Negative pole piece and preparation method thereof, lithium ion battery and power utilization device
By using negative electrode active materials containing heteroatomic functional groups in the negative electrode sheet of lithium-ion batteries and enhancing their grafting through plasma treatment, the lithium-ion battery problem is solved, and the cycle performance and life of the battery are significantly improved.
Patent Information
- Application Number
- CN202311515400.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-11-14
- Publication Date
- 2025-05-16
AI Technical Summary
The negative electrode lithium-ion battery has caused a decrease in cycle life, and how to effectively inhibit lithium-ion has become an urgent problem to be solved.
The negative electrode sheet is used, and the negative electrode film layer contains the negative electrode active material. The negative electrode active material contains heteroatomic functional groups. The mass content of heteroatomic functional groups is controlled between 0.5% and 5%. The grafting of heteroatomic functional groups is enhanced by plasma treatment, promoting the formation of solid electrolyte interface film, and improving the content of inorganic lithium salts and ionic conductivity.
Effectively suppress the lithium-ion phenomenon of negative electrode sheets in lithium-ion batteries and improve the circulation performance and life of the battery.
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Figure CN120015767A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the field of battery technology, and more specifically, to a negative electrode plate and a preparation method thereof, a lithium-ion battery and an electrical device. Background Art
[0002] In recent years, lithium-ion batteries have been widely used in energy storage power systems such as hydropower, thermal power, wind power and solar power stations, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, aerospace and other fields, and have thus achieved great development.
[0003] Due to the influence of factors such as process and use environment, lithium may be deposited on the negative electrode, resulting in a decrease in the cycle life of lithium-ion batteries. Therefore, how to improve lithium deposition in lithium-ion batteries has become an urgent problem to be solved. Summary of the invention
[0004] The present application is made in view of the above-mentioned technical problems, and its purpose is to provide a negative electrode plate, which can be used in lithium-ion batteries to effectively inhibit lithium plating and help improve the cycle performance of lithium-ion batteries.
[0005] In order to achieve the above-mentioned objectives, the present application provides a negative electrode plate and a preparation method thereof, a lithium-ion battery and an electrical device.
[0006] In a first aspect, a negative electrode plate is provided, comprising a negative electrode current collector; a negative electrode film layer, arranged on at least one side of the negative electrode current collector, the negative electrode film layer comprises a negative electrode active material, the negative electrode active material comprises a heteroatom functional group, and the mass content of the heteroatom functional group in the negative electrode active material ranges from 0.5% to 5%.
[0007] In the embodiment of the present application, the negative electrode film layer of the negative electrode plate includes a negative electrode active material, and the negative electrode active material includes a heteroatom functional group, and the mass content of the heteroatom functional group in the negative electrode active material ranges from 0.5% to 5%, so that when the negative electrode plate is used in a lithium-ion battery, the heteroatom functional group in the negative electrode active material can participate in the formation of a solid electrolyte interface (SEI) film, specifically, can form an inorganic lithium salt in the SEI film. At the same time, the mass content of the heteroatom functional group in the negative electrode active material is controlled to range from 0.5% to 5%, so as to increase the content of the inorganic lithium salt in the SEI film, thereby increasing the ionic conductivity of the SEI film, so as to reduce the difference in ionic conductivity at the interface between the SEI film and the electrolyte, improve the lithium precipitation problem of the negative electrode plate, and help improve the cycle performance of the lithium-ion battery.
[0008] In a possible implementation, the mass content of the heteroatom functional group in the negative electrode active material is in the range of 4% to 5%.
[0009] Further controlling the mass content of heteroatom functional groups in the negative electrode active material within the above range is beneficial to increasing the content of inorganic lithium salts in the SEI film, thereby improving the lithium plating problem of the negative electrode sheet and helping to improve the cycle performance of lithium-ion batteries.
[0010] In a possible implementation, the heteroatom functional group includes at least one of an oxygen-containing functional group, a nitrogen-containing functional group, and a fluorine-containing functional group.
[0011] In a possible implementation, the contact angle θ of the surface of the negative electrode plate is in the range of 10° to 60°. Optionally, the contact angle θ is in the range of 10° to 20°.
[0012] The contact angle θ of the surface of the negative electrode plate is controlled within the above range, so that when the negative electrode plate is used in a lithium-ion battery, it is beneficial to improve the wetting effect of the electrolyte on the surface of the negative electrode plate, thereby facilitating the negative electrode active material on the surface of the negative electrode plate to fully participate in the formation of the SEI film to form a dense SEI film.
[0013] In a possible implementation, the negative electrode active material includes at least one of natural graphite, artificial graphite, expanded graphite, hard carbon, soft carbon, carbon microspheres, silicon, silicon oxide, silicon carbon, and lithium titanate.
[0014] In a second aspect, a negative electrode plate is provided, comprising: a negative electrode current collector and a negative electrode film layer arranged on at least one side of the negative electrode current collector, the negative electrode film layer comprising a negative electrode active material, and the surface of the negative electrode active material comprising a heteroatom functional group; a SEI film, the SEI film is formed on the negative electrode film layer, the SEI film comprises an inorganic lithium salt, and the mass content of the inorganic lithium salt in the SEI film ranges from 30% to 50%.
[0015] In a possible implementation, the inorganic lithium salt includes at least one of lithium oxide, lithium fluoride, and lithium carbonate.
[0016] In a third aspect, a method for preparing a negative electrode sheet is provided, comprising: coating a negative electrode slurry on at least one side of a negative electrode current collector to obtain a negative electrode sheet to be treated; and subjecting the negative electrode sheet to be treated to plasma treatment to obtain the negative electrode sheet.
