Lithium-ion batteries, battery units, battery packs, and electrical devices

Abstract

The present application provides a lithium ion battery, comprising a positive electrode plate, a negative electrode plate, a separator, and an electrolyte, the ratio of the negative electrode capacity to the positive electrode capacity of the lithium ion battery is a, the electrolyte contains a thiourea compound with a content of b% by weight based on the total weight of the electrolyte, and the lithium ion battery satisfies the following relational formula: a<1.05, and 25×(1.05-a)≦b≦100×(1.05-a) Since the electrolyte contains a certain amount of a thiourea-based compound, the lithium ion battery has a relatively low CB value and good cycle performance.

Description

[Technical Field]

[0001] This application relates to lithium-ion batteries, and more particularly to lithium-ion batteries, battery units, battery packs, and electrical devices with high energy density. [Background technology]

[0002] In recent years, lithium-ion batteries have seen a wide range of applications and are used in many fields, including energy storage and power systems such as hydroelectric power plants, thermal power plants, wind power plants, and solar power plants, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, and aerospace.

[0003] In conventional wound lithium-ion batteries, to solve the problem of corner lithium deposition, the cell balance (CB) ratio (negative electrode capacity:positive electrode capacity) is generally set to 1.07 or higher, thereby ensuring the battery's cycle performance. However, when the CB value becomes relatively high, the battery's energy density decreases significantly. Therefore, it is desirable to lower the CB value of lithium-ion batteries to improve the battery's energy density while ensuring good battery cycle performance. [Overview of the project] [Problems that the invention aims to solve]

[0004] This application was made in view of the above-mentioned problems, and aims to provide a lithium-ion battery that has a low CB value and good cycle performance. [Means for solving the problem]

[0005] To achieve the above object, a first aspect of the present application provides a lithium-ion battery. The lithium-ion battery includes a positive electrode plate, a negative electrode plate, a separator, and an electrolyte. The ratio of the negative electrode capacity to the positive electrode capacity of the lithium-ion battery is a, and the electrolyte contains a thiourea-based compound with a content of b% by weight based on the total weight of the electrolyte. The lithium-ion battery satisfies the following relational expression. a < 1.05 and 25×(1.05 - a) ≤ b ≤ 100×(1.05 - a)

[0006] In the present application, by adding the above amount of the thiourea-based compound to the electrolyte, even if the CB value of the battery is relatively low, the battery has good cycle performance.

[0007] In any embodiment, the value of a / b is 0.8 to 2, and optionally is 1 to 1.8. If it is within this range, the energy density and cycle performance of the lithium-ion battery are further improved.

[0008] In any embodiment, a satisfies 0.9 ≤ a < 1.05, and optionally is 0.98 to 1.04. If it is within this range, the lithium-ion battery has a better balance between cycle performance and energy density.

[0009] In any embodiment, b is 0.2 to 5, and optionally is 0.5 to 2, and optionally is 0.5 to 1.0. By selecting the content of the thiourea-based compound, the cycle performance of the battery can be further improved.

[0010] In any embodiment, the thiourea-based compound has a structural formula as follows:

Chemical formula

[0011] In any embodiment, the electrolyte further contains at least one additive selected from metal nitrates, fluoroethylene carbonate, and vinylene carbonate. Optionally, the metal nitrate is one or more of lithium nitrate, magnesium nitrate, and copper(II) nitrate. Optionally, the content of the additive is 0.5 wt% to 2 wt% based on the total mass of the electrolyte. By adding the additive, the cycle performance of the battery can be further improved.

[0012] In any embodiment, in the negative electrode plate of the lithium-ion battery, the thickness of the negative electrode film layer is 140 μm or less. If it is within this range, the cycle performance of the battery is further improved.

[0013] The second aspect of the present application provides a battery unit. The battery unit includes the lithium-ion battery according to the first aspect of the present application.

[0014] The third aspect of the present application provides a battery pack. The battery pack includes the battery unit according to the second aspect of the present application.

[0015] The fourth aspect of the present application provides an electrical device. The electrical device includes at least one of the lithium-ion battery according to the first aspect of the present application, the battery unit according to the second aspect of the present application, or the battery pack according to the third aspect of the present application. [Brief explanation of the drawing]

[0016] [Figure 1] This is a schematic diagram of a lithium-ion battery according to one embodiment of the present application. [Figure 2] Figure 1 is an exploded view of a lithium-ion battery according to one embodiment of the present application. [Figure 3] This is a schematic diagram of a battery unit according to one embodiment of the present application. [Figure 4] This is a schematic diagram of a battery pack according to one embodiment of the present application. [Figure 5] Figure 4 is an exploded view of a battery pack according to one embodiment of this application. [Figure 6] This is a schematic diagram of an electrical device powered by a lithium-ion battery according to one embodiment of the present application. [Modes for carrying out the invention]

[0017] The embodiments of the lithium-ion battery, battery unit, battery pack, and electrical device relating to this application will be described in detail below with reference to the drawings. However, detailed explanations of non-essential matters may be omitted. For example, detailed explanations of well-known matters and redundant explanations of similar configurations may be omitted. This is to avoid making the following explanation unnecessarily long and to ensure that it is easily understood by those skilled in the art. Furthermore, the drawings and the following explanation are intended to enable those skilled in the art to fully understand this application and do not limit the subject matter described in the claims.

