme is as follows:
The first aspect of the present application provides an electrochemical device comprising a positive electrode current collector and a positive electrode active material layer provided on at least one surface of the positive electrode current collector, the positive electrode active material layer comprising a positive electrode active material, a negative electrode, a separator, and an electrolyte comprising phosphorus oxytrifluoride and a polycyano compound comprising at least two cyano groups.
In one embodiment of the application, the electrolyte comprises phosphorus trifluoride oxide (POF 3) and a polycyano compound, wherein the phosphorus trifluoride oxide can generate passivation reaction on a positive electrode to form a compact protective film, the polycyano compound can form stable adsorption coordination on the surface of the positive electrode, the phosphorus trifluoride oxide and the polycyano compound cooperate to form the compact stable protective film, and the oxidative decomposition reaction of the electrolyte under high voltage is inhibited, so that phenomena such as capacity attenuation, gas production, heat release and the like are avoided, and therefore, the problems of expanding gas of a lithium ion battery, rapid cycle capacity attenuation under high temperature and safety of thermal runaway under high temperature are effectively prevented, and remarkable effects are generated on the improvement of the high-temperature safety performance and the cycle performance of the lithium ion battery.
In one embodiment of the application phosphorus oxytrifluoride (POF 3) may be generated by decomposition of an additive in the electrolyte, such as lithium hexafluorophosphate.
The number of cyano groups in the polycyano compound is not particularly limited as long as at least two cyano groups are contained, and the object of the present application can be achieved. For example, 2,3, 4, 5, 6 or 7 cyano groups may be included in the polycyano compound. Different polycyano compound molecules have different spatial structures and have different improving effects on lithium ion batteries.
The electrochemical device provided by the application comprises a positive electrode, a negative electrode, a separation film and electrolyte, wherein the positive electrode comprises a positive electrode current collector and a positive electrode active material layer arranged on at least one surface of the positive electrode current collector, and the positive electrode active material layer comprises a positive electrode active material. Wherein the electrolyte comprises phosphorus oxytrifluoride and a polycyano compound comprising at least two cyano groups. The electrolyte can form a compact and stable protective film on the surface of the positive electrode, inhibit the oxidative decomposition of the electrolyte under high voltage, greatly reduce the phenomena of capacity attenuation, gas production, heat release and the like of the lithium ion battery caused by the decomposition reaction of the electrolyte under high voltage, and further effectively improve the high-temperature safety performance and the cycle performance of the electrochemical device.
In one embodiment of the present application, the mass percent content a of phosphorus trifluoride oxide is 0.001% to 5% based on the total mass of the electrolyte. In one embodiment of the application, the content of phosphorus oxytrifluoride a is 0.01% to 3% by mass, based on the total mass of the electrolyte. In one embodiment of the present application, the mass percent content a of phosphorus trifluoride oxide is 0.01% to 0.95% based on the total mass of the electrolyte. In one embodiment of the application, the polycyano compound has a mass percentage B of 0.1% to 10% based on the total mass of the electrolyte. In one embodiment of the application, the polycyano compound is present in an amount of 2 to 8% by mass based on the total mass of the electrolyte. For example, the lower limit value of the content A by mass of phosphorus trifluoride oxide may be included in the following numerical values of 0.001%, 0.2%, 0.5% or 1%, and the upper limit value of the content A by mass of phosphorus trifluoride oxide may be included in the following numerical values of 3% or 5%. The lower limit of the mass percentage content B of the polycyano compound may be included in the following numerical values of 0.1%, 0.5%, 1%, 2% or 3%, and the upper limit of the mass percentage content B of the polycyano compound may be included in the following numerical values of 5%, 7%, 8% or 10%. Without being limited to any theory, by controlling the mass percentage content a of the phosphorus trifluoride within the above-described range, the effect of the phosphorus trifluoride can be fully exerted when the positive electrode is lithiated to compensate for the protection defect. By controlling the mass percentage content B of the polycyano compound within the above range, the polycyano compound forms stable adsorption coordination on the positive electrode surface. By controlling the mass percentage A of phosphorus oxytrifluoride and the mass percentage B of polycyano compound within the above-mentioned preferred ranges, a correspondingly superior effect can be obtained.
