Modified current collector for secondary battery
Patent Information
- Application Number
- PCT/CN2023/101686
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2023-06-21
- Publication Date
- 2024-12-26
Smart Images

Figure CN2023101686_26122024_PF_FP_ABST
Abstract
Description
MODIFIED CURRENT COLLECTOR FOR SECONDARY BATTERYFIELD OF THE INVENTION
[0001] The present invention relates to the field of batteries. In particular, this invention relates to a modified current collector in a battery electrode in a secondary battery.BACKGROUND OF THE INVENTION
[0002] Among the various types of batteries on the market today, lithium-ion batteries (LIBs) in particular have become widely utilized for various applications over the past decades, especially in consumer electronics, because of their outstanding energy density, long cycle life and high discharging capability. Due to rapid market development of electric vehicles (EV) and grid energy storage, high-performance, low-cost LIBs are currently offering one of the most promising options for large-scale energy storage devices. However, many problems still exist in current lithium-ion battery technology, more specifically with respect to lithium-ion battery electrodes.
[0003] Generally, lithium-ion battery electrodes are manufactured by casting an organic-based slurry onto a current collector. The slurry contains electrode active material, conductive carbon, and binder in an organic solvent. The binder provides a good electrochemical stability, holds together the electrode active materials and adheres them to the current collector in the fabrication of electrodes. Polyvinylidene fluoride (PVDF) is currently one of the most commonly used binders in the commercial lithium-ion battery industry. However, PVDF is insoluble in water and can only dissolve in some specific organic solvents such as N-methyl-2-pyrrolidone (NMP) , which is flammable and toxic and hence requires specific handling.
[0004] An NMP recovery system must be in place during the drying process to recover NMP vapors. This generates significant costs in the manufacturing process since it requires a large capital investment. Given the drawbacks of organic-based slurries, the use of water-based slurries which utilize less expensive and more environmentally friendly solvents, such as aqueous solvents (most commonly water) are preferred in the present invention. These aqueous solvents are remarkably safer and easier to handle than NMP and do not require the implementation of a recovery system.
[0005] However, there are problems associated with the use of water-based slurries in the manufacture of lithium-ion batteries. In particular, the electrode active material may react with water to create undesirable effects on the current collector. The complications are particularly noticeable when nickel-containing cathode active materials, such as lithium nickel-manganese-cobalt oxides (NMC) , are used as they react strongly with water to form a basic solution. Consequently, when the nickel-containing water-based slurry is coated onto a current collector to form a cathode, the basicity of the slurry would likely corrode the current collector. This problem strongly discourages the use of nickel-containing cathode active materials in water-based manufacturing of batteries, despite the high specific capacities of such active materials.
[0006] It is worth noting that the above problems are not particular to lithium-ion batteries. Other types of batteries, such as sodium-ion batteries, may also encounter similar problems.
[0007] In view of the aforementioned problems, attempts have been made to mitigate the damage done to the current collector or to reduce the interfacial resistance between electrode layer and current collector in battery electrodes.
[0008] US Patent Application Publication No. 2013 / 0295458 A1 discloses a current collector comprising a metal foil and a layer comprising electrically conductive particles, a binding agent and an organic acid; wherein the layer is provided on one or both surfaces of the metal foil. Polysaccharides and derivatives thereof are preferably used as the binding agent owing to their excellent adherence with a metal foil and high ionic permeability. The organic acid serves as a cross-linking agent for the binding agent, allowing the electrically conductive particles to be more firmly attached onto the metal foil. With such a configuration, it is believed that the internal resistance and impedance of an electrochemical element comprising said current collector could be reduced. However, the shortcoming of this system lies in the need for an additional cross-linking agent in facilitating the adherence of the electrically conductive particles onto the metal foil; the simple use of a binding agent is insufficient in performing this function. The involvement of an organic acid as a cross-linking agent within the layer, upon contact with the metal foil in forming the current collector, would likely to give rise to corrosion of the underlying metal foil over time.
[0009] Chinese Patent Application Publication No. 108428855 A discloses a method of preparing a carbon-coated foil. A slurry is prepared by mixing together carbon nanotubes, a dispersant and an organic solvent, then graphene and a binder are added to the slurry to adjust the viscosity of the slurry, and finally the slurry is coated onto one or both sides of a piece of foil and dried to form the carbon coating. The binder is one or more of sodium polyacrylate, polyurethane, PVDF and polyvinyl alcohol, and the organic solvent is one or more of NMP, dibutyl carbonate, dimethyl carbonate, ethyl propyl carbonate, isopropyl alcohol, propylene glycol methyl ether and vinylidene carbonate. The prior art teaches that such a carbon coating prevents corrosion of the foil and reduces the internal resistance of the lithium-ion battery. However, the use of organic solvents makes the carbon-coated foil less environmentally friendly and the foil-making process more hazardous. Even if an electrode layer is formed on top of the carbon-coated foil using a water-based slurry, the non-eco-friendly carbon coating negates the environmental and safety benefits that might be brought about by the water-based electrode layer.
[0010] Accordingly, it is an aim of the present invention to present a modified current collector to be used in battery electrodes, where the modified current collector is less susceptible to the above-mentioned issues of conventional current collectors and the electrochemical performance of any battery comprising such an electrode can be enhanced.SUMMARY OF THE INVENTION
[0011] The aforementioned needs are met by various aspects and embodiments disclosed herein. In one aspect, provided herein is a modified current collector for a secondary battery, comprising a substrate and a conductive layer applied on one side or both sides of the substrate, wherein the conductive layer comprises a conductive material, and a binder material, wherein the binder material comprises a fluorine-containing copolymer.
[0012] In some embodiments, the fluorine-containing copolymer comprises a structural unit (a) , a structural unit (b) and a structural unit (c) , wherein the structural unit (a) is derived from a fluorine-containing acrylate or methacrylate monomer. In some embodiments, one or both of the structural units (b) and (c) are derived from an acrylate or methacrylate monomer. In some embodiments, the monomer from which the structural unit (b) is derived has a glass transition temperature below 0 ℃. In certain embodiments, the monomer from which the structural unit (c) is derived has a glass transition temperature of 0 ℃ or above. In certain embodiments, one or both of the structural units (b) and (c) are fluorine-free.
[0013] In some embodiments, the fluorine-containing copolymer additionally comprises a structural unit (d) derived from a function-enhancing monomer. In certain embodiments, the fluorine-containing copolymer additionally comprises a structural unit (e) derived from a crosslinking monomer.
[0014] In another aspect, provided herein is a conductive layer slurry that can be used to prepare the conductive layer of the modified current collector. The conductive layer slurry comprises a conductive material, a binder material and an aqueous solvent, wherein the binder material comprises a fluorine-containing polymer. In some embodiments, the conductive layer slurry further comprises a stabilizing agent. In certain embodiments, the stabilizing agent comprises a stabilizing polymer comprising a structural unit (i) and a structural unit (ii) . In some embodiments, the stabilizing agent further comprises a structural unit (iii) .
[0015] In yet another aspect, provided herein is an electrode, comprising the modified current collector and an electrode layer located on the surface of the conductive layer, and wherein the electrode layer comprises an electrode active material and a binding agent.
[0016] The invention as disclosed herein solves the above-mentioned problems that affect current collectors in battery electrodes. Firstly, the conductive layer of the modified current collector can act as a physical barrier between the substrate and the alkaline electrode active material in the electrode layer. This prevents the corrosion of the substrate without compromising the conductivity within the electrode. Secondly, the conductive material in the conductive layer of the modified current collector reduces interfacial resistance between the electrode layer and the modified current collector itself, which improves the output performance of the electrode.
[0017] Furthermore, both the conductive layer of the modified current collector and the electrode layer of the electrode can be prepared with water-based slurries. When a water-based electrode slurry is applied on the conductive layer of the modified current collector to form the electrode layer, the binder material in the conductive layer of the modified current collector disclosed herein remains adhered to the substrate and does not dissolve into the electrode slurry, thus delamination of the conductive layer as a result of this dissolution of the binder material does not occur. This helps to reduce the environmental impact and improve the safety of the electrode manufacturing process.
[0018] As a result of the above advantages, batteries comprising electrodes that are produced using a modified current collector of the present invention exhibit exceptional electrochemical performance.BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figures 1a and 1b show the simplified views of two different embodiments of the modified current collector disclosed herein within an electrode.DETAILED DESCRIPTION OF THE INVENTION
[0020] In one aspect, provided herein is a modified current collector in an electrode for a battery, wherein the modified current collector comprises a substrate and a conductive layer located on one side or both sides of the substrate. The conductive layer itself comprises a binder material and a conductive material, wherein the binder material comprises a fluorine-containing copolymer. The conductive layer can be produced by coating a conductive layer slurry on the substrate, wherein the conductive layer slurry comprises the conductive material, the binder material and a solvent. In another aspect, provided herein is an electrode, comprising the modified current collector and an electrode layer located on top of the modified current collector, wherein the electrode layer comprises an electrode active material and a binding agent, and may additionally comprise a conductive agent. The electrode layer can be produced by coating an electrode slurry onto the modified current collector of the present invention, wherein the electrode slurry comprises the electrode active material, the binding agent and an aqueous solvent (and optionally, the conductive agent) .
[0021] The term “electrode” refers to a “cathode” or an “anode. ”
[0022] The term “electrode component” refers to any substance that is present in an electrode layer of an electrode, including but not limited to electrode active materials, conductive agents, and binding agents.
[0023] The term “positive electrode” is used interchangeably with cathode. Likewise, the term “negative electrode” is used interchangeably with anode.
[0024] The term “binder” , “binder material” or “binding agent” refers to a chemical compound, a mixture of compounds or a polymer that is used to hold material (s) in place and adhere them onto a surface. In some embodiments, the binder material refers to a chemical compound, mixture of compounds, or polymer that is used to hold a conductive material in place and adhere it onto a substrate to form a modified current collector. In some embodiments, the binding agent refers to a chemical compound, mixture of compounds, or polymer that is used to hold an electrode material and / or a conductive agent in place and adhere them onto a modified current collector to form an electrode. In some embodiments, the electrode does not comprise any conductive material or conductive agent. In some embodiments, the binder material and / or the binding agent independently forms a colloid in an aqueous solvent such as water. In some embodiments, the binder material and / or the binding agent independently forms a solution or dispersion in an aqueous solvent such as water.
[0025] The term “conductive material” or “conductive agent” refers to a material that has good electrical conductivity. Therefore, a conductive material is often added in the making of a modified current collector to improve its electrical conductivity. In some embodiments, a conductive agent is mixed with an electrode active material at the time of forming an electrode to improve electrical conductivity of the electrode. In some embodiments, each of the conductive material and the conductive agent is independently chemically active. In some embodiments, each of the conductive material and the conductive agent is independently chemically inactive.
[0026] The term “aqueous solvent” refers to a solution containing water as the major component and one or more minor components in addition to water, or a solution that consists solely of water.
[0027] With respect to a slurry, the term “water-based” means that the solvent of the slurry is an aqueous solvent. With respect to a mode of manufacturing electrodes or batteries, the term “water-based” means that at least one element of the electrode or battery is wholly or partially formed using a water-based slurry.
[0028] The term “unsaturated” refers to a moiety having one or more units of unsaturation.
[0029] The term “alkyl” or “alkyl group” refers to a univalent group having the general formula CnH2n+1 derived from removing a hydrogen atom from a saturated, unbranched or branched aliphatic hydrocarbon, where n is an integer.
[0030] The term “cycloalkyl” or “cycloalkyl group” refers to a saturated or unsaturated cyclic non-aromatic hydrocarbon radical having a single ring or multiple condensed rings. A cycloalkyl group can be unsubstituted or substituted by one or more suitable substituents. Furthermore, the cycloalkyl group can be monocyclic or polycyclic.