[0018] The “range” disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit. The selected lower limit and upper limit define the limits of a particular range. The range thus defined may or may not include the limit and can be in any combination; that is, it is possible to define a range with any combination of a lower limit and an upper limit. For example, if the ranges 60-120 and 80-110 are given for a particular parameter, it should be understood that the ranges 60-110 and 80-120 are also predictable. Also, if the lower limits are 1 and 2 and the upper limits are 3, 4 and 5, then any of the ranges 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5 are also predictable. In this application, unless otherwise stated, “a-b” in numerical ranges is an abbreviation for any combination of real numbers between real number a and real number b. For example, the numerical range "0 to 5" includes all real numbers between "0 to 5" as specified in the specification, and "0 to 5" is merely an abbreviated representation of combinations of these numbers. Also, if a parameter is expressed as an integer of 2 or more, it is equivalent to disclosing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0019] Unless otherwise stated, all embodiments and optional embodiments of this application can be combined to form new technical inventions. Unless otherwise stated, all technical features of this application and the selectable technical features can be combined to form a new technical invention.

[0020] Unless otherwise stated, all steps of this application may be performed sequentially or randomly. It is preferable that they be performed sequentially. For example, if the method includes step (a) and step (b), the method may include step (a) and step (b) performed in order, or step (b) and step (a) performed in order. For example, the method may further include step (c), and step (c) may be incorporated into the method in any order, for example, step (a), step (b) and step (c), step (a), step (c) and step (b), or step (c), step (a) and step (b), and so on.

[0021] Unless otherwise specified, the terms “includes” and “inclusion” in this application may be open or closed. For example, when “includes” and “inclusion” are used, they may include or include elements not listed, or they may include or include only the listed elements.

[0022] Unless otherwise stated, the term "or" in this application is a broad expression. For example, the phrase "A or B" means "A, B, or A and B." More specifically, the conditions "A or B" are met when A is true (or exists) and B is false (or does not exist), when A is false (or does not exist) and B is true (or exists), and when both A and B are true (or exist).

[0023] In conventional lithium-ion batteries, the ratio of negative electrode capacity to positive electrode capacity (negative electrode capacity:positive electrode capacity), i.e., the CB (cell balance) value, is relatively high, generally 1.07 or higher, and sometimes exceeding 1.1. When the CB value is relatively high, the negative electrode capacity significantly exceeds the positive electrode capacity. This provides sufficient space for lithium during the charge and discharge process, preventing lithium from accumulating on the negative electrode surface and forming dendrites, thus resulting in relatively good cycle performance for the battery. However, a relatively high CB value leads to wasted negative electrode space and a relatively low energy density. Therefore, it is desirable to lower the CB value of lithium-ion batteries to improve the energy density while ensuring good cycle performance.

[0024] This application describes how adding a specific amount of thiourea-based compound to the electrolyte of a lithium-ion battery can result in a lithium-ion battery having a lower cycle value than conventional lithium-ion batteries, thereby providing a lithium-ion battery with good cycle performance.

[0025] In one embodiment of this application, the present application provides a lithium-ion battery. The lithium-ion battery comprises a positive electrode plate, a negative electrode plate, a separator, and an electrolyte, the ratio of the negative electrode capacity to the positive electrode capacity of the lithium-ion battery is a, the electrolyte contains a thiourea-based compound in a content of b% by weight relative to the total weight of the electrolyte, and the lithium-ion battery satisfies the following relational expression.

[0026] a < 1.05 and 25 × (1.05 - a) ≤ b ≤ 100 × (1.05 - a)

[0027] Although the detailed mechanism is not yet understood, the applicant has discovered the following: In this application, by adding the above amount of thiourea-based compound to the electrolyte, the battery has good cycle performance even with a relatively low CB value. If the content of the thiourea-based compound is too low, the cycle performance cannot be sufficiently improved, and if the content of the thiourea-based compound is too high, gas will be generated in the battery during storage due to the oxidation of thiourea. A lithium-ion battery designed as described above has good cycle performance and energy density.

[0028] The negative electrode capacity and positive electrode capacity of a battery can be measured by the following methods. After completely discharging a lithium-ion battery (for example, discharging to 2.5V in the lithium-ion battery of this application constitutes complete discharge), the battery is disassembled to obtain the positive and negative electrodes. A coin-type battery is then assembled using metallic lithium as the counter electrode for each of the positive and negative electrodes, and a capacity discharge is performed at 0.1mA to measure the corresponding capacity. For the specific process of measuring the CB value, refer to the section describing the measurement method in the embodiment of this application.

[0029] In some embodiments, the value of a / b is between 0.8 and 2, and optionally between 1 and 1.8. Keeping it within this range further improves the energy density and cycle performance of the lithium-ion battery.

[0030] In some embodiments, a is 0.9 ≤ a < 1.05, and optionally 0.98 to 1.04. Within this range, lithium-ion batteries achieve a better balance between cycle performance and energy density.

[0031] In some embodiments, b is 0.2 to 5, optionally 0.5 to 2, and optionally 0.5 to 1.0. By selecting the content of the thiourea compound, the battery's cycle performance can be further improved.