In one embodiment of the present application, the ratio of the mass percent A of phosphorus oxytrifluoride to the mass percent B of polycyano compound is 0.15% or more and 11% or less. In one embodiment of the present application, the ratio of the mass percent A of phosphorus oxytrifluoride to the mass percent B of polycyano compound is 2.5% or more and A+B or less than 10% or less. For example, the lower limit of the sum of A and B may include 0.15%, 1.5%, 2%, 2.2%, 2.5%, 3%, 4% or 5%, and the upper limit of the sum of A and B may include 6%, 7%, 8%, 9% or 10%. Without being limited by any theory, by controlling the sum of A and B within the above range, the synergistic adsorption reaction of phosphorus trifluoride oxide and polycyano compound has high film formation efficiency, and a dense, stable and low-impedance interface protective film can be rapidly formed.
In one embodiment of the present application, the polycyano compound includes at least one of the compounds of structural formula (I):
Wherein R is selected from C 1 -C 15 alkyl, C 1 -C 15 alkenyl or C 1 -C 15 alkynyl, a and C are each independently 0 or positive integer, a and C are not simultaneously 0, 2-a+c-7, 0-b-6, and the number b of alkylene groups connected by each cyano group can be the same or different.
Preferably, the compound represented by structural formula (I) includes any one of the following formulas (1) to (62):
In one embodiment of the present application, the electrolyte solution includes at least one of formulas (1) to (9) and at least one of formulas (10) to (62). The polycyano compounds with different structures act together, so that the high-temperature safety performance and the cycle performance of the lithium ion battery can be further improved while other performances are not influenced.
In one embodiment of the present application, the total content of at least one polycyano compound in the formulas (1) to (9) is B1%, and the total content of at least one polycyano compound in the formulas (10) to (62) is B2%, satisfying B1> B2, based on the total mass of the electrolyte. When the content satisfies the above range, the electrolyte has a more suitable viscosity value, and the lithium ion battery has better comprehensive performance.
In one embodiment of the present application, the electrolyte solution includes at least one of formulas (1) to (9) and at least one of formulas (14) to (23).
In one embodiment of the present application, the electrolyte comprises at least one of formulas (1) to (9), at least one of formulas (14) to (23), and at least one of formulas (38) to (48). The polycyano compound with ether bond and polycyano compound without ether bond act together to make the performance of lithium ion battery reach better state.
In one embodiment of the present application, the electrolyte further comprises at least one of a fluoroester compound, a cyclic sulfonate, or a cyclic carbonate containing an unsaturated bond. When at least one of the above-mentioned fluoroester compound, cyclic sulfonate or unsaturated bond-containing cyclic carbonate is contained in the electrolyte, the electrolyte can form a stable protective layer at both the positive electrode and the negative electrode, and the high-temperature safety performance and cycle performance of the lithium ion battery can be improved more effectively.
In one embodiment of the present application, the mass percentage of the fluoro-ester compound C is 0.1% to 15%, and/or the mass percentage of the cyclic sulfonate D is 0.1% to 5%, and/or the mass percentage of the unsaturated bond-containing cyclic carbonate E is 0.01% to 2%, based on the total mass of the electrolyte. For example, the lower limit value of the mass percentage content C of the fluorinated ester compound may be included in the following numerical values of 0.1%, 5% or 7.6%, and the upper limit value of the mass percentage content C of the fluorinated ester compound may be included in the following numerical values of 8%, 10% or 15%. The lower limit of the mass percentage D of the cyclic sulfonate may be included in the following numerical values of 0.1%, 1% or 2.5%, and the upper limit of the mass percentage D of the cyclic sulfonate may be included in the following numerical values of 3% or 5%. The lower limit of the amount of the unsaturated bond-containing cyclic carbonate E may be 0.01%, 0.1% or 0.5% by mass, and the upper limit of the amount of the unsaturated bond-containing cyclic carbonate E may be 1.4% or 2% by mass. Without being limited by any theory, the stability of the electrolyte at high voltage can be further improved by controlling the mass percentage of the fluoroester compound C, the mass percentage of the cyclic sulfonate D and the mass percentage of the cyclic carbonate containing unsaturated bonds E within the above ranges, and the decomposition reaction of the electrolyte at high voltage can be more effectively avoided, so that the high-temperature safety performance and the cycle performance of the lithium ion battery are further remarkably improved.