[0017] In an embodiment of the present application, the negative electrode plate to be treated is subjected to plasma treatment, so that the negative electrode active material is grafted with heteroatom functional groups, and the mass content of the heteroatom functional groups in the negative electrode active material is increased, so that when the negative electrode plate is used in a lithium-ion battery, it is beneficial to increase the content of inorganic lithium salts in the SEI film, thereby increasing the ionic conductivity of the SEI film, so as to reduce the difference in ionic conductivity at the interface between the SEI film and the electrolyte, improve the lithium plating problem of the negative electrode plate, and help improve the cycle performance of the lithium-ion battery.
[0018] In a possible implementation, the step of subjecting the negative electrode sheet to be treated with plasma to obtain the negative electrode sheet comprises: placing the negative electrode sheet to be treated into a plasma device; introducing a gas into the plasma device; and subjecting the negative electrode sheet to be treated with plasma using the plasma device to obtain the negative electrode sheet.
[0019] In a possible implementation, the gas includes at least one of carbon tetrafluoride, oxygen, nitrogen, and compressed air. Optionally, the gas includes oxygen.
[0020] In a possible implementation, the processing time t of the plasma treatment of the negative electrode plate to be processed by the plasma equipment is in the range of 1 min to 5 min. Optionally, the processing time t is in the range of 2.5 min to 3.5 min.
[0021] Controlling the treatment time of the plasma treatment of the negative electrode sheet to be treated within the above range is beneficial to the surface grafting of an appropriate amount of heteroatom functional groups on the negative electrode active material, thereby helping to improve the ionic conductivity of the SEI film, thereby improving the lithium plating problem of the negative electrode sheet and helping to improve the cycle performance of the lithium-ion battery.
[0022] In a possible implementation, the working power P of the plasma equipment for performing plasma treatment on the negative electrode plate to be treated is in the range of 100W to 1000W. Optionally, the value range of P is 450W to 550W.
[0023] Setting the working power P of the plasma equipment within the above range is beneficial to the grafting of heteroatom functional groups on the negative electrode active material, and ensures the normal and stable operation of the plasma equipment.
[0024] In a fourth aspect, a lithium-ion battery is provided, comprising at least one of the negative electrode sheet in any possible implementation of the first aspect, the negative electrode sheet in any possible implementation of the second aspect, and the negative electrode sheet prepared by the preparation method in any possible implementation of the third aspect.
[0025] In a fifth aspect, an electrical device is provided, wherein the electrical device comprises the lithium-ion battery in the fourth aspect. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments of the present application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on the drawings without paying creative work.
[0027] Figure 1 A schematic diagram of a negative electrode sheet disclosed in one embodiment of the present application;
[0028] Figure 2 A schematic diagram of a negative electrode sheet disclosed in one embodiment of the present application;
[0029] Figure 3 A schematic flow chart of a method for preparing a negative electrode sheet of the present application;
[0030] Figure 4 A schematic diagram of a battery cell disclosed in an embodiment of the present application;
[0031] Figure 5 A schematic diagram of the exploded structure of a battery cell disclosed in one embodiment of the present application;
[0032] Figure 6 A schematic diagram of the exploded structure of a battery disclosed in one embodiment of the present application;
[0033] Figure 7 A schematic diagram of an electrical device disclosed in an embodiment of the present application. DETAILED DESCRIPTION
[0034] Below, the embodiments of the negative electrode plate and its preparation method, lithium-ion battery and electric device of the present application are specifically disclosed in detail with appropriate reference to the drawings. However, there are cases where unnecessary detailed descriptions are omitted. For example, there are cases where detailed descriptions of well-known matters and repeated descriptions of actually the same structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the drawings and the following descriptions are provided for those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.
[0035] In the description of the present application, it should be noted that, unless otherwise specified, "multiple" means more than two; the directions or positional relationships indicated by the terms "upper", "lower", "left", "right", "inner", "outer", etc. are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific direction, be constructed and operated in a specific direction, and therefore cannot be understood as limiting the present application. In addition, the terms "first", "second", "third", etc. are only used for descriptive purposes and cannot be understood as indicating or implying relative importance.
[0036] "Scope" disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range. The scope limited in this way can be including end values or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4 and 5 are listed, the following scope can be all expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
[0037] If there is no special explanation, all steps of the present application can be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
[0038] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.
[0039] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.
[0040] Next, embodiments of the present application are introduced.
[0041] In recent years, secondary batteries have been widely used in power tools, electronic products, electric vehicles, aerospace and other fields due to their high energy density and long service life, and have achieved great development. Usually, a secondary battery includes a positive electrode sheet, a negative electrode sheet, an electrolyte and a separator. During the charge and discharge process of the battery, active ions are embedded and released back and forth between the positive electrode sheet and the negative electrode sheet. Among them, the electrolyte plays a role in conducting active ions between the positive electrode sheet and the negative electrode sheet. The separator is arranged between the positive electrode sheet and the negative electrode sheet, which allows active ions to pass through while preventing the positive and negative electrodes from short-circuiting, so that the electrochemical reaction of the secondary battery proceeds normally.
[0042] Take lithium-ion batteries as an example. Lithium-ion batteries are a typical secondary battery. Because they rely on the chemical reaction of lithium ions intercalating and disintercalating between the positive and negative electrodes for charging and discharging, lithium-ion batteries are also called rocking-chair batteries. During the charging process of lithium-ion batteries, lithium ions are released from the positive electrode active material, move to the negative electrode through the conduction of the electrolyte and embed into the negative electrode active material; and during the discharge process, lithium ions are released from the negative electrode active material, move to the positive electrode through the conduction of the electrolyte and embed into the positive electrode active material.
[0043] It should be understood that the "lithium insertion" and "embedding" processes described in this application refer to the process in which lithium ions are embedded in the positive electrode active material or the negative electrode active material due to an electrochemical reaction, and the "extraction", "delithium" and "extraction" processes described in this application refer to the process in which lithium ions are extracted from the positive electrode active material or the negative electrode active material due to an electrochemical reaction.