[0032] In some embodiments, the thiourea-based compound has the following structural formula: [Chemical Formula] R and X are each independently selected from H, a C1-C 10 alkyl group, a C1-C 10 alkenyl group, or a phenyl group, or R and X together represent a C1-C 10 alkylene group or a C1-C 10 alkenylene group, and the C1-C 10 alkylene group or the C1-C 10 alkenylene group is optionally substituted with an oxygen group. Optionally, R and X are each independently selected from H, a C1-C6 alkyl group, a C1-C6 alkenyl group, or R and X together represent a C1-C6 alkylene group or a C1-C6 alkenylene group, and the C1-C6 alkylene group or the C1-C6 alkenylene group is optionally substituted with an oxygen group. Optionally, the thiourea-based compound has one of the following structures. [Chemical Formula] By selecting the thiourea-based compound, the cycle performance of the lithium-ion battery can be further improved.

[0033] In some embodiments, the electrolyte further contains at least one additive selected from metal nitrates, fluoroethylene carbonate, and vinylene carbonate. Optionally, the metal nitrate is one or more of lithium nitrate, magnesium nitrate, and copper(II) nitrate. Optionally, the content of the additive is 0.5 wt% to 2 wt%. By adding the additive, the cycle performance of the battery can be further improved.

[0034] In some embodiments, the thickness of the negative electrode film layer in the negative electrode plate of the lithium-ion battery is 140 micrometers or less. Keeping it within this range further improves the battery's cycle performance.

[0035] The lithium-ion battery, battery unit, battery pack, and electrical device related to this application will be described below with reference to the drawings.

[0036] One embodiment of this application provides a lithium-ion battery. Generally, a lithium-ion battery includes a positive electrode plate, a negative electrode plate, an electrolyte, and a separator. During the charging and discharging process of the battery, active ions are repeatedly inserted into and removed from between the positive and negative electrode plates. The electrolyte transports ions between the positive and negative electrode plates. The separator is placed between the positive and negative electrode plates and primarily prevents short circuits between the positive and negative electrodes while allowing ions to pass through.

[0037] [Positive plate] The positive electrode plate includes a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector. The positive electrode film layer includes a positive electrode active material according to the first aspect of this application. For example, the positive electrode current collector has two opposing surfaces in its thickness direction, and the positive electrode film layer is provided on one or both of the two opposing surfaces of the positive electrode current collector.

[0038] In some embodiments, a metal foil or a composite current collector is used as the positive electrode current collector. For example, aluminum foil can be used as the metal foil. The composite current collector may include a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector can be formed by providing a metal material (such as aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy) on a polymer material substrate (for example, a substrate such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), or polyethylene (PE)).

[0039] In some embodiments, the positive electrode active material can be any positive electrode active material for batteries that is well known in the art. For example, the positive electrode active material may include at least one of an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and a modified compound thereof. This application is not limited to these materials, and other conventional materials that can be used as positive electrode active materials for batteries may be used. These positive electrode active materials may be used alone or in combination of two or more. Examples of lithium transition metal oxides include lithium cobalt oxide (e.g., LiCoO2), lithium nickel oxide (e.g., LiNiO2), lithium manganese oxide (e.g., LiMnO2, LiMn2O4), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, and lithium nickel cobalt manganese oxide (e.g., LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2 (simply NCM) 333 (Sometimes referred to as) LiNi 0.5 Co 0.2 Mn 0.3 O2 (simply NCM) 523 (Sometimes referred to as) LiNi 0.5 Co 0.25 Mn 0.25 O2 (simply NCM) 211 (Sometimes referred to as) LiNi 0.6 Co 0.2 Mn 0.2 O2 (simply NCM) 622 (Sometimes referred to as) LiNi 0.8 Co 0.1 Mn 0.1 O2 (simply NCM) 811 (sometimes referred to as), lithium nickel cobalt aluminum oxide (e.g., LiNi 0.85 Co 0.15 Al 0.05This includes, but is not limited to, at least one of the following: O2) and modified compounds thereof. Examples of lithium-containing phosphates with an olivine structure include, but is not limited to, at least one of the following: lithium iron phosphate (e.g., LiFePO4 (sometimes simply referred to as LFP)), lithium iron phosphate and carbon composites, lithium manganese phosphate (e.g., LiMnPO4), lithium manganese phosphate and carbon composites, lithium iron manganese phosphate, and lithium iron manganese phosphate and carbon composites.

[0040] In some embodiments, the positive electrode film layer optionally further includes a binder. For example, the binder includes at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a ternary copolymer of vinylidene fluoride-tetrafluoroethylene-propylene, a ternary copolymer of vinylidene fluoride-hexafluoropropene-tetrafluoroethylene, a copolymer of tetrafluoroethylene-hexafluoropropene, and a fluorine-containing acrylic resin.

[0041] In some embodiments, the cathode film layer optionally further contains a conductive agent. For example, the conductive agent includes at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

[0042] In some embodiments, a positive electrode plate can be prepared by the following method: The above components for preparing a positive electrode plate, such as a positive electrode active material, a conductive agent, a binder, and other optional components, are dispersed in a solvent (e.g., N-methylpyrrolidone) to form a positive electrode slurry, the positive electrode slurry is applied to a positive electrode current collector, and the positive electrode plate is obtained through processes such as drying and cold pressing.