[0031] The term “alkenyl” refers to a univalent group derived from the removal of a hydrogen atom from any carbon atom of an unsaturated aliphatic hydrocarbon with at least one carbon-carbon double bond. Similarly, the term “alkynyl” refers to a univalent group derived from the removal of a hydrogen atom from any carbon atom of an unsaturated aliphatic hydrocarbon with at least one carbon-carbon triple bond. Furthermore, the term “enynyl” refers to a univalent group derived from the removal of a hydrogen atom from any carbon atom of an unsaturated aliphatic hydrocarbon with at least one carbon-carbon double bond and at least one carbon-carbon triple bond. The unsaturated aliphatic hydrocarbon of an alkenyl, alkynyl or enynyl may be branched or unbranched.
[0032] The term “alkoxy” refers to an alkyl group, as previously defined, attached to the principal carbon chain through an oxygen atom. An alkoxy group may be substituted or unsubstituted.
[0033] The term “aryl” or “aryl group” refers to an organic radical derived from a monocyclic or polycyclic aromatic hydrocarbon by removing a hydrogen atom. An aryl group can be unsubstituted or substituted with one or more suitable substituents.
[0034] The term “alkylamino” refers to a group derived from the removal of a hydrogen atom from a primary or secondary amine. Alkylamino embraces the terms “N-alkylamino” and “N, N-dialkylamino” , wherein the amino group is independently substituted with one or two alkyl groups, respectively. The alkylamino group is optionally substituted with one or more substituents.
[0035] The term “alkylthio” refers to a group containing a branched or unbranched alkyl group attached to a divalent sulfur atom. The alkylthio group is optionally substituted with one or more substituents.
[0036] The term “heteroatom” refers to one or more of oxygen (O) , sulfur (S) , nitrogen (N) , phosphorus (P) or silicon (Si) , including any oxidized form of nitrogen (N) , sulfur (S) or phosphorus (P) ; the quaternized form of any basic nitrogen; or a substitutable nitrogen of a heterocyclic ring.
[0037] The term “aliphatic” refers to a non-aromatic hydrocarbon or groups derived therefrom.
[0038] The term “aromatic” refers to groups comprising aromatic hydrocarbon rings, optionally including heteroatoms or substituents.
[0039] The term “substituted” is used to describe a compound or chemical moiety wherein at least one hydrogen atom of that compound or chemical moiety is replaced with a second chemical moiety. Examples of substituents include, but are not limited to, halogen; alkyl; heteroalkyl; alkenyl; alkynyl; enynyl; aryl, heteroaryl; hydroxyl; alkoxyl; amino; nitro; thiol; alkylthio; imine; cyano; amido; phosphonato; phosphinato; carboxyl; thiocarbonyl; sulfonyl; sulfonamide; acyl; formyl; acyloxy; alkoxycarbonyl; oxo; haloalkyl; carbocyclic cycloalkyl; carbocyclic or heterocyclic aryl; amino, monoalkylamino and dialkylamino; o-lower alkyl; o-aryl, aryl; aryl-lower alkyl; -CO2CH3; -CONH2; -OCH2CONH2; -NH2; -SO2NH2; -OCHF2; -CF3; -OCF3; –NH (alkyl) ; –N (alkyl) 2; –NH (aryl) ; –N (alkyl) (aryl) ; –N (aryl) 2; –CHO; –CO (alkyl) ; -CO (aryl) ; -CO2 (alkyl) ; and –CO2 (aryl) ; and such moieties can also be optionally substituted by a fused-ring structure or bridge. These substituents can optionally be further substituted with one or more substituents. All chemical groups disclosed herein can be substituted, unless specified otherwise.
[0040] The term “halogen” or “halo” refers to F, Cl, Br or I.
[0041] The term “polymer” refers to a compound prepared by polymerizing monomers, whether of the same type or of different types. The generic term “polymer” embraces the terms “homopolymer” and “copolymer” .
[0042] The term “homopolymer” refers to a polymer prepared by the polymerization of the same type of monomer.
[0043] The term “copolymer” refers to a polymer prepared by the polymerization of two or more different types of monomers.
[0044] The term “monomeric unit” refers to the constitutional unit derived from a single monomer to the structure of a polymer.
[0045] The term “structural unit” refers to the total monomeric units derived from the same monomer type in a polymer.
[0046] The term “homogenizer” refers to an equipment that can be used to homogenize materials, i.e., to distribute materials uniformly throughout a fluid. Where homogenization is disclosed herein, any conventional homogenizer can be used for the homogenization process.
[0047] The term “applying” refers to an act of laying or spreading a substance on a surface.
[0048] The term “solid content” refers to the amount of non-volatile material remaining after evaporation.
[0049] The term “current collector” refers to any conductive substrate, which is capable of conducting an electrical current flowing in electrodes during discharging or charging of a secondary battery. Some non-limiting examples of the current collector include a single metal layer or single substrate. In some embodiments, the current collector may be in contact with an electrode layer.
[0050] The term “modified current collector” refers to a substrate with a conductive layer applied on one side or both sides of the substrate.
[0051] The term “electrode layer” refers to a layer that comprises an electrochemically active material. In some embodiments, the electrode layer is in contact with a current collector, a modified current collector or a substrate. In some embodiments, the electrode layer is made by applying a coating on to a current collector, a modified current collector or a substrate and drying the coating. In some embodiments, the electrode layer is located on the surface of the current collector or the modified current collector. In other embodiments, a three-dimensional porous current collector or modified current collector is coated conformally with an electrode layer.
[0052] The term “room temperature” refers to indoor temperatures from about 18 ℃ to about 30 ℃, e.g., 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 ℃. In some embodiments, room temperature refers to a temperature of about 20 ℃ + / -1 ℃ or + / -2 ℃ or + / -3 ℃. In other embodiments, room temperature refers to a temperature of about 22 ℃ or about 25 ℃.
[0053] The term “peeling strength” refers to the amount of force required to separate two materials that are adhered to each other, such as a current collector and an electrode layer. It is a measure of the binding strength between such two materials and is usually expressed in N / cm.
[0054] The term “adhesive strength” refers to the amount of force required to separate a substrate and a binder material adhered to the substrate. It is a measure of the adhesion strength between such two materials and is usually expressed in N / cm.
[0055] The term “ampere-hour (Ah) ” refers to a unit used in specifying the storage capacity of a battery. For example, a battery with 1 Ah capacity can supply a current of one ampere for one hour or 0.5 A for two hours, etc. Therefore, 1 ampere-hour (Ah) is the equivalent of 3,600 coulombs of electrical charge. Similarly, the term “milliampere-hour (mAh) ” also refers to a unit of the storage capacity of a battery and is 1 / 1,000 of an ampere-hour.
[0056] The term “capacity” is a characteristic of an electrochemical cell that refers to the total amount of electrical charge an electrochemical cell, such as a battery, is able to hold. Capacity is typically expressed in units of ampere-hours. The term “specific capacity” refers to the capacity output of an electrochemical cell, such as a battery, per unit weight, usually expressed in Ah / kg or mAh / g.
[0057] In the following description, all numbers disclosed herein are approximate values, regardless of whether the word “about” or “approximate” is used in connection therewith. They may vary by 1 percent, 2 percent, 5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical range with a lower limit, RL, and an upper limit, RU, is disclosed, any number falling within the range is specifically disclosed. In particular, the following numbers within the range are specifically disclosed: R=RL+k* (RU-RL) , wherein k is a variable ranging from 0 percent to 100 percent. Moreover, any numerical range defined by two R numbers as defined above is also specifically disclosed.
[0058] In the present description, all references to the singular include references to the plural and vice versa. In the present description, where the context allows, references to an “aqueous solvent” may also specifically refer to water.
[0059] Battery electrodes commonly comprise a current collector and an electrode layer located on one side or both sides of the current collector. Typically, the electrode is prepared by dispersing an electrode active material and a binding agent in a solvent to form an electrode slurry, then coating the electrode slurry onto a current collector and drying it to form the electrode layer. Said electrode slurry (and hence, the resultant electrode layer) may additionally comprise conductive carbon. Regardless of the components present in the electrode layer, the discontinuity between the electrode layer and the current collector of the electrode means that significant interfacial resistance exists between the electrode layer and the current collector. Batteries comprising such electrodes would then have suboptimal electrochemical performances as a result of such interfacial resistances.
[0060] Among batteries, lithium-ion batteries are some of the most widely researched and used. A common electrode slurry composition for lithium-ion batteries comprises PVDF as a binding agent and NMP as a solvent, but the use of NMP presents significant environmental, health and safety risks, in addition to incurring additional costs associated with a recovery system. Therefore, water-based electrode slurries comprising an aqueous solvent, such as water, have been proposed as an alternative.
[0061] However, corrosion of current collectors is particularly pronounced in cathodes produced using a water-based slurry that comprises a nickel-containing cathode active material, such as NMC, since such a slurry would be quite basic.
[0062] To solve the aforementioned problems, inventors of the present invention have proposed the use of a novel modified current collector, comprising a substrate and a conductive layer located on one side or both sides of the substrate. In a battery electrode, the conductive layer of the modified current collector disclosed herein reduces interfacial resistance between the electrode layer and the modified current collector and acts as a physical barrier between the substrate and the electrode layer, which helps alleviate the corrosion tendency of the substrate. In addition, the conductive layer of the present invention has an edge on not reverting to a fluid when a water-based electrode slurry is applied on top of the conductive layer.
[0063] The modified current collector as described herein refers to a substrate with a conductive layer applied on one side or both sides of the substrate, wherein the conductive layer comprises a conductive material and a binder material. Figure 1a shows a simplified view of an embodiment of the modified current collector of the present invention, represented by 10, within an electrode 100. The modified current collector 10 comprises a substrate 101 with a conductive layer 102 applied on one side of the substrate 101. In battery electrode production, an electrode layer 20 may be located on the surface of the conductive layer 102.
[0064] Figure 1b shows a simplified view of another embodiment of the modified current collector of the present invention, represented by 11, within an electrode 110. The modified current collector 11 comprises a substrate 111 with conductive layers 112a and 112b applied on both sides of the substrate 111. In the process of manufacturing a battery electrode, electrode layers 21a and 21b could be applied on the surface of the conductive layers 112a and 112b respectively.
[0065] When applied in a battery system, the substrate within the modified current collector of the present invention specifically acts to collect electrons generated by electrochemical reactions of the cathode active material or to supply electrons required for the electrochemical reactions.
[0066] In some embodiments, the substrate may be in the form of a foil, sheet, film or porous body with a three-dimensional network structure. In some embodiments, the substrate may be made of a polymeric or metallic material or a metalized polymer. In some embodiments, the substrate is covered with a conformal carbon layer. In some embodiments, the substrate is made of a single material. In other embodiments, the substrate is made of more than one material.
[0067] In some embodiments, the substrate is a metal. In some embodiments, the substrate has a single-layer structure. In some embodiments, the substrate is selected from the group consisting of stainless steel, titanium, nickel, aluminum, copper, platinum, gold, silver, chromium, zirconium, tungsten, molybdenum, silicon, tin, vanadium, zinc, cadmium, alloys thereof, electrically-conductive resin, and combinations thereof.
[0068] In certain embodiments, the substrate has a two-layered structure comprising an outer layer and an inner layer, wherein the outer layer comprises a conductive additive and the inner layer comprises an insulating material or another conductive additive; for example, aluminum mounted with a conductive resin layer or a polymeric insulating material coated with an aluminum layer. In some embodiments, the conductive additive is selected from the group consisting of stainless steel, titanium, nickel, aluminum, copper, platinum, gold, silver, chromium, zirconium, tungsten, molybdenum, silicon, tin, vanadium, zinc, cadmium, alloys thereof, electrically-conductive resin, and combinations thereof.
[0069] In some embodiments, the substrate has a three-layered structure comprising an outer layer, a middle layer, and an inner layer, wherein the outer and inner layers comprise a conductive additive, and the middle layer comprises an insulating material or another conductive additive; for example, plastic coated with a metal film on both sides. In certain embodiments, each of the outer layer, middle layer and inner layer is independently selected from the group consisting of stainless steel, titanium, nickel, aluminum, copper, platinum, gold, silver, chromium, zirconium, tungsten, molybdenum, silicon, tin, vanadium, zinc, cadmium, alloys thereof, electrically-conductive resin, and combinations thereof.