In one embodiment of the present application, the content of phosphorus oxytrifluoride A and the content of cyclic sulfonate D are 0.1% to 20% by mass. For example, the lower limit of the sum of A and D may include 0.1%, 1%, 3.001%, 3.05%, 3.2%, 3.5%, 4%, 6% or 8%, and the upper limit of the sum of A and D may include 10%, 15% or 20%. Without being limited by any theory, by controlling the sum of A and D within the above range, the cyclic sulfonate and the phosphorus trifluoride oxide cooperate to improve the composition of the positive electrode protective film, and the passivation of the phosphorus trifluoride oxide in the positive electrode reaction can be more effectively enhanced to make up for the protection defect.
In one embodiment of the present application, the kind of the fluoroester compound is not particularly limited as long as the object of the present application can be achieved. For example, the fluoroester compound may include at least one of fluoroethylene carbonate (FEC), difluoroethylene carbonate, fluoroethylmethyl carbonate, fluorodimethylcarbonate, fluorodiethylcarbonate, fluoropropionate, fluoropropylpropionate, fluoropropionate methyl ester, fluoroacetate methyl ester, fluoroacetate propyl ester, fluoroethylene carbonate, difluoroethylene carbonate, and trifluoromethylcarbonate.
In another embodiment of the present application, the kind of the cyclic sulfonate is not particularly limited as long as the object of the present application can be achieved. For example, the cyclic sulfonate may comprise at least one of 1, 3-Propane Sultone (PS) or 1, 4-butane sultone.
In still another embodiment of the present application, the type of the unsaturated bond-containing cyclic carbonate is not particularly limited as long as the object of the present application can be achieved. For example, the unsaturated bond-containing cyclic carbonate may contain at least one of Vinylene Carbonate (VC) or vinyl ethylene carbonate.
In one embodiment of the application, the electrolyte comprises a fluoroester compound and a cyclic sulfonate.
In one embodiment of the application, 0.2.ltoreq.C+D.ltoreq.15. For example, the sum of C and D may be 0.3, 0.5, 1.5, 2,4, 5, 7, 9, 11, 12, or 15, or a range of any two values therein.
In one embodiment of the present application, the electrolyte contains a fluoroester compound, a cyclic sulfonate, and a cyclic carbonate containing an unsaturated bond. When the electrolyte simultaneously contains the substances, the negative electrode can be better protected, and the performance of the lithium ion battery is improved.
In one embodiment of the present application, the metal element other than lithium in the positive electrode active material satisfies 600> F/A >10 between the mass percentage F of the metal element in the positive electrode active material and the mass percentage A of the phosphorus oxytrifluoride in the electrolyte. For example, the lower limit of F/A may include one of 12, 20, 60, 120, or 300, and the upper limit of F/A may include one of 400, 500, or 600. In the present application, the kind of the metal element other than lithium is not particularly limited as long as the object of the present application can be achieved. For example, at least one of Fe, co, ni, mn, ti, mg, al, zr, la, Y, V, cr, ge, ru, sn, ti, nb, mo may be included. Without being limited to any theory, the passivation protection effect of the phosphorus oxytrifluoride on the surface of the positive electrode can be better exerted by limiting the relation between the mass percentage content F of the transition metal element in the positive electrode active material and the mass percentage content A of the phosphorus oxytrifluoride in the electrolyte.