[0044] During the cycle of lithium-ion batteries, the process of lithium ion embedding into the negative electrode active material is hindered by factors such as battery preparation technology and battery aging, and lithium deposition will occur on the surface of the negative electrode. For example, the low ion conductivity of the SEI film and the large difference in ion conductivity between it and the electrolyte interface will lead to lithium deposition problems, causing the reversible capacity of the battery to decay and the cycle life to decrease.
[0045] In view of this, the embodiment of the present application provides a negative electrode plate and a preparation method thereof, a lithium ion battery and an electric device. The negative electrode plate includes a negative electrode current collector and a negative electrode film layer disposed on at least one side of the negative electrode current collector, the negative electrode film layer includes a negative electrode active material, the negative electrode active material includes a heteroatom functional group, and the mass content of the heteroatom functional group in the negative electrode active material ranges from 0.5% to 5%.
[0046] When the negative electrode sheet is used in a lithium-ion battery, the heteroatom functional groups in the negative electrode active material can participate in the formation of the SEI film, specifically, can form an inorganic lithium salt in the SEI film. At the same time, the mass content of the heteroatom functional groups in the negative electrode active material is controlled to be in the range of 0.5% to 5% to increase the content of the inorganic lithium salt in the SEI film, thereby increasing the ionic conductivity of the SEI film, reducing the difference in ionic conductivity at the interface between the SEI film and the electrolyte, improving the lithium precipitation problem of the negative electrode sheet, and helping to improve the cycle performance of the lithium-ion battery.
[0047] Generally, a lithium-ion battery includes a positive electrode sheet, a negative electrode sheet, an electrolyte, and a separator. Next, the lithium-ion battery provided in the present application and various parts of the lithium-ion battery are introduced.
[0048] [Negative electrode]
[0049] The present application first provides a negative electrode sheet, such as Figure 1 As shown, the negative electrode plate 1 includes a negative electrode current collector 11 and a negative electrode film layer 12 arranged on at least one side of the negative electrode current collector 11, the negative electrode film layer 12 includes a negative electrode active material, the negative electrode active material includes a heteroatom functional group, and the mass content of the heteroatom functional group in the negative electrode active material ranges from 0.5% to 5%.
[0050] As an example, the negative electrode current collector 11 has two surfaces opposite to each other in its thickness direction, and the negative electrode film layer 12 is disposed on any one or both of the two opposite surfaces of the negative electrode current collector 11. Figure 1 As shown, negative electrode film layers 12 are provided on both surfaces of the negative electrode current collector 11 .
[0051] Figure 2 Schematic diagram of a negative electrode sheet of an embodiment of the present application. In some other embodiments, such as Figure 2 As shown, a negative electrode film layer 12 is provided on one of two surfaces of the negative electrode current collector 11 that are opposite to each other in the thickness direction.
[0052] The negative electrode current collector may be a metal foil or a composite current collector. For example, as the metal foil, a copper foil may be used. The composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
[0053] The negative electrode active material may be a negative electrode active material for a battery known in the art. As an example, the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, expanded graphite, soft carbon, hard carbon, carbon microspheres, silicon-based materials, tin-based materials, lithium titanate, etc. The silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon-carbon composites, silicon-nitrogen composites, and silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin oxide compounds, and tin alloys. However, the present application is not limited to these materials, and other traditional materials that can be used as negative electrode active materials for batteries may also be used. These negative electrode active materials may be used alone or in combination of two or more.
[0054] Heteroatom functional groups are usually formed by covalent bonding of one or more heteroatoms, such as oxygen-containing functional groups (hydroxyl, carboxyl, carbonyl, etc.) containing oxygen atoms, nitrogen-containing functional groups (amino, etc.) containing nitrogen atoms, fluorine-containing functional groups containing fluorine atoms, etc. Heteroatoms include any atom that is not a carbon atom or a hydrogen atom, such as oxygen atoms, nitrogen atoms, fluorine atoms, sulfur atoms, phosphorus atoms, chlorine atoms, etc.
[0055] The mass content of the heteroatom functional group in the negative electrode active material ranges from 0.5% to 5%. Specifically, the mass content of the heteroatom functional group in the negative electrode active material can be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, or a value within the range obtained by combining any two of the above values.
[0056] In the embodiment of the present application, the negative electrode film layer of the negative electrode plate includes a negative electrode active material, and the negative electrode active material includes a heteroatom functional group, and the mass content of the heteroatom functional group in the negative electrode active material ranges from 0.5% to 5%, so that when the negative electrode plate is used in a lithium-ion battery, the heteroatom functional group in the negative electrode active material can participate in the formation of the SEI film, specifically, can form an inorganic lithium salt in the SEI film. At the same time, the mass content of the heteroatom functional group in the negative electrode active material is controlled to range from 0.5% to 5% to increase the content of the inorganic lithium salt in the SEI film, thereby increasing the ionic conductivity of the SEI film, reducing the difference in ionic conductivity at the interface between the SEI film and the electrolyte, improving the lithium precipitation problem of the negative electrode plate, and helping to improve the cycle performance of the lithium-ion battery.
[0057] Optionally, in some embodiments, the mass content of the heteroatom functional group in the negative electrode active material is in the range of 4% to 5%.
[0058] Further controlling the mass content of heteroatom functional groups in the negative electrode active material within the above range is beneficial to increasing the content of inorganic lithium salts in the SEI film, thereby improving the lithium plating problem of the negative electrode sheet and helping to improve the cycle performance of lithium-ion batteries.
[0059] In some embodiments, the heteroatom functional group includes at least one of an oxygen-containing functional group, a nitrogen-containing functional group, and a fluorine-containing functional group.
[0060] In some embodiments, the contact angle θ of the surface of the negative electrode plate ranges from 10° to 60°. Optionally, the contact angle θ ranges from 10° to 20°.
[0061] The contact angle refers to the angle between the solid-liquid interface, through the liquid interior, and the gas-liquid interface at the interface of solid, liquid, and gas. In the present application, the surface contact angle θ of the negative electrode sheet can be the angle between the surface of the negative electrode sheet and the interface of the electrolyte, through the electrolyte interior, and the interface between the air and the electrolyte.