[0070] In some embodiments, the insulating material is a polymeric material selected from the group consisting of polycarbonate, polyacrylate, polyacrylonitrile, polyester, polyamide, polystyrene, polyurethane, polyepoxy, poly (acrylonitrile butadiene styrene) , polyimide, polyolefin, polyethylene, polypropylene, polyphenylene sulfide, poly (vinyl ester) , polyvinyl chloride, polyether, polyphenylene oxide, cellulose polymer, and combinations thereof. In certain embodiments, the substrate has more than three layers.
[0071] In a battery electrode comprising the modified current collector of the present invention and an electrode layer, the conductive material in the conductive layer of the modified current collector provides conductive pathways for electrons in travelling in-between the electrode layer and the substrate of the modified current collector. This significantly reduces the interfacial resistance between the electrode layer and the modified current collector i.e., at the electrode layer-modified current collector interface.
[0072] In some embodiments, the conductive material in the conductive layer is a carbonaceous material selected from the group consisting of natural graphite particulate, synthetic graphite particulate, hard carbon, soft carbon, mesocarbon microbeads (MCMB) , carbon black, graphite, expanded graphite, graphene, graphene nanoplatelets, carbon fibers, carbon nano-fibers, graphitized carbon flake, carbon tubes, carbon nanotubes, activated carbon, Super P, KS6, vapor grown carbon fibers (VGCF) , mesoporous carbon, and combinations thereof. Using a combination of conductive materials that have different particle sizes can improve the packing and thus the conductivity of the conductive material, further improving battery performance.
[0073] In a battery electrode comprising the modified current collector of the present invention and an electrode layer, the binder material in the conductive layer of the modified current collector provides adhesion of component (s) within the conductive layer to one another, as well as to the substrate.
[0074] In some embodiments, the binder material in the conductive layer comprises a fluorine-containing copolymer. In some embodiments, the fluorine-containing copolymer comprises a structural unit (a) , a structural unit (b) and a structural unit (c) , wherein the structural unit (a) is derived from a fluorine-containing acrylate or methacrylate monomer.
[0075] In some embodiments, the fluorine-containing acrylate or methacrylate monomer from which structural unit (a) is derived is selected from the group consisting of fluoroalkyl acrylate, fluoroaryl acrylate, fluoroaralkyl acrylate, fluoroalkyl methacrylate, fluoroaryl methacrylate, fluoroaralkyl methacrylate, and combinations thereof. In certain embodiments, the fluorine-containing acrylate or methacrylate monomer from which structural unit (a) is derived is selected from the group consisting of 2, 2, 2-trifluoroethyl acrylate, 2, 2, 3, 3-tetrafluoropropyl acrylate, 2, 2, 3, 4, 4, 4-hexafluorobutyl acrylate, 1H, 1H, 9H-perfluorononyl acrylate, perfluoroethyl acrylate, perfluorobutyl acrylate, perfluorohexyl acrylate, perfluorooctyl acrylate, perfluorododecyl acrylate, trifluoromethyl acrylate, methyl 2, 2, 2- (trifluoroethyl) acrylate, methyl 2, 2, 3, 3- (tetrafluoropropyl) acrylate, methyl 2, 2, 3, 4, 4, 4- (hexafluorobutyl) acrylate, methyl 1H, 1H, 9H- (perfluorononyl) acrylate, methyl 1H, 1H, 11H- (perfluoroundecyl) acrylate, methyl (perfluoroethyl) acrylate, methyl (perfluorobutyl) acrylate, methyl (perfluorohexyl) acrylate, methyl (perfluorooctyl) acrylate, methyl (perfluorodecyl) acrylate, methyl (perfluorododecyl) acrylate, methyl (trifluoromethyl) acrylate, (perfluorohexyl) ethyl methacrylate, (perfluorooctyl) ethyl methacrylate, 1H, 1H, 7H-perfluoroheptyl methacrylate, isomers thereof, and combinations thereof.
[0076] In some embodiments, one or both of the structural units (b) and (c) are derived from an acrylate or methacrylate monomer. In some embodiments, one or both of the structural units (b) and (c) do not contain fluorine.
[0077] In some embodiments, the monomer from which the structural unit (b) is derived has a glass transition temperature below 0 ℃. In certain embodiments, the monomer from which the structural unit (b) is derived is selected from the group consisting of 2-ethylhexyl acrylate, 4-cyanobutyl acrylate, butyl acrylate, dodecyl acrylate, ethyl acrylate, pentyl acrylate, hexyl acrylate, isobutyl acrylate, isopropyl acrylate, isooctyl acrylate, decyl acrylate, propyl acrylate, sec-butyl acrylate, tetrahydrofurfuryl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, hexyl methacrylate, isodecyl methacrylate, octyl methacrylate, tetradecyl methacrylate, octadecyl methacrylate, isomers thereof, and combinations thereof.
[0078] In some embodiments, the monomer from which the structural unit (c) is derived has a glass transition temperature of 0 ℃ or above. In certain embodiments, the monomer from which the structural unit (c) is derived is selected from the group consisting of 2-cyanobutyl acrylate, 2-cyanoethyl acrylate, 3, 3, 5-trimethylcyclohexyl acrylate, benzyl acrylate, cyanomethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methyl acrylate, octadecyl acrylate, phenoxyethyl acrylate, tert-butyl acrylate, methyl cyanoacrylate, ethyl cyanoacrylate, butyl cyanoacrylate, hexadecyl acrylate, 1- (diethylamino) ethyl methacrylate, 1- (dimethylamino) ethyl methacrylate, 2- (tert-butylamino) ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-phenylethyl methacrylate, 4- (tert-butyl) cyclohexyl methacrylate, ethyl methacrylate, glycidyl methacrylate, hexadecyl methacrylate, isobornyl methacrylate, isobutyl methacrylate, isopropyl methacrylate, methyl methacrylate, neopentyl methacrylate, octadecyl methacrylate, pentyl methacrylate, phenyl methacrylate, propyl methacrylate, tetrahydrofurfuryl methacrylate, isomers thereof, and combinations thereof.
[0079] Every structural unit of the binder material gives different desirable properties to the binder material. For example, the combination of structural units (a) , (b) and (c) provides the fluorine-containing copolymer with a good balance of hydrophobic and hydrophilic properties that make it possible for the conductive layer to be produced with a water-based slurry. The fluorine atoms in the structural unit (a) of the binder material are highly hydrophobic and allow the binder material to resist dissolution in water. This way, the conductive layer containing the binder material will not fall apart when a water-based electrode slurry is coated on top of it to produce an electrode layer. However, the binder material must also disperse sufficiently in water for it to be used in a water-based conductive layer slurry. The structural units (b) and (c) of the copolymer have more polar functional groups, giving the binder material enough hydrophilicity to disperse in water to form a homogenous slurry. The result is that the binder material can be thoroughly dispersed in water to create a homogenous slurry, while still hydrophobic enough to allow the conductive layer to resist collapse when a water-based electrode layer is coated on top of it.
[0080] It can be advantageous for the structural units (b) and (c) to have different glass transition temperatures. Structural unit (b) , with its lower glass transition temperature, is more fluid-like under normal conditions, and can therefore provide the binder material and the conductive layer with flexibility and better adhesive properties. This allows the conductive layer to bend and extend, decreasing the probability of the conductive layer breaking during the electrode manufacturing process. However, an excess of structural unit (b) will cause the conductive layer to be too soft and lack rigidity. On the other hand, structural unit (c) , having a higher glass transition temperature, is more solid-like under normal conditions. Thus, it provides mechanical strength to the binder material and the conductive layer. An excess of structural unit (c) , however, will make the conductive layer very brittle.
[0081] The proportions of each of the structural units (a) , (b) and (c) in the fluorine-containing copolymer of the binder material are important parameters. When the proportions of each of the structural units in the fluorine-containing copolymer of the binder material are within the ranges described below, the desirable properties described above (e.g., good dispersion in aqueous solvent, appropriate water resistance, flexibility of conductive layer, etc. ) can be achieved. Conversely, too much or too little of a certain structural unit in the binder material results in the loss of such desirable properties and can even bring about negative effects.
[0082] In some embodiments, the proportion of the structural unit (a) in the fluorine-containing copolymer of the binder material is from about 3%to about 30%, from about 5%to about 30%, from about 8%to about 30%, from about 10%to about 30%, from about 12%to about 30%, from about 15%to about 30%, from about 18%to about 30%, from about 20%to about 30%, from about 22%to about 30%, from about 25%to about 30%, from about 3%to about 25%, from about 5%to about 25%, from about 8%to about 25%, from about 10%to about 25%, from about 12%to about 25%, from about 15%to about 25%, from about 18%to about 25%, from about 20%to about 25%, from about 3%to about 20%, from about 5%to about 20%, from about 8%to about 20%, from about 10%to about 20%, from about 12%to about 20%, from about 15%to about 20%, from about 3%to about 15%, from about 5%to about 15%, from about 8%to about 15%, from about 10%to about 15%, from about 3%to about 10%, or from about 5%to about 10%by mole, based on the total number of moles of monomeric units in the fluorine-containing copolymer.
[0083] In some embodiments, the proportion of the structural unit (a) in the fluorine-containing copolymer of the binder material is at least 3%, at least 5%, at least 8%, at least 10%, at least 12%, at least 15%, at least 18%, at least 20%, at least 22%, or at least 25%by mole, based on the total number of moles of monomeric units in the fluorine-containing copolymer. In some embodiments, the proportion of the structural unit (a) in the fluorine-containing copolymer of the binder material is at most 30%, at most 28%, at most 25%, at most 22%, at most 20%, at most 18%, at most 15%, at most 12%, at most 10%, or at most 8%by mole, based on the total number of moles of monomeric units in the fluorine-containing copolymer.
[0084] In some embodiments, the proportion of each of the structural unit (b) and the structural unit (c) in the fluorine-containing copolymer of the binder material is independently from about 20%to about 60%, from about 25%to about 60%, from about 30%to about 60%, from about 35%to about 60%, from about 40%to about 60%, from about 45%to about 60%, from about 50%to about 60%, from about 55%to about 60%, from about 20%to about 55%, from about 25%to about 55%, from about 30%to about 55%, from about 35%to about 55%, from about 40%to about 55%, from about 45%to about 55%, from about 50%to about 55%, from about 20%to about 50%, from about 25%to about 50%, from about 30%to about 50%, from about 35%to about 50%, from about 40%to about 50%, from about 45%to about 50%, from about 20%to about 45%, from about 25%to about 45%, from about 30%to about 45%, from about 35%to about 45%, from about 40%to about 45%, from about 20%to about 40%, from about 25%to about 40%, from about 30%to about 40%, from about 35%to about 40%, from about 20%to about 35%, from about 25%to about 35%, from about 30%to about 35%, from about 20%to about 30%, from about 25%to about 30%, or from about 20%to about 25%by mole, based on the total number of moles of monomeric units in the fluorine-containing copolymer.
[0085] In some embodiments, the proportion of each of the structural unit (b) and the structural unit (c) in the fluorine-containing copolymer of the binder material is independently at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, or at least 55%by mole, based on the total number of moles of monomeric units in the fluorine-containing copolymer. In some embodiments, the proportion of each of the structural unit (b) and the structural unit (c) in the fluorine-containing copolymer of the binder material is independently at most 60%, at most 55%, at most 50%, at most 45%, at most 40%, at most 35%, at most 30%, or at most 25%by mole, based on the total number of moles of monomeric units in the fluorine-containing copolymer.
[0086] In some embodiments, the fluorine-containing copolymer of the binder material additionally comprises a structural unit (d) derived from a function-enhancing monomer. The function-enhancing monomer may perform a variety of functions, such as improving the stability of the polymerization process that produces the copolymer, enhancing the adhesive performance of the copolymer, and improving the dispersion of the copolymer in an aqueous solvent. The exact function of the function-enhancing monomer may depend on the type of function-enhancing monomer used.