[0043] [negative electrode plate] The negative electrode plate includes a negative electrode current collector and a negative electrode film layer provided on at least one surface of the negative electrode current collector. The negative electrode film layer contains a negative electrode active material. For example, the negative electrode current collector has two opposing surfaces in its thickness direction, and the negative electrode film layer is provided on one or both of the two opposing surfaces of the negative electrode current collector.

[0044] In some embodiments, a metal foil or a composite current collector is used as the negative electrode current collector. For example, copper foil can be used as the metal foil. The composite current collector may include a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector can be formed by providing a metal material (such as copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, silver, and silver alloys) on a polymer material substrate (for example, a substrate such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), or polyethylene (PE)).

[0045] In some embodiments, the negative electrode active material can be any negative electrode active material for batteries that is well known in the art. For example, the negative electrode active material may include at least one of artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, and lithium titanate. The silicon-based material is at least one selected from elemental silicon, silicon oxide, silicon-carbon composite, silicon-nitrogen composite, and silicon alloy. The tin-based material is at least one selected from elemental tin, tin oxide, and tin alloy. This application is not limited to these materials, and other conventional materials usable as negative electrode active materials for batteries may be used. These negative electrode active materials may be used individually or in combination of two or more.

[0046] In some embodiments, the negative electrode film layer optionally further includes a binder. The binder is at least one selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).

[0047] In some embodiments, the negative electrode film layer optionally further contains a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

[0048] In some embodiments, the negative electrode film layer may optionally contain other additives, such as thickeners (e.g., sodium carboxymethylcellulose (CMC-Na)).

[0049] In some embodiments, the negative electrode plate can be prepared by the following method. The above components for preparing the negative electrode plate, such as a negative electrode active material, a conductive agent, a binder, and other optional components, are dispersed in a solvent (e.g., deionized water) to form a negative electrode slurry. The negative electrode slurry is applied to a negative electrode current collector, and the negative electrode plate is obtained through processes such as drying and cold pressing.

[0050] [Electrolytes] The electrolyte transports ions between the positive and negative electrodes. This application does not specifically limit the type of electrolyte, and it can be selected as needed. For example, the electrolyte may be liquid, gel-like, or all-solid.

[0051] In some embodiments, an electrolyte solution is used as the electrolyte. The electrolyte solution comprises an electrolyte salt and a solvent.

[0052] In some embodiments, the electrolyte salt is at least one selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalatoborate, lithium bisoxalatoborate, lithium difluorobis(oxalato)phosphate, and lithium tetrafluoro(oxalato)phosphate.

[0053] In some embodiments, the solvent is at least one selected from ethylene carbonate, propylene carbonate, ethylmethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butanoate, ethyl butanoate, γ-butyrolactone, sulfolane, dimethyl sulfone, ethylmethyl sulfone, and diethyl sulfone.

[0054] In some embodiments, the electrolyte may optionally further contain other additives. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain performance characteristics of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high-temperature performance of the battery, or additives that improve the low-temperature performance of the battery.

[0055] [Separator] In some embodiments, the lithium-ion battery further includes a separator. This application does not particularly limit the type of separator, and any well-known porous separator having good chemical and mechanical stability may be used.

[0056] In some embodiments, the material of the separator is at least one selected from glass fiber, nonwoven fabric, polyethylene, polypropylene, and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. If the separator is a multilayer composite thin film, the materials of each layer may be the same or different, and is not particularly limited.

[0057] In some embodiments, the positive electrode plate, negative electrode plate, and separator are manufactured as an electrode assembly by a winding process or a lamination process.

[0058] In some embodiments, the lithium-ion battery includes a package, which is used to enclose the electrode assembly and electrolyte.

[0059] In some embodiments, the lithium-ion battery package may be a rigid case, such as a rigid plastic case, an aluminum case, or a steel case, or a soft pack, such as a bag-shaped soft pack. The material of the soft pack can be a plastic, such as polypropylene, polybutylene terephthalate, or polybutylene succinate.

[0060] In this application, the shape of the lithium-ion battery is not particularly limited and may be cylindrical, rectangular, or any other shape. For example, Figure 1 shows a lithium-ion battery 5 with a rectangular structure as an example.

[0061] In some embodiments, as shown in Figure 2, the package includes a housing 51 and a cover plate 53. The housing 51 includes a bottom plate and side plates connected to the bottom plate, the bottom plate and side plates forming a housing chamber. The housing 51 has an opening that communicates with the housing chamber, and the cover plate 53 is provided to close the opening and seal the housing chamber. The positive electrode plate, negative electrode plate and separator are formed as an electrode assembly 52 by a winding process or a lamination process. The electrode assembly 52 is sealed inside the housing chamber. The electrolyte permeates the electrode assembly 52. ​​The number of electrode assemblies 52 included in the lithium-ion battery 5 may be one or more, and can be selected according to the actual requirements of those skilled in the art.

[0062] In some embodiments, lithium-ion batteries can be assembled as battery units, and the number of lithium-ion batteries contained in a battery unit may be one or more, the specific number of which can be selected by those skilled in the art depending on the application and capacity of the battery unit.

[0063] Figure 3 shows an example of a battery unit 4. As shown in Figure 3, in the battery unit 4, multiple lithium-ion batteries 5 are arranged sequentially along the length of the battery unit 4. Of course, they may be arranged in any other manner. Furthermore, the multiple lithium-ion batteries 5 may be fixed in place by fixing members.