[0062] Specifically, the contact angle θ of the surface of the negative electrode plate can be 10°, 20°, 30°, 40°, 50°, 60°, or a value thereof within the range obtained by combining any two of the above values.
[0063] The following is a contact angle test method: drop an electrolyte droplet on the surface of the negative electrode, observe the shape of the droplet through a camera or microscope, and measure the angle between the droplet and the solid surface. The contact angle value can be calculated based on the Young-Laplace equation, or it can be measured using a protractor.
[0064] It should be understood that in the embodiments of the present application, the test method for the contact angle θ of the surface of the negative electrode plate includes but is not limited to the above method, and the contact angle θ of the surface of the negative electrode plate of the present application can be tested using any known contact angle test method.
[0065] The contact angle θ of the surface of the negative electrode plate is controlled within the above range, so that when the negative electrode plate is used in a lithium-ion battery, it is beneficial to improve the wetting effect of the electrolyte on the surface of the negative electrode plate, thereby facilitating the negative electrode active material on the surface of the negative electrode plate to fully participate in the formation of the SEI film to form a dense SEI film.
[0066] In some embodiments, the negative electrode film layer may further include a binder, which may include at least one of 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).
[0067] In some embodiments, the negative electrode film layer may further include a conductive agent, which includes at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
[0068] In some embodiments, the negative electrode film layer may optionally include other additives, such as a thickener (eg, sodium carboxymethyl cellulose (CMC-Na)).
[0069] In some embodiments, the negative electrode sheet can be prepared in the following manner: the components for preparing the negative electrode sheet, such as the negative electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode collector, and after drying, cold pressing and other processes, the negative electrode sheet can be obtained.
[0070] [Positive electrode]
[0071] The positive electrode sheet 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.
[0072] As an example, the positive electrode current collector has two surfaces facing each other in its thickness direction, and the positive electrode active material layer is disposed on any one or both of the two facing surfaces of the positive electrode current collector.
[0073] In one embodiment, the positive electrode current collector may be a metal foil or a composite current collector. For example, aluminum foil may be used as the metal foil. The composite current collector may include a polymer material base and a metal layer formed on at least one surface of the polymer material base. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
[0074] In one embodiment, the positive electrode active material may adopt a positive electrode active material for a battery that is well known in the art. As an example, the positive electrode active material may include at least one of the following materials: a lithium-containing phosphate with an olivine structure, a lithium transition metal oxide, and their respective modified compounds. However, the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials for batteries may also be used. These positive electrode active materials may be used alone or in combination of two or more. Among them, examples of lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide (such as LiCoO2), lithium nickel oxide (such as LiNiO2), lithium manganese oxide (such as LiMnO2, LiMn2O4), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2 (also referred to as NCM333), LiNi 0.5 Co 0.2 Mn 0.3O2 (also referred to as NCM523), LiNi 0.5 Co 0.25 Mn 0.25 O2 (also referred to as NCM211), LiNi 0.6 Co 0.2 Mn 0.2 O2 (also referred to as NCM622), LiNi 0.8 Co 0.1 Mn 0.1 O2 (also referred to as NCM811), lithium nickel cobalt aluminum oxide (such as LiNi 0.85 Co 0.15 Al 0.05 O2) and its modified compounds, etc. Examples of lithium-containing phosphates with an olivine structure may include, but are not limited to, at least one of lithium iron phosphate (such as LiFePO4 (also referred to as LFP)), a composite material of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO4), a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
[0075] The battery will be accompanied by Li deintercalation and consumption during the charging and discharging process. The molar content of Li in the positive electrode active material is different when the battery is discharged to different states. In the list of positive electrode active materials in this application, the molar content of Li is the initial state of the material, that is, the state before feeding. The positive electrode active material is used in the battery system. After the charge and discharge cycle, the molar content of Li will change. In the list of positive electrode active materials in this application, the molar content of O is only an ideal state value. Lattice oxygen release will cause the molar content of O to change, and the actual molar content of O will fluctuate.
[0076] In one embodiment, the positive electrode active material layer further includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorine-containing acrylate resin.
[0077] In one embodiment, the positive electrode active material layer further includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
[0078] In one embodiment, the positive electrode sheet can be prepared in the following manner: the components for preparing the positive electrode sheet are respectively formed into positive electrode slurries. For example, the first positive electrode active material and / or the second positive electrode active material, the conductive agent, the binder and any other components are dispersed in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry. Then, the positive electrode slurry is coated on the positive electrode current collector, and after drying, rolling and other processes, the positive electrode sheet can be obtained.
[0079] [Electrolyte]
[0080] The electrolyte plays a role in conducting ions between the positive electrode and the negative electrode. The present application has no specific restrictions on the type of electrolyte, which can be selected according to needs. The electrolyte may include an electrolyte salt and a solvent.
[0081] In some embodiments, the electrolyte salt can be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalatoborate, lithium dioxalatoborate, lithium difluorodioxalatophosphate, and lithium tetrafluorooxalatophosphate.
[0082] In some embodiments, the solvent can be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1,4-butyrolactone, cyclopentane sulfone, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
[0083] In some embodiments, the electrolyte may further include additives, such as negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
[0084] [Isolator]
[0085] In some embodiments, the lithium-ion battery further includes a separator. The present application has no particular limitation on the type of separator, and any known porous structure separator with good chemical stability and mechanical stability can be selected.
[0086] In some embodiments, the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The isolation membrane can be a single-layer film or a multi-layer composite film, without particular limitation. When the isolation membrane is a multi-layer composite film, the materials of each layer can be the same or different, without particular limitation.
[0087] The above embodiments introduce negative electrode sheets that can effectively inhibit lithium deposition. Next, the negative electrode sheet obtained after the lithium-ion battery formed by assembling the above negative electrode sheet with the positive electrode sheet, electrolyte and separator is introduced.