[0087] In certain embodiments, the function-enhancing polymer is derived from an acid group-containing monomer, an amide group-containing monomer, a nitrile group-containing monomer, or combinations thereof. In certain embodiments, the acid-group containing monomer is a carboxylic acid or a salt thereof. In some embodiments, the salt of the carboxylic acid is a salt comprising an alkali metal cation. Some non-limiting examples of alkali metal cations include lithium, sodium and potassium. In certain embodiments, the salt of the carboxylic acid comprises an ammonium cation.
[0088] In some embodiments, the carboxylic acid is acrylic acid, methacrylic acid, crotonic acid, 2-butyl crotonic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, tetraconic acid, or a combination thereof. In certain embodiments, the carboxylic acid is 2-ethylacrylic acid, isocrotonic acid, cis-2-pentenoic acid, trans-2-pentenoic acid, angelic acid, tiglic acid, 3, 3-dimethyl acrylic acid, 3-propyl acrylic acid, trans-2-methyl-3-ethyl acrylic acid, cis-2-methyl-3-ethyl acrylic acid, 3-isopropyl acrylic acid, trans-3-methyl-3-ethyl acrylic acid, cis-3-methyl-3-ethyl acrylic acid, 2-isopropyl acrylic acid, trimethyl acrylic acid, 2-methyl-3, 3-diethyl acrylic acid, 3-butyl acrylic acid, 2-butyl acrylic acid, 2-pentyl acrylic acid, 2-methyl-2-hexenoic acid, trans-3-methyl-2-hexenoic acid, 3-methyl-3-propyl acrylic acid, 2-ethyl-3-propyl acrylic acid, 2, 3-diethyl acrylic acid, 3, 3-diethyl acrylic acid, 3-methyl-3-hexyl acrylic acid, 3-methyl-3-tert-butyl acrylic acid, 2-methyl-3-pentyl acrylic acid, 3-methyl-3-pentyl acrylic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-hexenoic acid, 3-methyl-2-ethyl-2-hexenoic acid, 3-tert-butyl acrylic acid, 2, 3-dimethyl-3-ethyl acrylic acid, 3, 3-dimethyl-2-ethyl acrylic acid, 3-methyl-3-isopropyl acrylic acid, 2-methyl-3-isopropyl acrylic acid, trans-2-octenoic acid, cis-2-octenoic acid, trans-2-decenoic acid, α-acetoxyacrylic acid, β-trans-aryloxyacrylic acid, α-chloro-β-E-methoxyacrylic acid, methyl maleic acid, dimethyl maleic acid, phenyl maleic acid, bromo maleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, difluoro maleic acid, nonyl hydrogen maleate, decyl hydrogen maleate, dodecyl hydrogen maleate, octadecyl hydrogen maleate, fluoroalkyl hydrogen maleate, maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, acrylic anhydride, methacrylic anhydride, methacrolein, methacryloyl chloride, methacryloyl fluoride, methacryloyl bromide, a derivative thereof, an isomer thereof, or a combination thereof.
[0089] In some embodiments, the amide group-containing monomer is acrylamide, methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-n-propyl methacrylamide, N-isopropyl methacrylamide, isopropyl acrylamide, N-n-butyl methacrylamide, N-isobutyl methacrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, N, N-diethyl methacrylamide, N-methylol methacrylamide, N- (methoxymethyl) methacrylamide, N- (ethoxymethyl) methacrylamide, N- (propoxymethyl) methacrylamide, N- (butoxymethyl) methacrylamide, N, N-dimethylaminopropyl methacrylamide, N, N-dimethylaminoethyl methacrylamide, N, N-dimethylol methacrylamide, diacetone methacrylamide, diacetone acrylamide, methacryloyl morpholine, N-hydroxyl methacrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N, N’-methylene-bis-acrylamide (MBA) , N-hydroxymethyl acrylamide, a derivative thereof, an isomer thereof, or a combination thereof.
[0090] In some embodiments, the nitrile group-containing monomer is or comprises an α, β-ethylenically unsaturated nitrile monomer. In some embodiments, the nitrile group-containing monomer is acrylonitrile, α-halogenoacrylonitrile, α-alkylacrylonitrile, or a combination thereof. In some embodiments, the nitrile group-containing monomer is α-chloroacrylonitrile, α-bromoacrylonitrile, α-fluoroacrylonitrile, methacrylonitrile, α- ethylacrylonitrile, α-isopropylacrylonitrile, α-n-hexylacrylonitrile, α-methoxyacrylonitrile, 3-methoxyacrylonitrile, 3-ethoxyacrylonitrile, α-acetoxyacrylonitrile, α-phenylacrylonitrile, α-tolylacrylonitrile, α- (methoxyphenyl) acrylonitrile, α- (chlorophenyl) acrylonitrile, α- (cyanophenyl) acrylonitrile, vinylidene cyanide, a derivative thereof, an isomer thereof, or a combination thereof.
[0091] In some embodiments, the proportion of the structural unit (d) in the fluorine-containing copolymer of the binder material is from 0.1%to about 10%, from about 0.2%to about 10%, from about 0.5%to about 10%, from about 1%to about 10%, from about 2%to about 10%, from about 3%to about 10%, from about 4%to about 10%, from about 5%to about 10%, from about 6%to about 10%, from about 7%to about 10%, from about 8%to about 10%, from about 1%to about 8%, from about 2%to about 8%, from about 3%to about 8%, from about 4%to about 8%, from about 5%to about 8%, from about 6%to about 8%, from about 1%to about 6%, from about 2%to about 6%, from about 3%to about 6%, from about 4%to about 6%, from about 1%to about 4%, or from about 2%to about 4%by mole, based on the total number of moles of monomeric units in the copolymer.
[0092] In some embodiments, the proportion of the structural unit (d) in the fluorine-containing copolymer of the binder material is at least 0.1%, at least 0.2%, at least 0.5%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 6%, at least 7%, or at least 8%by mole, based on the total number of moles of monomeric units in the copolymer. In some embodiments, the proportion of the structural unit (d) in the fluorine-containing copolymer of the binder material is at most 10%, at most 9%, at most 8%, at most 7%, at most 6%, at most 5%, at most 4%, at most 3%, at most 2%, at most 1%, at most 0.5%, or at most 0.2%by mole, based on the total number of moles of monomeric units in the copolymer. In certain embodiments, the fluorine-containing copolymer of the binder material does not comprise structural unit (d) .
[0093] In some embodiments, the fluorine-containing copolymer of the binder material further comprises a structural unit (e) derived from a crosslinking monomer. The crosslinking monomers can be activated by certain reagents, causing chemical reactions to occur between the crosslinking monomers and forming a crosslinked structure. Such a structure improves the chemical stability of the binder material, allowing it to better withstand the charge / discharge cycles of battery operation and thus improving the cyclability performance of the battery.
[0094] In some embodiments, the crosslinking monomer is selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, tri (propylene glycol) dimethacrylate, tetra (ethylene glycol) diacrylate, N, N’-methylenebis (acrylamide) , poly (ethylene glycol) diacrylate, poly (ethylene glycol) dimethacrylate, poly (propylene glycol) diacrylate, poly (propylene glycol) dimethacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxylate triacrylate, divinylbenzene, polyester dimethacrylate, divinyl ether, trimethylolpropane trimethacrylate, bisphenol A ethoxylate dimethacrylate, 1, 4-butylene glycol diacrylate, 1, 6-hexylene glycol diacrylate, di (trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol ethoxylate tetraacrylate, di (pentaerythritol) pentaacrylate, di (pentaerythritol) hexaacrylate, glycerol triacrylate, glycerol trimethacrylate, glycerol propoxylate triacrylate, derivatives thereof, isomers thereof, and combinations thereof.
[0095] In some embodiments, the proportion of the structural unit (e) in the fluorine-containing copolymer of the binder material is from about 0.001%to about 2%, from about 0.001%to about 1.5%, from about 0.001%to about 1%, from about 0.001%to about 0.5%, from about 0.005%to about 2%, from about 0.005%to about 1.5%, from about 0.005%to about 1%, from about 0.005%to about 0.5%, from about 0.01%to about 2%, from about 0.01%to about 1.5%, from about 0.01%to about 1%, from about 0.01%to about 0.5%, from about 0.02%to about 2%, from about 0.02%to about 1.5%, from about 0.02%to about 1%, from about 0.02%to about 0.5%, from about 0.05%to about 2%, from about 0.05%to about 1.5%, from about 0.05%to about 1%, from about 0.05%to about 0.5%, from about 0.1%to about 2%, from about 0.1%to about 1.5%, from about 0.1%to about 1%, from about 0.1%to about 0.5%, from about 0.2%to about 2%, from about 0.2%to about 1.5%, from about 0.2%to about 1%, from about 0.2%to about 0.5%, from about 0.5%to about 2%, from about 0.5%to about 1.5%, from about 0.5%to about 1%, or from about 1%to about 2%by mole, based on the total number of moles of monomeric units in the copolymer.
[0096] In some embodiments, the proportion of the structural unit (e) in the fluorine-containing copolymer of the binder material is at least 0.001%, at least 0.002%, at least 0.005%, at least 0.01%, at least 0.02%, at least 0.05%, at least 0.1%. at least 0.2%, at least 0.5%, or at least 1%by mole, based on the total number of moles of monomeric units in the copolymer. In some embodiments, the proportion of the structural unit (e) in the fluorine-containing copolymer of the binder material is at most 2%, at most 1.5%, at most 1%, at most 0.5%, at most 0.2%, at most 0.1%, at most 0.05%, at most 0.02%, at most 0.01%, or at most 0.005%by mole, based on the total number of moles of monomeric units in the copolymer. In certain embodiments, the copolymer of the binder material does not comprise a structural unit (e) .
[0097] In some embodiments, the copolymer of the binder material comprises other structural units in lieu of the structural units (d) and / or (e) . In certain embodiments, the fluorine-containing copolymer of the binder material further comprises one or more structural units beyond structural units (a) , (b) , (c) , (d) and (e) .
[0098] In some embodiments, the weight-average molecular weight of the copolymer of the binder material is from about 200,000 g / mol to about 500,000 g / mol, from about 200,000 g / mol to about 450,000 g / mol, from about 200,000 g / mol to about 400,000 g / mol, from about 200,000 g / mol to about 350,000 g / mol, from about 200,000 g / mol to about 300,000 g / mol, from about 200,000 g / mol to about 250,000 g / mol, from about 250,000 g / mol to about 500,000 g / mol, from about 250,000 g / mol to about 450,000 g / mol, from about 250,000 g / mol to about 400,000 g / mol, from about 250,000 g / mol to about 350,000 g / mol, from about 250,000 g / mol to about 300,000 g / mol, from about 300,000 g / mol to about 500,000 g / mol, from about 300,000 g / mol to about 450,000 g / mol, from about 300,000 g / mol to about 400,000 g / mol, from about 300,000 g / mol to about 350,000 g / mol, from about 350,000 g / mol to about 500,000 g / mol, from about 350,000 g / mol to about 450,000 g / mol, from about 350,000 g / mol to about 400,000 g / mol, from about 400,000 g / mol to about 500,000 g / mol, from about 400,000 g / mol to about 450,000 g / mol, or from about 450,000 g / mol to about 500,000 g / mol. When the weight-average molecular weight of the copolymer of the binder material is within these ranges, the copolymer can provide sufficient adhesion without being too bulky to disperse well in the solvent of a conductive layer slurry.
[0099] In some embodiments, the binder material is in the form of a solution, colloid or emulsion. In certain embodiments, the binder material comprises a solvent. In some embodiments, the solvent of the binder material is an aqueous solvent.
[0100] The binder material used in the present invention exhibits strong adhesive performance, ensuring that the conductive layer adheres strongly to the substrate. In some embodiments, the adhesive strength between the binder material and the substrate is from about 2 N / cm to about 8 N / cm, from about 2 N / cm to about 7 N / cm, from about 2 N / cm to about 6 N / cm, from about 2 N / cm to about 5 N / cm, from about 2 N / cm to about 4 N / cm, from about 2 N / cm to about 3 N / cm, from about 3 N / cm to about 8 N / cm, from about 4 N / cm to about 8 N / cm, from about 5 N / cm to about 8 N / cm, or from about 6 N / cm to about 8 N / cm.