[0064] Optionally, the battery unit 4 further comprises a housing having a housing space for accommodating a plurality of lithium-ion batteries 5.

[0065] In some embodiments, the above-described battery unit can be assembled as a battery pack, and the number of battery units included in the battery pack may be one or more, the specific number of which can be selected by those skilled in the art depending on the application and capacity of the battery pack.

[0066] Figures 4 and 5 show an example of a battery pack 1. As shown in Figure 5, the battery pack 1 comprises a battery box and a plurality of battery units 4 installed in the battery box. The battery box includes an upper box 2 and a lower box 3, with the upper box 2 covering the lower box 3, thus forming a sealed space for housing the battery units 4. The plurality of battery units 4 are arranged in the battery box in any manner.

[0067] Furthermore, this application provides an electrical device comprising at least one of a lithium-ion battery, battery unit, or battery pack according to this application. The lithium-ion battery, battery unit, or battery pack may be used as a power source for the electrical device or as an energy storage unit for the electrical device. The electrical device includes, but is not limited to, portable devices (e.g., mobile phones, laptops, etc.), electric vehicles (e.g., fully electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), trains, ships and satellites, and energy storage systems.

[0068] For the aforementioned electrical device, a lithium-ion battery, battery unit, or battery pack can be selected according to the usage requirements.

[0069] Figure 6 shows an example of an electrical device, such as a fully electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle. To meet the high rate and high energy density requirements for lithium-ion batteries in the electrical device, a battery pack or battery unit can be used.

[0070] Other examples include mobile phones, tablets, and laptop computers. Since these devices are generally required to be lightweight and thin, lithium-ion batteries can be used as a power source. [Examples]

[0071] The following describes embodiments of this application. The embodiments described are illustrative and are for interpretation purposes only, and do not limit this application. The absence of specific technical or conditional descriptions in the embodiments can be done in accordance with technical or conditional or product specifications described in the literature in the art. For reagents or instruments whose manufacturers are not specified, commercially available conventional products can be used. The thiourea additives used in the examples and comparative examples are as follows:

[0072] [ka]

[0073] (Comparative Example 1) [Preparation of electrolyte solution] In a glove box under an argon gas atmosphere with a water content of less than 10 ppm, 26.25 g of EC (ethylene carbonate), 61.25 g of EMC (ethylmethyl carbonate), and 12.5 g of LiPF6 were placed in a beaker and thoroughly stirred to dissolve them, thereby obtaining the electrolyte of this comparative example.

[0074] [Manufacturing of positive electrode plates] Nickel-cobalt-manganese ternary material for cathode active material (LiNi 0.8 Co 0.1 Mn 0.1 O2 (with a capacity of 180 mAh / g), polyvinylidene fluoride (a binder), and acetylene black (a conductive agent) were mixed in a mass ratio of 8:1:1. NMP (N-methylpyrrolidone) was added as a solvent, and the mixture was treated with a vacuum stirrer to obtain a positive electrode slurry. 0.2826 g (dry weight) of the positive electrode slurry was collected at 1540.25 mm. 2 The material was uniformly applied to a 13 μm thick aluminum foil for the positive electrode current collector. After drying the aluminum foil at room temperature, it was dried in a 120°C oven for 1 hour, and then cold-pressed and cut to obtain the positive electrode plate.

[0075] [Manufacturing of negative electrode plates] Artificial graphite (with a capacity of 350 mAh / g), conductive carbon black, and binder acrylate were mixed in a mass ratio of 92:2:6, deionized water was added, and a negative electrode slurry was obtained by processing in a vacuum agitator. 0.1290 g (dry weight) of the negative electrode slurry was measured at 1540.25 mm. 2 The material was uniformly applied to a copper foil for a negative electrode current collector with a thickness of 8 μm. After drying the copper foil at room temperature, it was dried in a 120°C oven for 1 hour. Then, cold pressing was performed until the thickness of the negative electrode film layer was 100 micrometers, and the negative electrode plate was obtained by cutting it.

[0076] [Separator] The separator was obtained from Cellgard, and its model number was Cellgard2400.

[0077] [Manufacturing of lithium-ion batteries] A positive electrode plate, a separator, and a negative electrode plate were stacked in sequence with the separator separating the positive and negative electrode plates, and then wound up to obtain a bare cell. The bare cell was placed in a foil package, 8.6 g of the prepared electrolyte was injected into the dried battery, and a lithium-ion battery was obtained through processes such as vacuum packaging, standing, chemical formation, and shaping.

[0078] (Comparative Example 2) The manufacturing process of the lithium-ion battery was basically the same as that of Comparative Example 1, but differed from Comparative Example 1 in the following respects. Electrolyte manufacturing step: In a glove box under an argon gas atmosphere with a water content of less than 10 ppm, 26.1 g of EC, 60.9 g of EMC, 12.5 g of LiPF6, and 0.5 g of thiourea compound 1 were placed in a beaker and thoroughly stirred to dissolve, thereby obtaining the electrolyte of this comparative example.

[0079] (Comparative Example 3) The manufacturing process for the lithium-ion battery was basically the same as that of Comparative Example 1, but differed from Comparative Example 1 in the following respects. Electrolyte preparation steps: In a glove box under an argon gas atmosphere with a water content of less than 10 ppm, 25.29 g of EC, 59.01 g of EMC, 12.5 g of LiPF6, and 3.2 g of thiourea compound 1 were placed in a beaker and thoroughly stirred to dissolve, thereby obtaining the electrolyte of this comparative example.