[0088] The present application provides a negative electrode plate, which includes: a negative electrode current collector and a negative electrode film layer arranged on at least one side of the negative electrode current collector, the negative electrode film layer includes a negative electrode active material, and the surface of the negative electrode active material includes heteroatom functional groups; an SEI film, the SEI film is formed on the negative electrode film layer, the SEI film includes an inorganic lithium salt, and the mass content of the inorganic lithium salt in the SEI film is (to be supplemented).
[0089] Generally speaking, after the lithium-ion battery is formed, a layer of SEI film will be formed on the surface of the negative electrode film layer. The SEI film is a passivation layer covering the surface of the negative electrode film layer formed by the reaction between the electrode material and the electrolyte at the solid-liquid interface during the formation process of the lithium-ion battery. Therefore, the heteroatom functional groups included in the negative electrode active material in the negative electrode film layer in this embodiment can participate in the formation of the SEI film, so that after the lithium-ion battery is formed, a SEI film including an inorganic lithium salt is formed, and the mass content of the inorganic lithium salt in the SEI film is, which is beneficial to improve the ionic conductivity of the SEI film, so as to reduce the difference in ionic conductivity at the interface between the SEI film and the electrolyte, improve the lithium precipitation problem of the negative electrode plate, and help improve the cycle performance of the lithium-ion battery.
[0090] In one embodiment, the inorganic lithium salt includes at least one of lithium oxide, lithium fluoride, and lithium carbonate.
[0091] [Method for preparing negative electrode sheet]
[0092] The embodiment of the present application also provides a method for preparing a negative electrode plate. Figure 3 FIG. 1 is a schematic flow chart of a method for preparing a negative electrode sheet. Figure 3 As shown, the preparation method 300 includes the following steps.
[0093] Step 310, coating the negative electrode slurry on at least one side of the negative electrode current collector to obtain a negative electrode sheet to be processed;
[0094] Step 320, subjecting the negative electrode sheet to be processed to plasma treatment to obtain a negative electrode sheet.
[0095] Specifically, the preparation method 300 includes:
[0096] (a) A negative electrode slurry is prepared, wherein the negative electrode slurry includes a negative electrode active material.
[0097] (b) applying the negative electrode slurry to at least one side of the negative electrode current collector.
[0098] (c) drying the negative electrode slurry to form a negative electrode coating layer on the negative electrode current collector.
[0099] (d) rolling the negative electrode current collector and the negative electrode coating layer to obtain a negative electrode sheet to be processed.
[0100] (e) subjecting the negative electrode sheet to be treated to plasma treatment to obtain the negative electrode sheet.
[0101] Thus, in the negative electrode sheet prepared by the above steps (a)-(e), the negative electrode active material in the negative electrode film layer is grafted with heteroatom functional groups, and the mass content of the heteroatom functional groups in the negative electrode active material ranges from 0.5% to 5%.
[0102] In one embodiment, subjecting the negative electrode piece to be treated to plasma treatment may include: placing the negative electrode piece to be treated into a plasma device; introducing gas into the plasma device; and subjecting the negative electrode piece to be treated to plasma treatment using the plasma device.
[0103] In one embodiment, the gas introduced into the plasma device includes at least one of carbon tetrafluoride, oxygen, nitrogen, and compressed air. Optionally, the gas includes oxygen.
[0104] In one embodiment, the treatment time t of the negative electrode plate to be treated by plasma treatment using a plasma device ranges from 1 min to 5 min. Optionally, the treatment time t ranges from 2.5 min to 3.5 min.
[0105] Specifically, the treatment time t of the negative electrode plate to be treated by plasma treatment using a plasma device can be 1 min, 1.5 min, 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min, 5 min, or its value is within the range obtained by combining any two of the above values.
[0106] Controlling the treatment time of the plasma treatment of the negative electrode sheet to be treated within the above range is beneficial to the surface grafting of an appropriate amount of heteroatom functional groups on the negative electrode active material, thereby helping to improve the ionic conductivity of the SEI film, thereby improving the lithium plating problem of the negative electrode sheet and helping to improve the cycle performance of the lithium-ion battery.
[0107] In one embodiment, the working power P of the plasma equipment for performing plasma treatment on the negative electrode plate to be treated is in the range of 100W to 1000W. Optionally, the working power P is in the range of 450W to 550W.
[0108] Specifically, the operating power P of the plasma equipment for plasma treatment of the negative electrode plate to be treated can be 100W, 200W, 300W, 400W, 500W, 600W, 700W, 800W, 900, 1000W, or its value is within the range obtained by combining any two of the above values.
[0109] Setting the working power P of the plasma equipment within the above range is beneficial to the grafting of heteroatom functional groups on the negative electrode active material, and ensures the normal and stable operation of the plasma equipment.
[0110] The present application also provides a lithium-ion battery, which includes the negative electrode plate in any of the aforementioned embodiments, and / or the negative electrode plate prepared by the preparation method in any of the aforementioned embodiments.
[0111] In one embodiment, the negative electrode sheet, the positive electrode sheet and the separator may be formed into an electrode assembly by a winding process or a lamination process.
[0112] In one embodiment, the battery cell may include an outer packaging, which may be used to encapsulate the electrode assembly and the electrolyte.
[0113] In one embodiment, the outer packaging of the battery cell may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc. The outer packaging of the battery cell may also be a soft package, such as a bag-type soft package. The material of the soft package may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
[0114] The present application has no particular limitation on the shape of the battery cell, which may be cylindrical, square or any other shape. Figure 4 The battery cell 40 is a square structure as an example.
[0115] It should be understood that the battery cell 40 may include the lithium-ion battery in the aforementioned embodiment.