The electrolyte of the present application also includes a lithium salt and a nonaqueous solvent. The lithium salt is not particularly limited as long as the object of the present application can be achieved. For example, the lithium salt may comprise at least one of lithium hexafluorophosphate (LiPF6)、LiBF4、LiB(C6H5)4、LiCH3SO3、LiCF3SO3、LiN(SO2CF3)2、LiC(SO2CF3)3、LiSiF6、LiBOB or lithium difluoroborate. Preferably, the lithium salt may comprise LiPF 6, because LiPF 6 may give high ionic conductivity and improve the cycle performance of the lithium ion battery. The nonaqueous solvent is not particularly limited as long as the object of the present application can be achieved. For example, the nonaqueous solvent may comprise at least one of a carbonate compound, a carboxylate compound, an ether compound, or other organic solvent. The carbonate compound may be at least one of a chain carbonate compound and a cyclic carbonate compound. Examples of the above chain carbonate compound are at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC) or methylethyl carbonate (MEC). Examples of the cyclic carbonate compound are at least one of Ethylene Carbonate (EC), propylene Carbonate (PC) or Butylene Carbonate (BC). 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, propyl propionate. Examples of the above ether compound are at least one of dibutyl ether, tetraglyme, diglyme, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran or tetrahydrofuran. Examples of the above-mentioned other organic solvents are at least one of dimethyl sulfoxide, 1, 2-dioxolane, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidone, N-methyl-2-pyrrolidone, formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, or phosphoric acid esters.
The positive electrode of the present application includes 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 current collector is not particularly limited as long as the object of the present application can be achieved. For example, the positive electrode current collector may include an aluminum foil, an aluminum alloy foil, a composite current collector, or the like. The positive electrode active material layer of the present application contains a positive electrode active material. The kind of the positive electrode active material is not particularly limited as long as the object of the present application can be achieved. For example, the positive electrode active material may include at least one of lithium nickel cobalt manganese oxide (811, 622, 523, 111), lithium nickel cobalt aluminate, lithium iron phosphate, lithium-rich manganese-based material, lithium cobaltate, lithium manganate, lithium manganese iron phosphate, lithium titanate, or the like. In the present application, the positive electrode active material may further contain non-metal elements such as fluorine, phosphorus, boron, chlorine, silicon, sulfur, etc., which can further improve the stability of the positive electrode active material. 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 5 μm to 20 μm, or 6 μm to 18 μm. The thickness of the single-sided positive electrode active material layer is 30 μm to 120 μm. In the present application, the positive electrode active material layer may be provided on one surface (first surface) in the thickness direction of the positive electrode current collector, or may be provided on both surfaces (first surface and second surface) in the thickness direction of the positive electrode current collector. The "surface" here may be the entire region of the positive electrode current collector or may be a partial region of the positive electrode current collector, and the present application is not particularly limited as long as the object of the present application can be achieved. Optionally, the positive electrode tab 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, and may be a conductive layer commonly used in the art. The conductive layer includes a conductive agent and a binder.
The negative electrode of the present application is not particularly limited as long as the object of the present application can be achieved. For example, the anode includes an anode current collector and an anode active material layer. The negative electrode current collector is not particularly limited as long as the object of the present application can be achieved. For example, the negative electrode current collector may include a copper foil, a copper alloy foil, a nickel foil, a stainless steel foil, a titanium foil, a foam nickel, a foam copper, or a composite current collector, or the like. The anode active material layer of the present application contains an anode active material. The kind of the negative electrode active material is not particularly limited as long as the object of the present application can be achieved. For example, the anode active material may include at least one of natural graphite, artificial graphite, intermediate phase micro carbon spheres (MCMB), hard carbon, soft carbon, silicon-carbon composite, siO x (0 < x < 2), li-Sn alloy, li-Sn-O alloy, sn, snO, snO 2, spinel-structured lithium titanate Li 4Ti5O12, li-Al alloy, metallic lithium, and the like. In the present application, the thicknesses of the anode current collector and the anode 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 anode current collector is 6 μm to 10 μm, and the thickness of the anode active material layer is 30 μm to 120 μm. In the present application, the anode active material layer may be provided on one surface (first surface) in the anode current collector thickness direction, or may be provided on both surfaces (first surface and second surface) in the anode current collector thickness direction. The "surface" here may be the entire region of the negative electrode current collector or may be 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. Optionally, the negative electrode tab 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, and may be a conductive layer commonly used in the art. The conductive layer includes a conductive agent and a binder.