[0080] (Example 1) The manufacturing process of the lithium-ion battery was basically the same as that of Comparative Example 1, but differed from Comparative Example 1 in the following respects. Electrolyte manufacturing step: In a glove box under an argon gas atmosphere with a water content of less than 10 ppm, 25.95 g of EC, 60.55 g of EMC, 12.5 g of LiPF6, and 1 g of thiourea compound 1 were placed in a beaker and thoroughly stirred to dissolve, thereby obtaining the electrolyte of this example.

[0081] (Example 2) The manufacturing process of the lithium-ion battery was basically the same as that of Comparative Example 1, but differed from Comparative Example 1 in the following respects. Electrolyte manufacturing step: In a glove box under an argon gas atmosphere with a water content of less than 10 ppm, 26.01 g of EC, 60.69 g of EMC, 12.5 g of LiPF6, and 0.8 g of thiourea compound 1 were placed in a beaker and thoroughly stirred to dissolve, thereby obtaining the electrolyte of this example.

[0082] (Example 3) The manufacturing process for the lithium-ion battery was basically the same as that of Comparative Example 1, but differed from Comparative Example 1 in the following respects. Electrolyte preparation steps: In a glove box under an argon gas atmosphere with a water content of less than 10 ppm, 25.8 g of EC, 60.2 g of EMC, 12.5 g of LiPF6, and 1.5 g of thiourea compound 1 were placed in a beaker and thoroughly stirred to dissolve, thereby obtaining the electrolyte of this example.

[0083] (Example 4) The manufacturing process for the lithium-ion battery was basically the same as that of Comparative Example 1, but differed from Comparative Example 1 in the following respects. Electrolyte preparation steps: In a glove box under an argon gas atmosphere with a water content of less than 10 ppm, 25.9 g of EC, 60.4 g of EMC, 12.5 g of LiPF6, and 1.2 g of thiourea compound 1 were placed in a beaker and thoroughly stirred to dissolve them, thereby obtaining the electrolyte of this example.

[0084] (Example 5) The manufacturing process for the lithium-ion battery was basically the same as that of Comparative Example 1, but differed from Comparative Example 1 in the following respects. 0.1315g (dry weight) of negative electrode slurry / 1540.25mm 2 The amount was uniformly applied to a copper foil for the negative electrode current collector with a thickness of 8 μm. Then, in the electrolyte preparation step: in a glove box with an argon gas atmosphere having a water content of less than 10 ppm, 26.07 g of EC, 60.83 g of EMC, 12.5 g of LiPF6, and 0.6 g of thiourea compound 1 were placed in a beaker and stirred thoroughly to dissolve, thereby obtaining the electrolyte of this example.

[0085] (Example 6) The manufacturing process for the lithium-ion battery was basically the same as that of Comparative Example 1, but differed from Comparative Example 1 in the following respects. 0.1315g (dry weight) of negative electrode slurry / 1540.25mm 2 The amount was uniformly coated onto a copper foil for the negative electrode current collector with a thickness of 8 μm. Then, in the electrolyte preparation step: in a glove box with an argon gas atmosphere having a water content of less than 10 ppm, 26.085 g of EC, 60.865 g of EMC, 12.5 g of LiPF6, and 0.55 g of thiourea compound 1 were placed in a beaker and stirred thoroughly to dissolve, thereby obtaining the electrolyte of this example.

[0086] (Example 7) The manufacturing process for the lithium-ion battery was basically the same as that of Comparative Example 1, but differed from Comparative Example 1 in the following respects. 0.1315g (dry weight) of negative electrode slurry / 1540.25mm 2The amount was uniformly applied to a copper foil for the negative electrode current collector with a thickness of 8 μm. Then, in the electrolyte preparation step: in a glove box with an argon gas atmosphere having a water content of less than 10 ppm, 26.1 g of EC, 60.9 g of EMC, 12.5 g of LiPF6, and 0.5 g of thiourea compound 1 were placed in a beaker and stirred thoroughly to dissolve, thereby obtaining the electrolyte of this example.

[0087] (Example 8) The manufacturing process for the lithium-ion battery was basically the same as that of Comparative Example 1, but differed from Comparative Example 1 in the following respects. 0.1239g (dry weight) of negative electrode slurry / 1540.25mm 2 The amount was uniformly applied to a copper foil for the negative electrode current collector with a thickness of 8 μm. Then, in the electrolyte preparation step: in a glove box with an argon gas atmosphere having a water content of less than 10 ppm, 25.65 g of EC, 59.85 g of EMC, 12.5 g of LiPF6, and 2 g of thiourea compound 1 were placed in a beaker and stirred thoroughly to dissolve, thereby obtaining the electrolyte of this example.

[0088] (Example 9) The manufacturing process for the lithium-ion battery was basically the same as that of Comparative Example 1, but differed from Comparative Example 1 in the following respects. 0.115g (dry weight) of negative electrode slurry / 1540.25mm 2 The amount was uniformly applied to a copper foil for the negative electrode current collector with a thickness of 8 μm. Then, in the electrolyte preparation step: in a glove box with an argon gas atmosphere having a water content of less than 10 ppm, 25.05 g of EC, 58.45 g of EMC, 12.5 g of LiPF6, and 4 g of thiourea compound 1 were placed in a beaker and stirred thoroughly to dissolve, thereby obtaining the electrolyte of this example.