[0116] In some embodiments, reference Figure 5 , the outer packaging may include a shell 41 and a cover plate 43. Among them, the shell 41 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity. The shell 41 has an opening connected to the receiving cavity, and the cover plate 43 can be covered on the opening to close the receiving cavity. The positive electrode sheet, the negative electrode sheet and the isolation membrane can form an electrode assembly 42 through a winding process or a lamination process. The electrode assembly 42 is encapsulated in the receiving cavity. The electrolyte is infiltrated in the electrode assembly 22. The number of electrode assemblies 42 contained in the battery cell 40 can be one or more, and those skilled in the art can choose according to specific actual needs.
[0117] In some embodiments, the battery 50 may include a plurality of battery cells 40. For example, Figure 6 , which is a schematic diagram of the structure of a battery 50 according to an embodiment of the present application, wherein the battery 50 may include a plurality of battery cells 40. The battery 50 may also include a box 51, wherein the box 51 is a hollow structure, and the plurality of battery cells 40 are accommodated in the box 51. For example, the plurality of battery cells 40 are connected in parallel, in series, or in a mixed combination and then placed in the box 51.
[0118] Optionally, the battery 50 may also include other structures, which are not described one by one here. For example, the battery 50 may also include a busbar component, which is used to realize electrical connection between multiple battery cells 40, such as parallel connection, series connection or mixed connection. Specifically, the busbar component can realize electrical connection between battery cells 40 by connecting the electrode terminals of the battery cells 40. Further, the busbar component can be fixed to the electrode terminals of the battery cells 40 by welding. The electrical energy of multiple battery cells 40 can be further led out through the box 51 through a conductive mechanism. Optionally, the conductive mechanism may also belong to the busbar component.
[0119] According to different power requirements, the number of battery cells 40 can be set to any value. Multiple battery cells 40 can be connected in series, parallel or hybrid to achieve a larger capacity or power. Since the number of battery cells 40 included in each battery 50 may be large, for ease of installation, the battery cells 40 can be grouped, and each group of battery cells 40 constitutes a battery module. The number of battery cells 40 included in the battery module is not limited and can be set according to demand. The battery can include multiple battery modules, which can be connected in series, parallel or hybrid.
[0120] In addition, the present application also provides an electric device, which includes at least one of the battery cells, battery modules or batteries provided in the present application. The battery cells, battery modules or batteries can be used as the power source of the electric device, and can also be used as the energy storage unit of the electric device. The electric device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited thereto.
[0121] As the electrical device, a battery cell, a battery module or a battery can be selected according to its usage requirements.
[0122] Figure 7The power consumption device is taken as an example. The power consumption device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle. In order to meet the high power and high energy density requirements of the power consumption device for battery cells, batteries or battery modules can be used.
[0123] Another example of a device may be a mobile phone, a tablet computer, a notebook computer, etc. Such a device is usually required to be light and thin, and a battery cell may be used as a power source.
[0124] Hereinafter, the embodiments of the present application will be described. The embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If no specific techniques or conditions are indicated in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. If the manufacturer is not indicated in the reagents or instruments used, they are all conventional products that can be obtained commercially.
[0125] 1. Preparation of negative electrode sheet
[0126] Negative electrode sheet 1: The active material artificial graphite, the conductive agent carbon black, the binder styrene-butadiene rubber (SBR), and the thickener sodium hydroxymethyl cellulose (CMC) are dissolved in the solvent deionized water at a weight ratio of 97.2:0.8:0.8:1.2, and the mixture is evenly mixed to prepare a negative electrode slurry; the negative electrode slurry is evenly coated on the negative electrode current collector copper foil, and the negative electrode sheet to be processed is obtained after drying, cold pressing, and slitting.
[0127] The negative electrode plate to be treated is placed in a plasma device, oxygen is introduced into the device at an air flow rate of 100 ml / min, and then the device is started to perform plasma treatment on the negative electrode plate. The device power is 500 W and the treatment time is 3 minutes to obtain a negative electrode plate 1.
[0128] Negative electrode sheet 2: The preparation of negative electrode sheet 2 is similar to that of negative electrode sheet 1, except that during the preparation of negative electrode sheet 2, the gas passed into the plasma device is carbon tetrafluoride.
[0129] Negative electrode sheet 3: The preparation of negative electrode sheet 3 is similar to that of negative electrode sheet 1, except that during the preparation of negative electrode sheet 3, the gas passing through the plasma equipment is nitrogen.
[0130] Negative electrode sheet 4: The preparation of the negative electrode sheet 4 is similar to that of the negative electrode sheet 1, except that during the preparation of the negative electrode sheet 4, the gas passing through the plasma device is compressed air.
[0131] Negative electrode sheet 5: The preparation of negative electrode sheet 5 is similar to that of negative electrode sheet 1, except that, during the preparation of negative electrode sheet 5, the plasma treatment time of the negative electrode sheet by plasma equipment is 1 minute.
[0132] Negative electrode sheet 6: The preparation of negative electrode sheet 6 is similar to that of negative electrode sheet 1, except that, during the preparation of negative electrode sheet 6, the plasma treatment time of the negative electrode sheet by plasma equipment is 2.5 minutes.
[0133] Negative electrode sheet 7: The preparation of negative electrode sheet 7 is similar to that of negative electrode sheet 1, except that, during the preparation of negative electrode sheet 7, the plasma treatment time of the negative electrode sheet by plasma equipment is 3.5 minutes.
[0134] Negative electrode sheet 8: The preparation of negative electrode sheet 8 is similar to that of negative electrode sheet 1, except that, during the preparation of negative electrode sheet 8, the plasma treatment time of the negative electrode sheet by plasma equipment is 5 minutes.
[0135] Negative electrode plate 9: The preparation of negative electrode plate 9 is similar to that of negative electrode plate 1, except that during the preparation of negative electrode plate 9, the working power of the plasma equipment for plasma treatment of the negative electrode plate is 100W.
[0136] Negative electrode sheet 10: The preparation of negative electrode sheet 10 is similar to that of negative electrode sheet 1, except that during the preparation of negative electrode sheet 10, the working power of the plasma equipment for plasma treatment of the negative electrode sheet is 450W.