[0101] In some embodiments, the adhesive strength between the binder material and the substrate is less than 8 N / cm, less than 7 N / cm, less than 6 N / cm, less than 5 N / cm, less than 4 N / cm, or less than 3 N / cm. In some embodiments, the adhesive strength between the binder material and the substrate is more than 2 N / cm, more than 3 N / cm, more than 4 N / cm, more than 5 N / cm, more than 6 N / cm, or more than 7 N / cm.
[0102] In some embodiments, the conductive layer of the modified current collector further comprises additional components. In certain embodiments, the conductive layer further comprises a stabilizing agent. In certain embodiments, the conductive layer further comprises a surfactant and / or a dispersant. In some embodiments, the conductive layer does not comprise any additional components.
[0103] The proportions of each of the binder material and the conductive material within the conductive layer of the modified current collector greatly affect the effectiveness of the conductive layer in forming an unyielding conductive layer structure, reducing corrosion tendency of the substrate, and minimizing the interfacial resistance between the electrode layer and the modified current collector. An inadequate amount of conductive material within the conductive layer would fail to form a conductive network that can facilitate efficient and effective transfer of electrons between the electrode layer and the substrate. Meanwhile, insufficient binder material within the conductive layer would have difficulty in holding the entire conductive layer in place. The conductive layer may easily disintegrate and thus fail to improve conductivity and prevent corrosion of the substrate.
[0104] In some embodiments, the proportion of each of the binder material and the conductive material within the conductive layer of the modified current collector is independently from about 20%to about 80%, from about 25%to about 80%, from about 30%to about 80%, from about 35%to about 80%, from about 40%to about 80%, from about 45%to about 80%, from about 50%to about 80%, from about 55%to about 80%, from about 60%to about 80%, from about 20%to about 75%, from about 25%to about 75%, from about 30%to about 75%, from about 35%to about 75%, from about 40%to about 75%, from about 45%to about 75%, from about 50%to about 75%, from about 55%to about 75%, from about 60%to about 75%, from about 20%to about 70%, from about 25%to about 70%, from about 30%to about 70%, from about 35%to about 70%, from about 40%to about 70%, from about 45%to about 70%, from about 50%to about 70%, from about 55%to about 70%, from about 20%to about 65%, from about 25%to about 65%, from about 30%to about 65%, from about 35%to about 65%, from about 40%to about 65%, from about 45%to about 65%, from about 50%to about 65%, from about 20%to about 60%, from about 25%to about 60%, from about 30%to about 60%, from about 35%to about 60%, from about 40%to about 60%, from about 45%to about 60%, from about 20%to about 55%, from about 25%to about 55%, from about 30%to about 55%, from about 35%to about 55%, from about 40%to about 55%, from about 20%to about 50%, from about 25%to about 50%, from about 30%to about 50%or from about 35%to about 50%by weight, based on the total weight of the conductive layer.
[0105] In some embodiments, the proportion of each of the binder material and the conductive material within the conductive layer of the modified current collector is independently less than 75%, less than 70%, less than 65%, less than 60%, less than 55%, less than 50%, less than 45%, less than 40%, less than 35%less than 30%or less than 25%by weight, based on the total weight of the conductive layer. In some embodiments, the proportion of each of the binder material and the conductive material within the conductive layer of the modified current collector is independently more than 20%, more than 25%, more than 30%, more than 35%, more than 40%, more than 45%, more than 50%, more than 55%, more than 60%, more than 65%or more than 70%by weight, based on the total weight of the conductive layer. Parameters of the conductive layer such as thickness, surface density, density etc. are also important as they affect the electrochemical characteristics of the conductive layer, such as conductivity. When these parameters are within the ranges described below, the conductive layer has good electrochemical performance.
[0106] In some embodiments, the thickness of the conductive layer is from about 0.5 μm to about 15 μm, from about 0.5 μm to about 12 μm, from about 0.5 μm to about 10 μm, from about 0.5 μm to about 8 μm, from about 0.5 μm to about 5 μm, from about 0.8 μm to about 15 μm, from about 0.8 μm to about 12 μm, from about 0.8 μm to about 10 μm, from about 0.8 μm to about 8 μm, from about 0.8 μm to about 5 μm, from about 1 μm to about 15 μm, from about 1 μm to about 12 μm, from about 1 μm to about 10 μm, from about 1 μm to about 8 μm, or from about 1 μm to about 5 μm.
[0107] In some embodiments, the thickness of the conductive layer is at least 0.5 μm, at least 0.8 μm, at least 1 μm, at least 1.2 μm, at least 1.5 μm, at least 2 μm, at least 2.5 μm, or at least 3 μm, at least 4 μm, or at least 5 μm. In some embodiments, the thickness of the conductive layer is at most 15 μm, at most 12 μm, at most 10 μm, at most 9 μm, at most 8.5 μm, at most 8 μm, at most 7.5 μm, at most 7 μm, at most 6.5 μm, at most 6 μm, at most 5.5 μm, or at most 5 μm.
[0108] In some embodiments, the surface density of the conductive layer is from about 0.01 mg / cm2 to about 5 mg / cm2, from about 0.02 mg / cm2 to about 5 mg / cm2, from about 0.05 mg / cm2 to about 5 mg / cm2, from about 0.08 mg / cm2 to about 5 mg / cm2, from about 0.1 mg / cm2 to about 5 mg / cm2, from about 0.15 mg / cm2 to about 5 mg / cm2, from about 0.2 mg / cm2 to about 5 mg / cm2, from about 0.3 mg / cm2 to about 5 mg / cm2, from about 0.5 mg / cm2 to about 5 mg / cm2, from about 0.8 mg / cm2 to about 5 mg / cm2, from about 1 mg / cm2 to about 5 mg / cm2, from about 1.5 mg / cm2 to about 5 mg / cm2, from about 0.01 mg / cm2 to about 3 mg / cm2, from about 0.02 mg / cm2 to about 3 mg / cm2, from about 0.05 mg / cm2 to about 3 mg / cm2, from about 0.08 mg / cm2 to about 3 mg / cm2, from about 0.1 mg / cm2 to about 3 mg / cm2, from about 0.15 mg / cm2 to about 3 mg / cm2, from about 0.2 mg / cm2 to about 3 mg / cm2, from about 0.3 mg / cm2 to about 3 mg / cm2, from about 0.5 mg / cm2 to about 3 mg / cm2, from about 0.8 mg / cm2 to about 3 mg / cm2, from about 1 mg / cm2 to about 3 mg / cm2, from about 0.01 mg / cm2 to about 2.5 mg / cm2, from about 0.02 mg / cm2 to about 2.5 mg / cm2, from about 0.05 mg / cm2 to about 2.5 mg / cm2, from about 0.08 mg / cm2 to about 2.5 mg / cm2, from about 0.1 mg / cm2 to about 2.5 mg / cm2, from about 0.15 mg / cm2 to about 2.5 mg / cm2, from about 0.2 mg / cm2 to about 2.5 mg / cm2, from about 0.3 mg / cm2 to about 2.5 mg / cm2, from about 0.5 mg / cm2 to about 2.5 mg / cm2, from about 0.8 mg / cm2 to about 2.5 mg / cm2, from about 1 mg / cm2 to about 2.5 mg / cm2, from about 0.01 mg / cm2 to about 2 mg / cm2, from about 0.02 mg / cm2 to about 2 mg / cm2, from about 0.05 mg / cm2 to about 2 mg / cm2, from about 0.08 mg / cm2 to about 2 mg / cm2, from about 0.1 mg / cm2 to about 2 mg / cm2, from about 0.15 mg / cm2 to about 2 mg / cm2, from about 0.2 mg / cm2 to about 2 mg / cm2, from about 0.25 mg / cm2 to about 2 mg / cm2, from about 0.3 mg / cm2 to about 2 mg / cm2, or from about 0.5 mg / cm2 to about 2 mg / cm2.
[0109] In some embodiments, the surface density of the conductive layer is at least 0.01 mg / cm2, at least 0.02 mg / cm2, at least 0.05 mg / cm2, at least 0.1 mg / cm2, at least 0.15 mg / cm2, at least 0.2 mg / cm2, at least 0.3 mg / cm2, at least 0.5 mg / cm2, at least 0.8 mg / cm2, at least 1 mg / cm2, at least 1.2 mg / cm2, or at least 1.5 mg / cm2. In some embodiments, the surface density of the conductive layer is at most 5 mg / cm2, at most 3 mg / cm2, at most 2.8 mg / cm2, at most 2.5 mg / cm2, at most 2.2 mg / cm2, at most 2 mg / cm2, at most 1.8 mg / cm2, or at most 1.5 mg / cm2.
[0110] In some embodiments, the density of the conductive layer is from about 0.01 g / cm3 to about 15 g / cm3, from about 0.02 g / cm3 to about 15 g / cm3, from about 0.05 g / cm3 to about 15 g / cm3, from about 0.08 g / cm3 to about 15 g / cm3, from about 0.1 g / cm3 to about 15 g / cm3, from about 0.15 g / cm3 to about 15 g / cm3, from about 0.2 g / cm3 to about 15 g / cm3, from about 0.3 g / cm3 to about 15 g / cm3, from about 0.5 g / cm3 to about 15 g / cm3, from about 0.8 g / cm3 to about 15 g / cm3, from about 1 g / cm3 to about 15 g / cm3, from about 2 g / cm3 to about 15 g / cm3, from about 5 g / cm3 to about 15 g / cm3, from about 0.01 g / cm3 to about 12 g / cm3, from about 0.02 g / cm3 to about 12 g / cm3, from about 0.05 g / cm3 to about 12 g / cm3, from about 0.08 g / cm3 to about 12 g / cm3, from about 0.1 g / cm3 to about 12 g / cm3, from about 0.15 g / cm3 to about 12 g / cm3, from about 0.2 g / cm3 to about 12 g / cm3, from about 0.3 g / cm3 to about 12 g / cm3, from about 0.5 g / cm3 to about 12 g / cm3, from about 0.8 g / cm3 to about 12 g / cm3, from about 1 g / cm3 to about 12 g / cm3, from about 2 g / cm3 to about 12 g / cm3, from about 5 g / cm3 to about 12 g / cm3, from about 0.01 g / cm3 to about 10 g / cm3, from about 0.02 g / cm3 to about 10 g / cm3, from about 0.05 g / cm3 to about 10 g / cm3, from about 0.08 g / cm3 to about 10 g / cm3, from about 0.1 g / cm3 to about 10 g / cm3, from about 0.15 g / cm3 to about 10 g / cm3, from about 0.2 g / cm3 to about 10 g / cm3, from about 0.3 g / cm3 to about 10 g / cm3, from about 0.5 g / cm3 to about 10 g / cm3, from about 0.8 g / cm3 to about 10 g / cm3, from about 1 g / cm3 to about 10 g / cm3, from about 2 g / cm3 to about 10 g / cm3, from about 0.01 g / cm3 to about 8 g / cm3, from about 0.02 g / cm3 to about 8 g / cm3, from about 0.05 g / cm3 to about 8 g / cm3, from about 0.08 g / cm3 to about 8 g / cm3, from about 0.1 g / cm3 to about 8 g / cm3, from about 0.15 g / cm3 to about 8 g / cm3, from about 0.2 g / cm3 to about 8 g / cm3, from about 0.3 g / cm3 to about 8 g / cm3, from about 0.5 g / cm3 to about 8 g / cm3, from about 0.8 g / cm3 to about 8 g / cm3, from about 1 g / cm3 to about 8 g / cm3, or from about 2 g / cm3 to about 8 g / cm3.