The above-mentioned conductive agent is not particularly limited as long as the object of the present application can be achieved. For example, the conductive agent may include at least one of conductive carbon black (Super P), carbon Nanotubes (CNTs), carbon nanofibers, crystalline flake graphite, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, or graphene. For example, the binder may include at least one of polyacrylate, sodium polyacrylate, potassium polyacrylate, lithium polyacrylate, polyimide, polyamideimide, styrene Butadiene Rubber (SBR), polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl butyral (PVB), aqueous acrylic resin, carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose (CMC-Na), or the like.
The lithium ion battery also comprises a separation membrane for separating the positive electrode from the negative electrode, preventing the internal short circuit of the lithium ion battery, allowing electrolyte ions to pass freely, and completing the electrochemical charge and discharge process. The separator in the present application is not particularly limited as long as the object of the present application can be achieved. For example, a Polyolefin (PO) based separator mainly composed of Polyethylene (PE) and polypropylene (PP), a polyester film (for example, a polyethylene terephthalate (PET) film), a cellulose film, a polyimide film (PI), a polyamide film (PA), a spandex or aramid film, a woven film, a nonwoven film (nonwoven fabric), a microporous film, a composite film, a separator paper, a laminate film, a spun film, or the like. For example, the release film may include a substrate layer and a surface treatment layer. The substrate layer may be a nonwoven fabric, a film, or a composite film having a porous structure, and the material of the substrate layer may include at least one of polyethylene, polypropylene, polyethylene terephthalate, polyimide, and the like. Optionally, a polypropylene porous membrane, a polyethylene porous membrane, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric, or a polypropylene-polyethylene-polypropylene porous composite membrane may be used. Optionally, a surface treatment layer is disposed on at least one surface of the substrate layer, and the surface treatment layer may be a polymer layer or an inorganic layer, or may be a layer formed by mixing a polymer and an inorganic material. For example, the inorganic layer includes inorganic particles and a binder, and the inorganic particles are not particularly limited, and may be selected from 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, barium sulfate, and the like, for example. The binder is not particularly limited and may be, for example, one or a combination of several selected from polyvinylidene fluoride, a copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, and polyhexafluoropropylene. The polymer layer contains a polymer, and the material of the polymer comprises at least one of polyamide, polyacrylonitrile, acrylic polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly (vinylidene fluoride-hexafluoropropylene) and the like.
The electrochemical device of the present application is not particularly limited, and may include any device in which an electrochemical reaction occurs. In some embodiments, the electrochemical device may include, but is not limited to, a lithium metal secondary battery, a lithium ion secondary battery (lithium ion battery), a lithium polymer secondary battery, or a lithium ion polymer secondary battery, among others.
The process for preparing the electrochemical device is well known to those skilled in the art, and the present application is not particularly limited as long as the object of the present application can be achieved. For example, an electrochemical device may be manufactured by placing a separator between a positive electrode sheet and a negative electrode sheet, winding or stacking them as needed, placing them in a case, injecting an electrolyte into the case, and sealing the case, wherein the separator used is the separator provided in the present application. In addition, an overcurrent prevention element, a guide plate, or the like may be placed in the case as needed, thereby preventing the pressure inside the electrochemical device from rising and overcharging and discharging.
A second aspect of the present application provides an electronic device comprising the electrochemical device described in the embodiments of the present application, which has good high-temperature safety performance and cycle performance.
The electronic device of the present application is not particularly limited, and may be any electronic device known in the art. In some embodiments, the electronic device may include, but is not limited to, a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a portable telephone, a portable facsimile machine, a portable copier, a portable printer, a headset, a video recorder, a liquid crystal television, a portable cleaner, a portable CD player, a mini-compact disc, a transceiver, an electronic notepad, a calculator, a memory card, a portable audio 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 household large-sized battery, a lithium ion capacitor, and the like.