[0089] (Example 10) The manufacturing process for the lithium-ion battery was basically the same as in Example 1, but it differed from Example 1 in that the thiourea compound added in the electrolyte preparation of this example was thiourea compound 2.

[0090] (Example 11) The manufacturing process for the lithium-ion battery was basically the same as in Example 1, but it differed from Example 1 in that the thiourea compound added in the electrolyte preparation of this example was thiourea compound 3.

[0091] (Example 12) The manufacturing process for the lithium-ion battery was basically the same as in Example 1, but it differed from Example 1 in that the thiourea compound added in the electrolyte preparation of this example was thiourea compound 4.

[0092] (Example 13) The manufacturing process for the lithium-ion battery was basically the same as in Example 1, but it differed from Example 1 in that the thiourea compound added in the electrolyte preparation of this example was thiourea compound 5.

[0093] (Example 14) The manufacturing process for the lithium-ion battery was basically the same as in Example 1, but the electrolyte preparation process differed from Example 1 in the following respects. In a glove box under an argon gas atmosphere with a water content of less than 10 ppm, 25.35 g of EC, 59.15 g of EMC, 12.5 g of LiPF6, 1 g of thiourea compound 1, 1 g of FEC (fluoroethylene carbonate), and 1 g of LiNO3 were placed in a beaker and thoroughly stirred to dissolve them, thereby obtaining the electrolyte of this example.

[0094] (Example 15) The manufacturing process for the lithium-ion battery was basically the same as in Example 1, but the electrolyte preparation process differed from that example in the following respects. In a glove box under an argon gas atmosphere with a water content of less than 10 ppm, 25.35 g of EC, 59.15 g of EMC, 12.5 g of LiPF6, 1 g of thiourea compound 1, 1 g of FEC, and 1 g of Mg(NO3)2 were placed in a beaker and thoroughly stirred to dissolve them, thereby obtaining the electrolyte of this example.

[0095] (Example 16) The manufacturing process for the lithium-ion battery was basically the same as in Example 1, but the electrolyte preparation process differed from that example in the following respects. In a glove box under an argon gas atmosphere with a water content of less than 10 ppm, 25.35 g of EC, 59.15 g of EMC, 12.5 g of LiPF6, 1 g of thiourea compound 1, 1 g of VC (vinylene carbonate), and 1 g of LiNO3 were placed in a beaker and thoroughly stirred to dissolve them, thereby obtaining the electrolyte of this example.

[0096] (Example 17) The manufacturing process for the lithium-ion battery was basically the same as in Example 1, but the electrolyte preparation process differed from that example in the following respects. In a glove box under an argon gas atmosphere with a water content of less than 10 ppm, 25.35 g of EC, 59.15 g of EMC, 12.5 g of LiPF6, 1 g of thiourea compound 1, and 2 g of LiNO3 were placed in a beaker and thoroughly stirred to dissolve them, thereby obtaining the electrolyte of this example.

[0097] (Example 18) The manufacturing process for the lithium-ion battery was basically the same as in Example 1, but differed in that the thickness of the cold-pressed negative electrode film layer was 90 micrometers.

[0098] (Example 19) The manufacturing process for the lithium-ion battery was basically the same as in Example 1, but it differed in that the thickness of the cold-pressed negative electrode film layer was 140 micrometers.

[0099] (Example 20) The manufacturing process for the lithium-ion battery was basically the same as in Example 1, but it differed in that the thickness of the cold-pressed negative electrode film layer was 150 micrometers.

[0100] Measurement method 1. Measurement of CB value After discharging a lithium-ion battery to 2.5V, the battery was disassembled to obtain the negative electrode plate. A coin-type battery was assembled using metallic lithium as the counter electrode for the negative electrode plate. The coin-type battery used a standard metal case for a 2046 button cell, with the electrode plates cut into 14mm diameter discs, a 16mm diameter disc for the metallic lithium plate, and an 18mm diameter PP separator for the intermediate separator. The above coin-type battery was discharged to 0.05V at 36mA, and its discharge capacity was recorded as N1.

[0101] A lithium-ion battery was fully charged to 4.4V, and the battery was disassembled to obtain the positive electrode plate. A coin-type battery was assembled using metallic lithium as the counter electrode for the positive electrode plate. The coin-type battery used a standard metal case for a 2046 button cell, with the electrode plates cut into 14mm diameter discs, a 16mm diameter disc for the metallic lithium plate, and an 18mm diameter PP separator for the intermediate separator. The above coin-type battery was discharged to 3.0V at 18mA, and its discharge capacity was recorded as N2. This allowed us to obtain the CB value (CB value = N1 / N2) of the lithium-ion battery.