[0111] In some embodiments, the density of the conductive layer is at least 0.01 g / cm3, at least 0.02 g / cm3, at least 0.05 g / cm3, at least 0.08 g / cm3, at least 0.1 g / cm3, at least 0.15 g / cm3, at least 0.2 g / cm3, at least 0.3 g / cm3, at least 0.5 g / cm3, at least 0.8 g / cm3, at least 1 g / cm3, at least 1.2 g / cm3, at least 1.5 g / cm3, at least 2 g / cm3, or at least 5 g / cm3. In some embodiments, the density of the conductive layer is at most 15 g / cm3, at most 12 g / cm3, at most 11 g / cm3, at most 10 g / cm3, at most 9.5 g / cm3, at most 9 g / cm3, at most 8.5 g / cm3, at most 8 g / cm3, at most 7.5 g / cm3, at most 7 g / cm3, at most 6.5 g / cm3, at most 6 g / cm3, at most 5.5 g / cm3, or at most 5 g / cm3.
[0112] Another aspect of the present invention is a conductive layer slurry that can be used to prepare the conductive layer of the modified current collector. The conductive layer can be formed by coating the conductive layer slurry on to the substrate of the modified current collector and then drying it. In some embodiments, the conductive layer slurry comprises a conductive material, a binder material and an aqueous solvent, wherein the binder material comprises a fluorine-containing copolymer. The conductive material and the binder material are the ones contained in the conductive layer and have been described in detail above.
[0113] A key feature of the present invention is that the conductive layer slurry can be prepared with an aqueous solvent, which helps to reduce the negative environmental impact and improve the safety of the electrode manufacturing process. In some embodiments, the aqueous solvent is water.
[0114] In some embodiments, the aqueous solvent is a mixture of water and a minor component. Some non-limiting examples of the minor component include alcohols, lower aliphatic ketones, lower alkyl acetates, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and combinations thereof. Some non-limiting examples of the alcohols include C1-C4 alcohols, such as methanol, ethanol, isopropanol, n-propanol, tert-butanol, n-butanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, ethylene glycol, propylene glycol, glycerol, and combinations thereof. Some non-limiting examples of the lower aliphatic ketones include acetone, dimethyl ketone, methyl ethyl ketone (MEK) , methyl isobutyl ketone (MIBK) and combinations thereof. Some non-limiting examples of the lower alkyl acetates include ethyl acetate (EA) , isopropyl acetate, propyl acetate, butyl acetate (BA) , and combinations thereof.
[0115] In some embodiments, the weight ratio of the water to the minor component is from about 99: 1 to about 1: 99, from about 90: 10 to about 1: 99, from about 80: 20 to about 1: 99, from about 70: 30 to about 1: 99, from about 60: 40 to about 1: 99, from about 50: 50 to about 1: 99, from about 99: 1 to about 50: 50, from about 99: 1 to about 40: 60, from about 99: 1 to about 30: 70, from about 99: 1 to about 20: 80, or from about 99: 1 to about 10: 90. In certain embodiments, the solvent of the conductive layer slurry may be in the form of an emulsion or a colloid.
[0116] In some embodiments, the solid content of the conductive layer slurry is from about 1%to about 60%, from about 2%to about 60%, from about 5%to about 60%, from about 8%to about 60%, from about 10%to about 60%, from about 12%to about 60%, from about 15%to about 60%, from about 20%to about 60%, from about 25%to about 60%, from about 30%to about 60%, from about 1%to about 55%, from about 2%to about 55%, from about 5%to about 55%, from about 8%to about 55%, from about 10%to about 55%, from about 12%to about 55%, from about 15%to about 55%, from about 20%to about 55%, from about 25%to about 55%, from about 30%to about 55%, from about 1%to about 50%, from about 2%to about 50%, from about 5%to about 50%, from about 8%to about 50%, from about 10%to about 50%, from about 12%to about 50%, from about 15%to about 50%, from about 20%to about 50%, from about 25%to about 50%, from about 30%to about 50%, from about 1%to about 45%, from about 2%to about 45%, from about 5%to about 45%, from about 8%to about 45%, from about 10%to about 45%, from about 12%to about 45%, from about 15%to about 45%, from about 20%to about 45%, from about 25%to about 45%, from about 1%to about 42%, from about 2%to about 42%, from about 5%to about 42%, from about 8%to about 42%, from about 10%to about 42%, from about 12%to about 42%, from about 15%to about 42%, from about 20%to about 42%, from about 25%to about 42%, from about 1%to about 40%, from about 2%to about 40%, from about 5%to about 40%, from about 8%to about 40%, from about 10%to about 40%, from about 12%to about 40%, from about 15%to about 40%, from about 20%to about 40%, from about 1%to about 35%, from about 2%to about 35%, from about 5%to about 35%, from about 8%to about 35%, from about 10%to about 35%, from about 12%to about 35%, or from about 15%to about 35%, based on the total weight of the conductive layer slurry.
[0117] In some embodiments, the solid content of the conductive layer slurry is at least 1%, at least 2%, at least 5%, at least 8%, at least 10%, at least 12%, at least 15%, at least 20%, at least 25%, or at least 30%, based on the total weight of the conductive layer slurry. In some embodiments, the solid content of the conductive layer slurry is at most 60%, at most 55%, at most 50%, at most 45%, at most 40%, at most 35%, or at most 30%, based on the total weight of the conductive layer slurry.
[0118] The conductive layer slurry of the present invention can form a high-performance conductive layer even at a relatively low solid content. This conductive layer slurry has a relatively low viscosity, which would reduce the amount of energy needed to process it during electrode manufacturing. In some embodiments, the viscosity of the conductive layer slurry is from about 10 mPa·s to about 2,000 mPa·s, from about 50 mPa·s to about 2,000 mPa·s, from about 100 mPa·s to about 2,000 mPa·s, from about 200 mPa·s to about 2,000 mPa·s, from about 300 mPa·s to about 2,000 mPa·s, from about 400 mPa·s to about 2,000 mPa·s, from about 500 mPa·s to about 2,000 mPa·s, from about 800 mPa·s to about 2,000 mPa·s, from about 1,000 mPa·s to about 2,000 mPa·s, from about 1,200 mPa·s to about 2,000 mPa·s, from about 1,500 mPa·s to about 2,000 mPa·s, from about 10 mPa·s to about 1,500 mPa·s, from about 50 mPa·s to about 1,500 mPa·s, from about 100 mPa·s to about 1,500 mPa·s, from about 150 mPa·s to about 1,500 mPa·s, from about 170 mPa·s to about 1,500 mPa·s, from about 200 mPa·s to about 1,500 mPa·s, from about 300 mPa·s to about 1,500 mPa·s, from about 400 mPa·s to about 1,500 mPa·s, from about 500 mPa·s to about 1,500 mPa·s, from about 800 mPa·s to about 1,500 mPa·s, from about 1,000 mPa·s to about 1,500 mPa·s, from about 10 mPa·s to about 1,200 mPa·s, from about 50 mPa·s to about 1,200 mPa·s, from about 100 mPa·s to about 1,200 mPa·s, from about 200 mPa·s to about 1,200 mPa·s, from about 300 mPa·s to about 1,200 mPa·s, from about 400 mPa·s to about 1,200 mPa·s, from about 500 mPa·s to about 1,200 mPa·s, from about 10 mPa·s to about 1,000 mPa·s, from about 50 mPa·s to about 1,000 mPa·s, from about 100 mPa·s to about 1,000 mPa·s, from about 200 mPa·s to about 1,000 mPa·s, from about 300 mPa·s to about 1,000 mPa·s, from about 400 mPa·s to about 1,000 mPa·s, or from about 500 mPa·s to about 1,000 mPa·s.
[0119] In some embodiments, the viscosity of the conductive layer slurry is at least 10 mPa·s, at least 20 mPa·s, at least 50 mPa·s, at least 70 mPa·s, at least 100 mPa·s, at least 150 mPa·s, at least 170 mPa·s, at least 200 mPa·s, at least 250 mPa·s, at least 300 mPa·s, at least 350 mPa·s, at least 400 mPa·s, at least 450 mPa·s, at least 500 mPa·s, at least 600 mPa·s, at least 800 mPa·s, or at least 1,000 mPa·s. In some embodiments, the viscosity of the conductive layer slurry is at most 2,000 mPa·s, at most 1,900 mPa·s, at most 1,800 mPa·s, at most 1,700 mPa·s, at most 1,600 mPa·s, at most 1,500 mPa·s, at most 1,400 mPa·s, at most 1,300 mPa·s, at most 1,200 mPa·s, at most 1,100 mPa·s, at most 1,000 mPa·s, at most 900 mPa·s, at most 800 mPa·s, at most 700 mPa·s, at most 650 mPa·s, at most 600 mPa·s, at most 550 mPa·s, or at most 500 mPa·s.
[0120] In some embodiments, the conductive layer slurry further comprises a stabilizing agent. Adding the stabilizing agent in the conductive layer slurry facilitates homogenization of the slurry and helps to prevent separation of the various slurry components. In certain embodiments, the stabilizing agent comprises a stabilizing polymer comprising a structural unit (i) , a structural unit (ii) and a structural unit (iii) .
[0121] In some embodiments, the structural unit (i) is derived from an acid group-containing monomer. Any embodiments of monomers containing an acid group which structural unit (d) in the fluorine-containing copolymer of the binder material can be derived from are also suitable embodiments for which structural unit (i) is derived from. In certain embodiments, the monomers containing an acid group which structural unit (d) is derived from and the monomers which structural unit (i) is derived from respectively are the same, are different, or are partially different.
[0122] In some embodiments, the structural unit (ii) is derived from an amide group-containing monomer. Any embodiments of monomers containing an amide group which structural unit (d) in the fluorine-containing copolymer of the binder material can be derived from are also suitable embodiments for which structural unit (ii) is derived from. In certain embodiments, the monomers containing an amide group which structural unit (d) is derived from and the monomers which structural unit (ii) is derived from respectively are the same, are different, or are partially different.
[0123] In some embodiments, the structural unit (iii) is derived from a nitrile group- containing monomer. Any embodiments of monomers containing a nitrile group which structural unit (d) in the fluorine-containing copolymer of the binder material can be derived from are also suitable embodiments for which structural unit (iii) is derived from. In certain embodiments, the monomers containing a nitrile group which structural unit (d) is derived from and the monomers which structural unit (iii) is derived from respectively are the same, are different, or are partially different.
[0124] When the proportions of each of the structural units (i) , (ii) and (iii) are within the ranges described below, the copolymer of the stabilizing agent does well to promote homogenization and prevent the separation of the conductive layer slurry. In some embodiments, the proportion of the structural unit (i) in the copolymer of the stabilizing agent is from about 10%to about 70%, from about 12%to about 70%, from about 15%to about 70%, from about 18%to about 70%, from about 20%to about 70%, from about 22%to about 70%, from about 25%to about 70%, from about 28%to about 70%, from about 30%to about 70%, from about 35%to about 70%, from about 40%to about 70%, from about 10%to about 65%, from about 12%to about 65%, from about 15%to about 65%, from about 18%to about 65%, from about 20%to about 65%, from about 22%to about 65%, from about 25%to about 65%, from about 28%to about 65%, from about 30%to about 65%, from about 35%to about 65%, from about 10%to about 60%, from about 12%to about 60%, from about 15%to about 60%, from about 18%to about 60%, from about 20%to about 60%, from about 22%to about 60%, from about 25%to about 60%, from about 28%to about 60%, from about 30%to about 60%, from about 10%to about 50%, from about 12%to about 50%, from about 15%to about 50%, from about 18%to about 50%, or from about 20%to about 50%by mole, based on the total number of moles of monomeric units in the copolymer of the stabilizing agent.
[0125] In some embodiments, the proportion of the structural unit (i) in the copolymer of the stabilizing agent is at least 10%, at least 12%, at least 15%, at least 18%, at least 20%, at least 22%, at least 25%, at least 28%, at least 30%, at least 35%, or at least 40%by mole, based on the total number of moles of monomeric units in the copolymer of the stabilizing agent. In some embodiments, the proportion of structural unit (i) in the copolymer of the stabilizing agent is at most 70%, at most 65%, at most 60%, at most 55%, at most 50%, at most 45%, or at most 40%by mole, based on the total number of moles of monomeric units in the copolymer of the stabilizing agent.