The present application provides an electrochemical device and an electronic device, the electrochemical device comprising a positive electrode, a negative electrode, a separator, and an electrolyte comprising phosphorus oxytrifluoride and a polycyano compound comprising at least two cyano groups. The electrolyte can form a compact and stable protective film on the surface of the positive electrode, and inhibit the decomposition reaction of the electrolyte under high voltage. The electrochemical device containing the electrolyte has good high-temperature safety performance and cycle performance.
Examples
Hereinafter, embodiments of the present application will be described in more detail with reference to examples and comparative examples. The various tests and evaluations were carried out according to the following methods. Unless otherwise specified, "parts" and "%" are mass references.
Test method and apparatus:
And (3) testing the cycle performance:
At 25 ℃, standing the lithium ion battery for 30min, then charging to 4.45V at a constant current of 1C multiplying power, then charging to 0.05C at a constant voltage of 4.45V, standing for 5min, and then discharging to 3.0V at a constant current of 0.5C multiplying power, wherein the discharge capacity is the first discharge capacity of the lithium ion battery, and then carrying out 500 charge-discharge cyclic processes.
The capacity retention (%) after N charge and discharge cycles of the lithium ion battery=the discharge capacity of the nth cycle/the first discharge capacity×100%.
High temperature resistant safety performance test:
And placing the fully charged lithium ion battery in an oven, heating the oven at a temperature rising rate of 5 ℃ per minute, monitoring the temperature of the surface of the lithium ion battery, and recording the temperature of the oven when the lithium ion battery is burnt in thermal runaway.
< Preparation of electrolyte >
In a dry argon atmosphere, ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC) and Ethyl Propionate (EP) were mixed in a mass ratio EC: PC: DEC: ep=20:10:40:30 to obtain a nonaqueous organic solvent. LiPF 6, and optionally POF 3, a polycyano compound, a fluoro ester compound, a cyclic sulfonate and a cyclic carbonate containing an unsaturated bond were added to a nonaqueous organic solvent to give LiPF 6 having a concentration of 1.1mol/L, and the contents of POF 3, polycyano compound, fluoro ester compound, cyclic sulfonate and cyclic carbonate containing an unsaturated bond are shown in table 1.
< Preparation of Positive electrode >
2Kg of solvent N-methyl-2-pyrrolidone (NMP), 1.5kg of binder polyvinylidene fluoride solvent (PVDF, the mass percentage content of polyvinylidene fluoride is 10%), 0.15kg of conductive carbon black (Super P) as a conductive agent and 9.7kg of lithium cobalt oxide (LiCoO 2) as a positive electrode active material are weighed, fully mixed and stirred to obtain positive electrode slurry. Wherein the mass percentage content F of cobalt element in the LiCoO 2 in the positive electrode active material is 60%. And uniformly coating the positive electrode slurry on the first surface of the positive electrode current collector aluminum foil with the thickness of 12 mu m, and baking for 1h at 120 ℃ to obtain the positive electrode with the single-sided coating of the positive electrode slurry. And then repeating the steps on the second surface of the positive electrode to obtain the positive electrode with the double-sided coating positive electrode slurry. After coating, compacting and cutting to obtain the anode with the specification of 74mm multiplied by 867mm for later use.
< Preparation of negative electrode >
2.0Kg of thickener sodium carboxymethylcellulose (CMC, mass percent of sodium carboxymethylcellulose is 1.5%), 0.2kg of binder styrene-butadiene rubber emulsion (mass percent of styrene-butadiene rubber is 50%) and 4.8kg of negative electrode active material graphite powder (average particle size Dv50 is 11.5 μm) are weighed and uniformly mixed to obtain negative electrode slurry. The negative electrode slurry was uniformly coated on the first surface of a negative electrode current collector copper foil having a thickness of 8 μm, and baked at 120 ℃ for 1 hour, to obtain a negative electrode coated with the negative electrode slurry on one side. And then repeating the steps on the second surface of the negative electrode to obtain the negative electrode with the double-sided coating negative electrode slurry. After coating, compacting and cutting to obtain the negative electrode with the specification of 76mm multiplied by 851mm for standby.