[0137] Negative electrode sheet 11: The preparation of negative electrode sheet 11 is similar to that of negative electrode sheet 1, except that during the preparation of negative electrode sheet 11, the working power of the plasma equipment for plasma treatment of the negative electrode sheet is 550W.
[0138] Negative electrode plate 12: The preparation of the negative electrode plate 12 is similar to that of the negative electrode plate 1, except that during the preparation of the negative electrode plate 12, the working power of the plasma equipment for plasma treatment of the negative electrode plate is 1000W.
[0139] Negative electrode sheet 13: The preparation of negative electrode sheet 13 is similar to that of negative electrode sheet 1, except that negative electrode sheet 13 is not subjected to plasma treatment.
[0140] 2. Preparation of lithium-ion batteries
[0141] [Example 1]
[0142] (1) Preparation of positive electrode sheet
[0143] The positive electrode active material is lithium nickel cobalt manganese oxide (LiNi 0.5 Co 0.2 Mn 0.3O2), conductive carbon black, binder polyvinylidene fluoride, and solvent N-methylpyrrolidone are mixed and stirred in a weight ratio of 91:3:6:40 to obtain a positive electrode slurry, which is coated on a positive electrode current collector aluminum foil and vacuum dried to obtain a positive electrode sheet.
[0144] (2) Negative electrode
[0145] The negative electrode sheet adopts the negative electrode sheet 1 prepared as above.
[0146] (3) Preparation of isolation membrane
[0147] Polypropylene film is used as the isolation film.
[0148] (4) Preparation of electrolyte
[0149] In an argon atmosphere glove box (H2O<0.1ppm, O2<0.1ppm), the organic solvents ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed evenly in a volume ratio of 3:7, 1 mol / L lithium hexafluorophosphate (LiPF6) electrolyte salt was added and dispersed evenly, and then 2% of fluoroethylene carbonate was dissolved in the above organic solvent and stirred evenly to obtain an electrolyte.
[0150] (5) Assembly of lithium-ion batteries
[0151] The positive electrode sheet, the isolation film, and the negative electrode sheet 1 are stacked in order, so that the isolation film is placed between the positive electrode sheet and the negative electrode sheet 1 to play an isolating role, and then wound to obtain an electrode assembly; the electrode assembly is placed in a battery casing, and after drying, the electrolyte is injected, and then the lithium-ion secondary battery 1 is obtained through processes such as formation and standing, which is Example 1.
[0152] [Examples 2-12, Comparative Example 1]
[0153] The preparation methods of the lithium-ion batteries of Examples 2-12 and Comparative Example 1 are similar to those of the lithium-ion battery of Example 1, except that different negative electrode sheets are used (among which, Examples 1-12 use negative electrode sheets 1-12, respectively, and Comparative Example 1 uses negative electrode sheet 13), as shown in Table 1 for details.
[0154] The lithium-ion battery obtained after packaging is formed according to the following process, and the specific formation process is:
[0155] After standing for 1 minute, the battery was charged at a constant current of 8mA to 4.2V. Then, it was charged at a constant voltage of 4.2V with a cut-off current of 2mA. After standing for 10 minutes, it was discharged at a constant current of 8mA with a cut-off voltage of 2.5V. It was then left to stand for 50 hours.
[0156] Table 1: Product parameters and performance data of Examples 1-12 and Comparative Example 1
[0157]
[0158] In Table 1, "gas type" indicates the type of gas introduced into the plasma equipment when the negative electrode sheet to be treated is treated with the plasma equipment; "t" indicates the treatment time of the negative electrode sheet to be treated with the plasma equipment; "P" indicates the working power of the plasma equipment for plasma treatment of the negative electrode sheet to be treated; "θ" indicates the contact angle of the surface of the negative electrode sheet; "c" indicates the mass content of the inorganic lithium salt in the SEI film formed after the lithium-ion battery is formed; "inorganic lithium salt" includes lithium oxide, lithium fluoride, and lithium carbonate; "capacity retention rate" indicates the capacity retention rate of the lithium-ion battery after 100 cycles after formation.
[0159] It should be understood that the SEI film after formation also includes components such as organic matter that are not reflected in Table 1.
[0160] In the embodiment of the present application, the lithium-ion battery after cycling can be disassembled to observe whether there is lithium deposition on the surface of the negative electrode plate.
[0161] By comparing the results of Examples 1-12 in Table 1 with Comparative Example 1, it can be seen that the negative electrode plate obtained by plasma treatment has a higher proportion of heteroatom functional groups than the negative electrode plate obtained by conventional preparation. The negative electrode plate treated by plasma is applied to lithium-ion batteries. During the cycle of the lithium-ion battery, the lithium plating problem of the negative electrode plate is solved, the capacity retention rate of the lithium-ion battery is improved, and the cycle performance is effectively improved.
[0162] By comparing the results of Examples 1-4, it can be seen that when different types of gases are introduced into the plasma equipment, the performance of the obtained negative electrode plate is different. When oxygen is introduced into the plasma equipment, the contact angle of the obtained negative electrode plate is smaller. The negative electrode plate is applied to lithium-ion batteries, and the surface of the negative electrode plate is more easily wetted by the electrolyte, and the effect of improving the cycle performance of the lithium-ion battery is more significant.
[0163] By comparing the results of Examples 1, 5-8, it can be seen that the treatment time of the negative electrode plate for plasma treatment is controlled within an appropriate range, and when it is applied to a lithium-ion battery, the effect of improving the cycle performance of the lithium-ion battery is more significant. In the embodiment of the present application, under the same other conditions, the negative electrode plate is subjected to plasma treatment for 2.5min to 3.5min. When the negative electrode plate after the treatment is applied to a lithium-ion battery, the cycle performance of the lithium-ion battery is better.