[0126] In some embodiments, the proportion of the structural unit (ii) in the copolymer of the stabilizing agent is from about 5%to about 40%, from about 7%to about 40%, from about 10%to about 40%, from about 12%to about 40%, from about 15%to about 40%, from about 17%to about 40%, from about 20%to about 40%, from about 5%to about 37%, from about 7%to about 37%, from about 10%to about 37%, from about 12%to about 37%, from about 15%to about 37%, from about 17%to about 37%, from about 20%to about 37%, from about 5%to about 35%, from about 7%to about 35%, from about 10%to about 35%, from about 12%to about 35%, from about 15%to about 35%, from about 17%to about 35%, from about 20%to about 35%, from about 5%to about 32%, from about 7%to about 32%, from about 10%to about 32%, from about 12%to about 32%, from about 15%to about 32%, from about 5%to about 30%, from about 7%to about 30%, from about 10%to about 30%, from about 12%to about 30%, from about 15%to about 30%, from about 5%to about 27%, from about 7%to about 27%, from about 10%to about 27%, from about 12%to about 27%, from about 5%to about 25%, from about 7%to about 25%, or from about 10%to about 25%by mole, based on the total number of moles of monomeric units in the copolymer of the stabilizing agent.
[0127] In some embodiments, the proportion of the structural unit (ii) in the copolymer of the stabilizing agent is at least 5%, at least 7%, at least 10%, at least 12%, at least 15%, at least 17%, or at least 20%by mole, based on the total number of moles of monomeric units in the copolymer of the stabilizing agent. In some embodiments, the proportion of the structural unit (ii) in the copolymer of the stabilizing agent is at most 40%, at most 37%, at most 35%, at most 32%, at most 30%, at most 27%, at most 25%, at most 22%, or at most 20%by mole, based on the total number of moles of monomeric units in the copolymer of the stabilizing agent.
[0128] In some embodiments, the proportion of the structural unit (iii) in the copolymer of the stabilizing agent is from about 15%to about 70%, from about 20%to about 70%, from about 25%to about 70%, from about 30%to about 70%, from about 35%to about 70%, from about 40%to about 70%, from about 15%to about 65%, from about 20%to about 65%, from about 25%to about 65%, from about 30%to about 65%, from about 35%to about 65%, from about 40%to about 65%, from about 15%to about 60%, from about 20%to about 60%, from about 25%to about 60%, from about 30%to about 60%, from about 35%to about 60%, from about 15%to about 55%, from about 20%to about 55%, from about 25%to about 55%, from about 30%to about 55%, from about 15%to about 50%, from about 20%to about 50%, from about 25%to about 50%, or from about 30%to about 50%by mole, based on the total number of moles of monomeric units in the copolymer of the stabilizing agent.
[0129] In some embodiments, the proportion of the structural unit (iii) in the copolymer of the stabilizing agent is at least 15%, at least 17%, at least 20%, at least 22%, at least 25%, at least 27%, at least 30%, at least 32%, at least 35%, at least 37%, or at least 40%by mole, based on the total number of moles of monomeric units in the copolymer of the stabilizing agent. In some embodiments, the proportion of the structural unit (iii) in the copolymer of the stabilizing agent is at most 70%, at most 67%, at most 65%, at most 62%, at most 60%, at most 57%, at most 55%, at most 52%, at most 50%, at most 47%, at most 45%, at most 42%, or at most 40%by mole, based on the total number of moles of monomeric units in the copolymer of the stabilizing agent.
[0130] In other embodiments, one or more of the structural units of copolymer of the stabilizing agent are derived from monomers different to those listed herein. In further embodiments, the copolymer of the stabilizing agent comprises fewer or more structural units than those listed herein. In still further embodiments, the stabilizing agent does not comprise a copolymer, or the conductive layer slurry does not comprise a stabilizing agent in the first place.
[0131] In some embodiments, the proportion of the stabilizing agent in the conductive layer slurry is from about 0.1%to about 10%, from about 0.1%to about 8%, from about 0.1%to about 6%, from about 0.1%to about 5%, from about 0.1%to about 4%, from about 0.1%to about 3%, from about 0.1%to about 2%, from about 0.1%to about 1%, from about 0.5%to about 10%, from about 0.5%to about 8%, from about 0.5%to about 6%, from about 0.5%to about 5%, from about 0.5%to about 4%, from about 0.5%to about 3%, from about 0.5%to about 2%, from about 0.5%to about 1%, from about 1%to about 10%, from about 1%to about 8%, from about 1%to about 6%, from about 1%to about 5%, from about 1%to about 4%, from about 1%to about 3%, from about 1%to about 2%, from about 2%to about 10%, from about 2%to about 8%, from about 2%to about 6%, from about 2%to about 5%, or from about 2%to about 4%by weight, based on the solid content of the conductive layer slurry.
[0132] In some embodiments, the proportion of the stabilizing agent in the conductive layer slurry is at least 0.1%, at least 0.5%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 6%, or at least 8%by weight, based on the solid content of the conductive layer slurry. In some embodiments, the proportion of the stabilizing agent in the conductive layer slurry is at most 10%, at most 8%, at most 6%, at most 5%, at most 4%, at most 3%, at most 2%, at most 1%, or at most 0.5%by weight, based on the solid content of the conductive layer slurry.
[0133] To achieve the preferred proportions of the binder material and the conductive material in the conductive layer as previously described, the proportions of each of the binder material and the conductive material in the conductive layer slurry should be within the following ranges.
[0134] In some embodiments, the proportion of each of the binder material and the conductive material within the conductive layer slurry is independently from about 20%to about 80%, from about 25%to about 80%, from about 30%to about 80%, from about 35%to about 80%, from about 40%to about 80%, from about 45%to about 80%, from about 50%to about 80%, from about 55%to about 80%, from about 60%to about 80%, from about 20%to about 75%, from about 25%to about 75%, from about 30%to about 75%, from about 35%to about 75%, from about 40%to about 75%, from about 45%to about 75%, from about 50%to about 75%, from about 55%to about 75%, from about 60%to about 75%, from about 20%to about 70%, from about 25%to about 70%, from about 30%to about 70%, from about 35%to about 70%, from about 40%to about 70%, from about 45%to about 70%, from about 50%to about 70%, from about 55%to about 70%, from about 20%to about 65%, from about 25%to about 65%, from about 30%to about 65%, from about 35%to about 65%, from about 40%to about 65%, from about 45%to about 65%, from about 50%to about 65%, from about 20%to about 60%, from about 25%to about 60%, from about 30%to about 60%, from about 35%to about 60%, from about 40%to about 60%, from about 45%to about 60%, from about 20%to about 55%, from about 25%to about 55%, from about 30%to about 55%, from about 35%to about 55%, from about 40%to about 55%, from about 20%to about 50%, from about 25%to about 50%, from about 30%to about 50%or from about 35%to about 50%by weight, based on the solid content of the conductive layer slurry.
[0135] In some embodiments, the proportion of each of the binder material and the conductive material within the conductive layer slurry is independently less than 75%, less than 70%, less than 65%, less than 60%, less than 55%, less than 50%, less than 45%, less than 40%, less than 35%less than 30%or less than 25%by weight, based on the solid content of the conductive layer slurry. In some embodiments, the proportion of each of the binder material and the conductive material within the conductive layer slurry is independently more than 20%, more than 25%, more than 30%, more than 35%, more than 40%, more than 45%, more than 50%, more than 55%, more than 60%, more than 65%or more than 70%by weight, based on the solid content of the conductive layer slurry.
[0136] In some embodiments, the conductive layer slurry comprises additional components. In certain embodiments, the conductive layer slurry comprises a surfactant and / or a dispersant. In other embodiments, the conductive layer slurry does not comprise a surfactant or a dispersant.
[0137] It is important for the conductive layer to be smooth and uniform as unevenness in the layer damages battery performance. To achieve this, the conductive layer slurry can be homogenized before being coated on the substrate to form the conductive layer. There are no particular limitations to the method used to homogenize the conductive layer slurry as long as all components of the conductive layer slurry are thoroughly mixed to form a homogeneous slurry, e.g., via the use of a homogenizer. In some embodiments, all the materials used to produce the conductive layer slurry are added into the homogenizer in a single batch. In other embodiments, the components of the conductive layer slurry are added to the homogenizer in more than one batch, and each batch may comprise more than one component. Any homogenizer that can reduce or eliminate particle aggregation and / or promote homogeneous distribution of conductive layer components in the electrode slurry can be used herein. In some embodiments, the homogenizer is a planetary stirring mixer, a stirring mixer, a blender, or an ultrasonicator.
[0138] In addition, there are no particular limitations to the conditions (e.g., temperature, stirring speed, length of time, etc. ) of the homogenization process so long as a homogenous slurry is formed in the end. In particular, the temperature at which the homogenization of the conductive layer slurry is performed should not be too high as to cause boiling of solvent, but at the same time be sufficiently high to ensure the slurry would not be too viscous to easily process and that the binder material can be readily dissolved in the slurry.
[0139] In some embodiments, homogenization of the conductive layer slurry occurs at room temperature or at a temperature of from about 20 ℃ to about 95 ℃. In some embodiments, the homogenization of the conductive layer slurry is performed at a temperature less than 95 ℃, less than 85 ℃, less than 75 ℃, less than 65 ℃, less than 55 ℃, less than 50 ℃, less than 45 ℃, less than 40 ℃, less than 35 ℃, less 30 ℃ or less than 25 ℃. In some embodiments, homogenization of the conductive layer slurry occurs at a temperature of more than 20 ℃, more than 25 ℃, more than 30 ℃, more than 35 ℃, more than 40 ℃, more than 45 ℃, more than 50 ℃, more than 55 ℃, more than 60 ℃, more than 65 ℃, more than 70 ℃ or more than 75 ℃.
[0140] In some embodiments, after homogenization of the conductive layer slurry, the slurry can be coated onto one side or both sides of a substrate to form a conductive layer film. There are no particular limitations to the equipment and the conditions used in coating the conductive layer slurry, except that a homogeneous, flat and smooth coated layer should be formed as a result. In certain embodiments, the coating process is performed using a doctor blade coater, a slot-die coater, a transfer coater, a spray coater, a roll coater, a gravure coater, a dip coater, or a curtain coater.
[0141] In some embodiments, following the coating of the conductive layer slurry onto a substrate, the coating is dried to form a modified current collector of the present invention. Any equipment that can dry the coating in order to affix the resultant conductive layer to the substrate can be used herein. Some non-limiting examples of such drying equipment include a vacuum drying oven, batch drying oven, a conveyor drying oven, and a microwave drying oven.
[0142] There are no particular limitations to the conditions used for drying, except that the drying conditions should be sufficient to ensure that the conductive layer adheres strongly to the substrate. However, drying the conductive layer at temperatures above 100 ℃ may result in undesirable deformation of the resultant modified current collector, thus affecting the performance of any electrode prepared therefrom. The drying temperature should be optimized with respect to the other drying conditions, such as drying time, in order to ensure that the solvent is sufficiently removed from the conductive layer.
[0143] In some embodiments, the modified current collector is compressed mechanically following drying in order to increase the density of the conductive layer. In other embodiments, the modified current collector is not compressed. The final density, surface density and thickness of the conductive layer should be within the ranges described in the relevant passages above.
[0144] An electrode can subsequently be prepared by forming an electrode layer on the modified current collector of the present invention. There are no particular limitations on the composition of the electrode layer, and any compositions known in the art are suitable for use in the present invention, as long as any battery comprising such electrodes can achieve good electrochemical performance. The composition of such electrode layers depends on the type of battery that is being produced, as well as whether the electrode layer is to be used in an anode or a cathode of a battery. In some embodiments, the type of battery may be a primary battery or a secondary battery. Some non-limiting examples of battery types include alkaline batteries, aluminum-air batteries, lithium batteries, lithium air batteries, magnesium batteries, silver-oxide batteries, zinc-air batteries, aluminum-ion batteries, lead-acid batteries, lithium-ion batteries, magnesium-ion batteries, potassium-ion batteries, sodium-ion batteries, sodium-air batteries, silicon-air batteries, zinc-ion batteries, and sodium-sulfur batteries. Furthermore, depending on the state of the electrolyte being used (i.e., liquid or solid state) , batteries can be classified as conventional batteries (when liquid electrolyte is used) or solid-state batteries (when solid electrolyte is used) .