[0102] Cycle performance evaluation at 2.25℃ Under a temperature of 25°C, a lithium-ion battery was charged to 4.35V with a constant current of 0.5C, then charged at a constant voltage until the current dropped to 0.05C, and finally discharged to 2.8V with a constant current of 0.5C. The discharge capacity was recorded as U1. The above charge-discharge process was then repeated 600 times in a 25°C environment, and the discharge capacity of the 600th cycle was recorded as U2. The capacity retention rate of a lithium-ion battery after 600 cycles at a temperature of 25°C = [U2 / U1] × 100%

[0103] 3. Evaluation of storage performance at 60°C Under a temperature of 60°C, a lithium-ion battery was charged to 4.35V with a constant current of 0.5C, then charged with a constant voltage until the current was reduced to 0.05C. The thickness of the lithium-ion battery was measured and recorded as h0. The lithium-ion battery was then stored in a 60°C incubator for 30 days, and after being removed, its thickness was measured and recorded as h1. The thickness expansion rate of a lithium-ion battery stored for 30 days = [(h1-h0) / h0] × 100%

[0104] 4. Measurement of energy density Under a temperature of 25°C, a lithium-ion battery was charged to 4.3V with a constant current of 1A, and then charged at a constant voltage until the current was less than 0.5A. The battery was then discharged to 2.5V with a constant current of 1A, then to 2.5V with a constant current of 0.5A, and then to 2.5V with a constant current of 0.1A. The discharge capacity C (Ah) of the battery was recorded, and the voltage value U (V) of the battery when it was discharged to half its capacity was recorded. At this time, the weight of the battery was measured and its mass m (kg) was recorded. Battery energy W = C × U, battery energy density = W / m

[0105] The performance measurement results for each example and comparative example are shown in Tables 1-4 below. [Table 1]

[0106] [Table 2]

[0107] [Table 3]

[0108] [Table 4]

[0109] Comparative Examples 1-3 and Examples 1-20 all used low CB values, but Examples 1-20 showed better cycle performance than Comparative Examples 1-3. Also, because Comparative Example 2 had a relatively low content of thiourea compounds, the cycle performance improved compared to Comparative Example 1, which contained no thiourea compounds, but the improvement was only moderate. In Comparative Example 3, the content of thiourea compounds was relatively high, and the cycle performance improved relatively significantly, but the battery expansion rate after high-temperature storage was too high. As can be seen from Examples 1-4 and Examples 5-7, when the a / b value is within 0.8-2, especially 1-1.8, the cycle performance of the battery is further improved. When a is within 0.9 ≤ a < 1.05, especially 0.98-1.04, the cycle performance of the battery is further improved. Therefore, when b is within 0.5-2, especially 0.5-1.0, the cycle performance of lithium-ion batteries is further improved.

[0110] As can be seen from Examples 10-13, low CB values ​​and good cycling performance were achieved even when other thiourea compounds were used.

[0111] As can be seen from Examples 14-17, the battery's cycle performance is further improved when certain other additives are added to the electrolyte.

[0112] As can be seen from Examples 18-20, reducing the thickness of the negative electrode film layer to 140 μm or less further improves the battery's cycle performance.

[0113] This application is not limited to the embodiments described above. The embodiments described above are merely illustrative, and embodiments that have substantially the same configuration as the technical concept and can achieve similar effects within the scope of the technical idea of ​​this application also fall within the scope of this application. Furthermore, various modifications to the embodiments that can be conceived by a person skilled in the art, as long as they do not depart from the spirit of this application, and other methods formed by combining some of the components of the embodiments also fall within the scope of this application. [Explanation of Symbols]

[0114] 1 Battery pack 2 Upper box 3 Lower box 4 Battery Unit 5. Lithium-ion battery 51 Housing 52 Electrode Assembly 53 Cover Plate

Claims

1. Lithium-ion battery, It includes a positive electrode plate, a negative electrode plate, a separator, and an electrolyte. The lithium-ion battery has a ratio of negative electrode capacity to positive electrode capacity of a, and the electrolyte contains a thiourea-based compound in an amount of b% by weight relative to the total weight of the electrolyte, and the lithium-ion battery is, 0.9 ≤ a < 1.05, and 25×(1.05-a)≦b≦100×(1.05-a) The relationship satisfies, The thiourea compound has the following structural formula: 【Chemistry 1】 R and X are independently selected from H, C1-C10 alkyl groups, C1-C10 alkenyl groups, and phenyl groups, or R and X together represent a C1-C10 alkylene group or a C1-C10 alkenylene group, and the C1-C10 alkylene group or C1-C10 alkenylene group is optionally substituted with an oxygen group. The electrolyte further contains at least one additive selected from metal nitrates and fluoroethylene carbonate, wherein the metal nitrate is one or more of lithium nitrate, magnesium nitrate, and copper(II) nitrate. The content of the additive is 0.5% to 2% by weight relative to the total mass of the electrolyte. A lithium-ion battery characterized by the following features.

2. The value of a / b is between 0.8 and 2. The lithium-ion battery according to feature 1.

3. b is between 0.2 and 5. The lithium-ion battery according to feature 1.

4. In the negative electrode plate of the lithium-ion battery, the thickness of the negative electrode film layer is 90 μm to 140 μm. The lithium-ion battery according to feature 1.

5. Includes the lithium-ion battery described in claim 1 A battery unit characterized by the following features.

6. Includes the battery unit described in claim 5 A battery pack characterized by the following features.

7. The lithium-ion battery includes at least one of the following: the lithium-ion battery described in any one of claims 1 to 4, the battery unit described in claim 5, or the battery pack described in claim 6. An electrical device characterized by the following features.

Images