< Preparation of isolation Membrane >
Alumina was mixed with polyvinylidene fluoride in a mass ratio of 90:10 and dissolved in deionized water to form a ceramic slurry having a solids content of 50%. Subsequently, the ceramic slurry was uniformly coated on one surface of a porous substrate (polypropylene, thickness 7 μm, average pore diameter 0.073 μm, porosity 26%) by a gravure coating method, and dried to obtain a double layer structure of a ceramic coating layer and the porous substrate, the thickness of the ceramic coating layer being 50 μm.
Polyvinylidene fluoride (PVDF) was mixed with polyacrylate in a mass ratio of 96:4 and dissolved in deionized water to form a 50% solids polymer syrup. And then uniformly coating the polymer slurry on two surfaces of the ceramic coating and porous substrate double-layer structure by adopting a micro-concave coating method, and drying to obtain the isolating film, wherein the thickness of a single-layer coating formed by the polymer slurry is 2 mu m.
< Preparation of lithium ion Battery >
And stacking the prepared positive electrode, the prepared isolating film and the prepared negative electrode in sequence, enabling the isolating film to be positioned in the middle of the positive electrode and the negative electrode to play a role of isolation, and winding to obtain the electrode assembly. And (3) filling the electrode assembly into an aluminum foil packaging bag, baking at 80 ℃ for water removal, injecting the electrolyte prepared by the method, and carrying out the procedures of vacuum packaging, standing, formation, shaping and the like to obtain the lithium ion battery.
Examples 1 to 57, comparative examples 1 to 6, < preparation of electrolyte >, < preparation of positive electrode >, < preparation of negative electrode >, < preparation of separator > and < preparation of lithium ion battery > were all the same as each preparation step described above, and the changes of the relevant preparation parameters are shown in table 1:
As can be seen from examples 1 to 9 and comparative examples 1 and 5, the high-temperature safety performance and cycle performance of the lithium ion battery vary with the mass percentage a of phosphorus oxytrifluoride in the electrolyte. The lithium ion battery with the mass percent content A of the phosphorus trifluoride oxide in the electrolyte within the content range of the application is selected, and the high-temperature safety performance and the cycle performance are obviously better.
As can be seen from examples 7, 19 to 23 and comparative example 2, the high temperature safety performance and cycle performance of the lithium ion battery vary with the amount of polycyano compound B in the electrolyte. The lithium ion battery with the mass percent of the polycyano compound B in the electrolyte within the range of the application is selected, and the high-temperature safety performance and the cycle performance are obviously better.
The types and mass percentages of the fluoroester compound, the cyclic sulfonate compound and the unsaturated bond-containing cyclic carbonate in the electrolyte generally have an influence on the high-temperature safety performance and the cycle performance of the lithium ion battery. As can be seen from examples 39 to 51, as long as the kinds and contents of the fluoro-ester compound, the cyclic sulfonate compound and the unsaturated bond-containing cyclic carbonate in the electrolyte are made to fall within the scope of the present application, a lithium ion battery excellent in high-temperature safety performance and cycle performance can be obtained.
The sum A+B of the mass percent A of the phosphorus trifluoride oxide and the mass percent B of the polycyano compound and the sum A+D of the mass percent A of the phosphorus trifluoride oxide and the mass percent D of the cyclic sulfonate generally have an influence on the high-temperature safety performance and the cycle performance of the lithium ion battery. As can be seen from table 1, a+b or a+d is within the scope of the present application, a lithium ion battery having good high-temperature safety performance and cycle performance can be obtained.
The ratio F/A of the mass percent F of the transition metal element in the positive electrode active material to the mass percent A of the phosphorus trifluoride oxide in the electrolyte generally affects the high-temperature safety performance and the cycle performance of the lithium ion battery. As can be seen from examples 7, 53 to 57, the F/a is within the scope of the present application, and a lithium ion battery having excellent high-temperature safety performance and cycle performance can be obtained.