[0164] By comparing the results of Examples 1, 9-12, it can be seen that when the working power of the plasma device is controlled within an appropriate range, the negative electrode plate treated therefrom is applied to a lithium-ion battery, and the effect of improving the cycle performance of the lithium-ion battery is more significant. In the embodiment of the present application, under the same other conditions, the plasma device is set to a working power of 450W to 550W to treat the negative electrode plate. When the treated negative electrode plate is applied to a lithium-ion battery, the cycle performance of the lithium-ion battery is better.
[0165] The following is a brief introduction to the test methods of the physical and chemical parameters and performance parameters involved in the embodiments of the present application. It should be understood that the following test methods are only examples, and other test methods known in the art may also be used for testing.
[0166] 1. Test method for contact angle of negative electrode surface
[0167] Drop an electrolyte on the surface of the negative electrode, take a photo with a camera, and use a protractor to measure the interface between the electrolyte, negative electrode and air in the photo, and the angle from the negative electrode-electrolyte interface through the liquid to the air-electrolyte interface.
[0168] 2. Test method for mass content of heteroatom functional groups in negative electrode active materials
[0169] An X-ray photoelectron spectrometer (equipment model: LEEQ044H) is used to irradiate the surface of the negative electrode with X-rays of specific energy, and the excited photoelectrons are collected by a detector to calculate the mass content of heteroatom functional groups in the negative electrode active material.
[0170] 3. Test method for the mass content of inorganic lithium salt in SEI film
[0171] The lithium-ion battery after cycle was disassembled, the surface of the negative electrode was cleaned with DMC, and then an X-ray photoelectron spectroscopy test was performed. The content of organic components and inorganic lithium salt components in the SEI film on the surface of the negative electrode was calculated based on the energy spectrum intensity of lithium, oxygen, carbon, and fluorine elements.
[0172] 4. Test method for capacity retention rate of lithium-ion batteries
[0173] First, at 25°C, charge the lithium-ion battery to 4.4V at a constant current of 0.1C, and then discharge it to 2.5V at 0.1C. The resulting capacity is recorded as the initial capacity C0. Repeat the above charging and discharging steps, and record the discharge capacity Cn of the lithium-ion battery after the nth cycle at the same time. The battery capacity retention rate Pn after the nth cycle = Cn / C0×100%. For example, the discharge capacity of the lithium-ion battery after 100 cycles is C100, and the capacity retention rate P100 of the lithium-ion battery after 100 cycles is C100 / C0×100%.
[0174] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and the embodiments having the same structure as the technical idea and exerting the same effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the main purpose of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.
Claims
1. A negative electrode plate, characterized in that: include: Anode current collector; The negative electrode film layer is arranged on at least one side of the negative electrode current collector, the negative electrode film layer includes a negative electrode active material, the negative electrode active material includes a heteroatom functional group, and the mass content of the heteroatom functional group in the negative electrode active material ranges from 0.5% to 5%.
2. The negative electrode sheet according to claim 1, characterized in that: The mass content of the heteroatom functional group in the negative electrode active material is in the range of 4% to 5%.
3. The negative electrode sheet according to claim 1 or 2, characterized in that: The heteroatom functional group includes at least one of an oxygen-containing functional group, a nitrogen-containing functional group, and a fluorine-containing functional group.
4. The negative electrode sheet according to any one of claims 1 to 3, characterized in that: The contact angle θ of the surface of the negative electrode plate has a value range of 10° to 60°. Optionally, the value range of θ is 10° to 20°.
5. The negative electrode sheet according to any one of claims 1 to 4, characterized in that: The negative electrode active material includes at least one of natural graphite, artificial graphite, expanded graphite, hard carbon, soft carbon, carbon microspheres, silicon, silicon oxide, silicon carbon, and lithium titanate.
6. A negative electrode plate, characterized in that: include: A negative electrode current collector and a negative electrode film layer disposed on at least one side of the negative electrode current collector, wherein the negative electrode film layer comprises a negative electrode active material, and a surface of the negative electrode active material comprises a heteroatom functional group; A solid electrolyte interface membrane is formed on the negative electrode membrane layer, the solid electrolyte interface membrane comprises an inorganic lithium salt, and the mass content of the inorganic lithium salt in the solid electrolyte interface membrane ranges from 30% to 50%.
7. The negative electrode sheet according to claim 6, characterized in that: The inorganic lithium salt includes at least one of lithium oxide, lithium fluoride and lithium carbonate.
8. A method for preparing a negative electrode sheet, characterized in that: include: Applying negative electrode slurry on at least one side of the negative electrode current collector to obtain a negative electrode sheet to be processed; The negative electrode sheet to be treated is subjected to plasma treatment to obtain the negative electrode sheet.
9. The preparation method according to claim 8, characterized in that: The method of subjecting the negative electrode sheet to be treated to plasma treatment to obtain the negative electrode sheet comprises: Placing the negative electrode sheet to be treated into a plasma device; introducing gas into the plasma device; The negative electrode sheet to be processed is subjected to plasma treatment by using the plasma equipment to obtain the negative electrode sheet.
10. The preparation method according to claim 9, characterized in that: The gas includes at least one of carbon tetrafluoride, oxygen, nitrogen, and compressed air. Optionally, the gas includes oxygen.
11. The preparation method according to any one of claims 8 to 10, characterized in that: The treatment time t of the negative electrode plate to be treated by plasma treatment using a plasma device ranges from 1 min to 5 min. Optionally, the treatment time t ranges from 2.5 min to 3.5 min.
12. The preparation method according to any one of claims 8 to 11, characterized in that: The working power P of the plasma equipment for plasma treatment of the negative electrode plate to be treated is in the range of 100W to 1000W. Optionally, the value range of P is 450W to 550W.
13. A lithium ion battery, characterized in that: The lithium-ion battery comprises at least one of the negative electrode sheet according to any one of claims 1 to 5, the negative electrode sheet according to claim 6 or 7, and the negative electrode sheet prepared by the preparation method according to any one of claims 8 to 12.
14. An electrical device, characterized in that: The electric device comprises the lithium-ion battery as claimed in claim 13.