As is apparent from the above analysis, the electrochemical device provided by the present application comprises a positive electrode, a negative electrode, a separator, and an electrolyte comprising phosphorus oxytrifluoride and a polycyano compound comprising at least two cyano groups. The electrolyte can form a compact and stable protective film on the surface of the positive electrode, and inhibit the decomposition reaction of the electrolyte under high voltage. The electrochemical device containing the electrolyte has good high-temperature safety performance and cycle performance.
The foregoing description of the preferred embodiments of the application is not intended to limit the application to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the application are intended to be included within the scope of the application.
Claims (8)
1. An electrochemical device comprising a positive electrode, a negative electrode, a separator, and an electrolyte, the 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;
based on the total mass of the electrolyte, the mass percent A of the phosphorus trifluoride oxide is 0.9 to 3 percent, the mass percent B of the polycyano compound is 0.1 to 10 percent, and the mass percent A+B is more than or equal to 1.5 percent and less than or equal to 11 percent;
The polycyano compound comprises at least one of compounds shown in a structural formula (I):
Wherein R is selected from C 1 -C 15 alkyl, C 1 -C 15 alkenyl or C 1 -C 15 alkynyl, a and C are each independently 0 or positive integer, a and C are not simultaneously 0, 2-a+c-7, 0-b-6, and the number b of alkylene groups connected by each cyano group can be the same or different.
2. The electrochemical device according to claim 1, wherein the polycyano compound comprises any one of the following formulas (1) to (62):
3. The electrochemical device according to claim 1, wherein the electrolyte further comprises at least one of a fluoroester compound, a cyclic sulfonate, or a cyclic carbonate containing an unsaturated bond.
4. An electrochemical device according to claim 3, wherein the mass percent C of the fluoro-ester compound is 0.1% to 15% and/or the mass percent D of the cyclic sulfonate is 0.1% to 5% and/or the mass percent E of the unsaturated bond-containing cyclic carbonate is 0.01% to 2% based on the total mass of the electrolyte.
5. The electrochemical device according to claim 4, wherein the ratio of the mass percentage A of the phosphorus oxytrifluoride to the mass percentage D of the cyclic sulfonate is 1% to 7%.
6. The electrochemical device according to claim 3, wherein the fluoroester compound comprises at least one of fluoroethylene carbonate, difluoroethylene carbonate, fluoroethylmethyl carbonate, fluorodimethylcarbonate, fluorodiethylcarbonate, fluoroethylpropionate, fluoropropylate, methyl fluoropropionate, ethyl fluoroacetate, methyl fluoroacetate, propyl fluoroacetate, and trifluoromethylcarbonate;
The cyclic sulfonate comprises at least one of 1, 3-propane sultone or 1, 4-butane sultone;
The unsaturated bond-containing cyclic carbonate contains at least one of vinylene carbonate or vinyl ethylene carbonate.
7. The electrochemical device according to any one of claims 1to 6, wherein a mass percentage content F of a metal element other than lithium in a positive electrode active material in the positive electrode active material and a mass percentage content a of the phosphorus oxytrifluoride in the electrolyte satisfy 600> F/a >10.
8. An electronic device comprising the electrochemical device of any one of claims 1 to 7.
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| CN105742711A (en) * | 2016-05-12 | 2016-07-06 | 中国科学院宁波材料技术与工程研究所 | Electrolyte and lithium ion battery |
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| KR20080047642A (en) * | 2006-11-27 | 2008-05-30 | 주식회사 엘지화학 | Lithium Secondary Battery with Improved Operating Efficiency |
| CN102637894B (en) * | 2012-04-06 | 2014-11-05 | 宁德新能源科技有限公司 | Secondary battery with non-aqueous electrolyte |
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| JP6520064B2 (en) * | 2014-11-19 | 2019-05-29 | セントラル硝子株式会社 | Electrolyte for non-aqueous electrolyte battery and lithium non-aqueous electrolyte battery |
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| CN105742711A (en) * | 2016-05-12 | 2016-07-06 | 中国科学院宁波材料技术与工程研究所 | Electrolyte and lithium ion battery |
| CN112751081A (en) * | 2020-12-29 | 2021-05-04 | 东莞新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
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