[0145] In some embodiments, the electrode layer comprises an electrode active material and a binding agent. In certain embodiments, the electrode layer additionally comprises a conductive agent. The electrode active material in the electrode layer can be a cathode active material or an anode active material.
[0146] In some embodiments, the electrode active material is a cathode active material for a lithium-ion battery. In some embodiments, the cathode active material for a lithium-ion battery is selected from the group consisting of LiCoO2, LiNiO2, LiNi1-xMxO2, LiNixMnyO2, LiCoxNiyO2, Li1+zNixMnyCo1-x-yO2, LiNixCoyAlzO2, LiV2O5, LiTiS2, LiMoS2, LiMnO2, LiCrO2, LiMn2O4, Li2MnO3, LiFeO2, LiFePO4, and combinations thereof, wherein each x is independently from 0.1 to 0.9; each y is independently from 0 to 0.9; each z is independently from 0 to 0.4; and M is selected from the group consisting of Co, Mn, Al, Fe, Ti, Ga, Mg, and combinations thereof.
[0147] In certain embodiments, the cathode active material for a lithium-ion battery is selected from the group consisting of LiNixMnyO2, Li1+zNixMnyCo1-x-yO2 (NMC) , LiNixCoyAlzO2 (NCA) , LiCoxNiyO2, and combinations thereof, wherein each x is independently from 0.4 to 0.6; each y is independently from 0.2 to 0.4; and each z is independently from 0 to 0.1. In other embodiments, the cathode active material for a lithium-ion battery is not LiCoO2, LiNiO2, LiV2O5, LiTiS2, LiMoS2, LiMnO2, LiCrO2, LiMn2O4, LiFeO2 or LiFePO4. In further embodiments, the cathode active material for a lithium-ion battery is not LiNixMnyO2, Li1+zNixMnyCo1-x-yO2, LiNixCoyAlzO2 or LiCoxNiyO2, wherein each x is independently from 0.1 to 0.9; each y is independently from 0 to 0.45; and each z is independently from 0 to 0.2. In certain embodiments, the cathode active material is Li1+xNiaMnbCocAl (1-a-b-c) O2; wherein -0.2≤x≤0.2, 0≤a<1, 0≤b<1, 0≤c<1, and a+b+c≤1. In some embodiments, the cathode active material for a lithium-ion battery has the general formula LiMPO4, wherein M is selected from the group consisting of Fe, Co, Ni, Mn, Al, Mg, Zn, Ti, La, Ce, Sn, Zr, Ru, Si, Ge, and combinations thereof.
[0148] In some embodiments, the cathode active material for a lithium-ion battery is selected from the group consisting of LiFePO4, LiCoPO4, LiNiPO4, LiMnPO4, LiMnFePO4, LiMnxFe (1-x) PO4, and combinations thereof; wherein 0<x<1. In some embodiments, the cathode active material for a lithium-ion battery is LiNixMnyO4; wherein 0.1≤x≤0.9 and 0≤y≤2. In certain embodiments, the cathode active material for a lithium-ion battery is xLi2MnO3· (1-x) LiMO2, wherein M is selected from the group consisting of Ni, Co, Mn, and combinations thereof; and wherein 0<x<1. In some embodiments, the cathode active material for a lithium-ion battery is Li3V2 (PO4) 3, or LiVPO4F. In certain embodiments, the cathode active material for a lithium-ion battery has the general formula Li2MSiO4, wherein M is selected from the group consisting of Fe, Co, Mn, Ni, and combinations thereof.
[0149] In certain embodiments, the cathode active material for a lithium-ion battery is doped with a dopant selected from the group consisting of Co, Cr, V, Mo, Nb, Pd, F, Na, Fe, Ni, Mn, Al, Mg, Zn, Ti, La, Ce, Sn, Zr, Ru, Si, Ge, and combinations thereof. In some embodiments, the cathode active material for a lithium-ion battery is not doped with Co, Cr, V, Mo, Nb, Pd, F, Na, Fe, Ni, Mn, Mg, Zn, Ti, La, Ce, Ru, Si, or Ge. In certain embodiments, the cathode active material is not doped with Al, Sn or Zr.
[0150] In some embodiments, the cathode active material for a lithium-ion battery is LiNi0.33Mn0.33Co0.33O2 (NMC333) , LiNi0.4Mn0.4Co0.2O2, LiNi0.5Mn0.3Co0.2O2 (NMC532) , LiNi0.6Mn0.2Co0.2O2 (NMC622) , LiNi0.7Mn0.15Co0.15O2, LiNi0.7Mn0.1Co0.2O2, LiNi0.8Mn0.1Co0.1O2 (NMC811) , LiNi0.92Mn0.04Co0.04O2, LiNi0.85Mn0.075Co0.075O2, LiNi0.8Co0.15Al0.05O2, LiNi0.88Co0.1Al0.02O2, LiNiO2 (LNO) , or a combination thereof.
[0151] In other embodiments, the cathode active material for a lithium-ion battery is not LiCoO2, LiNiO2, LiMnO2, LiMn2O4 or Li2MnO3. In further embodiments, the cathode active material for a lithium-ion battery is not LiNi0.33Mn0.33Co0.33O2, LiNi0.4Mn0.4Co0.2O2, LiNi0.5Mn0.3Co0.2O2, LiNi0.6Mn0.2Co0.2O2, LiNi0.7Mn0.15Co0.15O2, LiNi0.7Mn0.1Co0.2O2, LiNi0.8Mn0.1Co0.1O2, LiNi0.92Mn0.04Co0.04O2, LiNi0.85Mn0.075Co0.075O2, LiNi0.8Co0.15Al0.05O2, or LiNi0.88Co0.1Al0.02O2.
[0152] In certain embodiments, the cathode active material for a lithium-ion battery comprises or is a core-shell composite having a core and shell structure, wherein the core comprises a lithium transition metal oxide selected from the group consisting of Li1+xNiaMnbCocAl (1-a-b-c) O2, LiCoO2, LiNiO2, LiMnO2, LiMn2O4, Li2MnO3, LiCrO2, Li4Ti5O12, LiV2O5, LiTiS2, LiMoS2, LiCoaNibO2, LiMnaNibO2, and combinations thereof; wherein -0.2≤x≤0.2, 0≤a<1, 0≤b<1, 0≤c<1, and a+b+c≤1. In some embodiments, the shell also comprises a lithium transition metal oxide. In certain embodiments, the lithium transition metal oxide of the shell is selected from the above-mentioned group of lithium transitional metal oxides used for the core. In other embodiments, the shell comprises a transition metal oxide. In certain embodiments, the transition metal oxide of the shell is selected from the group consisting of Fe2O3, MnO2, Al2O3, MgO, ZnO, TiO2, La2O3, CeO2, SnO2, ZrO2, RuO2, and combinations thereof. In certain embodiments, the shell comprises a lithium transition metal oxide and a transition metal oxide.
[0153] In certain embodiments, the core and the shell for a lithium-ion battery each independently comprises two or more lithium transition metal oxides. In some embodiments, one of the core or shell comprises only one lithium transition metal oxide, while the other comprises two or more lithium transition metal oxides. The lithium transition metal oxide or -oxides in the core and the shell may be the same, or they may be different or partially different. In some embodiments, the two or more lithium transition metal oxides are uniformly distributed over the core. In certain embodiments, the two or more lithium transition metal oxides are not uniformly distributed over the core.
[0154] In some embodiments, each of the lithium transition metal oxides and transition metal oxides in the core and the shell is independently doped with a dopant selected from the group consisting of Co, Cr, V, Mo, Nb, Pd, F, Na, Fe, Ni, Mn, Al, Mg, Zn, Ti, La, Ce, Sn, Zr, Ru, Si, Ge, and combinations thereof. In some embodiments, the cathode active material is not a core-shell composite.
[0155] In some embodiments, the electrode active material is a cathode active material for a sodium-ion battery. In some embodiments, the cathode active material for a sodium-ion battery is a Prussian blue-type sodium compound that satisfies the formula NaxMyAz, wherein M is one or more metals and A is one or more anions that comprise one or more of O, P, N, C, H or a halogen. In certain embodiments, the cathode active material for a sodium-ion battery is the sodium analogue of the cathode active materials discussed above, with lithium replaced by sodium. In some embodiments, the cathode active material for a sodium-ion battery is selected from the group consisting of NaCoO2, NaFeO2, NaNiO2, NaCrO2, NaVO2, and NaTiO2, NaFePO4, Na3V2 (PO4) 3, Na3V2 (PO4) 2F3, NMC-type mixed oxides, and combinations thereof. In some embodiments, the cathode active material for a sodium-ion battery is an organic material, such as disodium naphthalenediimide, doped quinone, pteridine derivatives, polyimides, polyamic acid, or a combination thereof.
[0156] In some embodiments, the cathode active material for a sodium-ion battery comprises or is a core-shell composite having a core and shell structure. In some embodiments, the cathode active material for a sodium-ion battery is doped with a dopant. The same dopants listed above for the cathode active material for a lithium-ion battery can be used to dope the cathode active material for a sodium-ion battery.
[0157] In some embodiments, the average diameter of the cathode active material particles is from about 0.1 μm to about 100 μm, from about 0.1 μm to about 50 μm, from about 0.5 μm to about 50 μm, from about 0.5 μm to about 30 μm, from about 0.5 μm to about 20 μm, from about 1 μm to about 20 μm, from about 5 μm to about 20 μm, from about 10 μm to about 20 μm, from about 5 μm to about 50 μm, from about 10 μm to about 50 μm, from about 20 μm to about 50 μm or from about 50 μm to about 100 μm.
[0158] In some embodiments, the average diameter of the cathode active material particles is less than 100 μm, less than 80 μm, less than 60 μm, less than 50 μm, less than 40 μm, less than 30 μm, less than 20 μm, less than 15 μm, less than 10 μm, less than 7.5 μm, less than 5 μm, less than 2.5 μm, less than 1 μm, less than 0.75 μm or less than 0.5 μm. In some embodiments, the average diameter of the cathode active material particles is more than 0.1 μm, more than 0.25 μm, more than 0.5 μm, more than 0.75 μm, more than 1 μm, more than 2.5 μm, more than 5 μm, more than 7.5 μm, more than 10 μm, more than 15 μm, more than 20 μm, more than 30 μm, more than 40 μm or more than 50 μm.
[0159] In some embodiments, the electrode active material is an anode active material. In some embodiments, the anode active material is selected from the group consisting of natural graphite particulate, synthetic graphite particulate, hard carbon, soft carbon, mesocarbon microbeads (MCMB) , Sn particulate, SnO2, SnO, Li4Ti5O12 particulate, Si particulate, Si-C composite particulate, and combinations thereof.
[0160] In certain embodiments, the anode active material is doped with a metallic element or a nonmetal element. In some embodiments, the metallic element is selected from the group consisting of Fe, Ni, Mn, Al, Mg, Zn, Ti, La, Ce, Sn, Zr, Ru, and combinations thereof. In some embodiments, the nonmetal element is B, Si, Ge, N, P, F, S, Cl, I, Se, or a combination thereof.
[0161] Modified current collectors of the present invention are particularly suitable for use in electrodes where the electrode layer is formed using a water-based electrode slurry and comprises a nickel-containing cathode active material. Such a slurry would be quite basic in nature and would therefore corrode a conventional current collector (most commonly aluminum foil) . However, when a basic water-based cathode slurry is coated onto a modified current collector of the present invention to form a cathode, the conductive layer in the modified current collector would form a physical barrier to prevent the conventional current collector (i.e., the substrate of the modified current collector) from coming into contact with the slurry. Corrosion of the substrate is hence prevented. Nonetheless, modified current collectors of the present invention are suitable for use in electrodes comprising any suitable electrode active materials (both cathode active materials and anode active materials) , for any type of battery, and using any method of formation of the electrode layer on the modified current collectors.
[0162] In some embodiments, the electrode slurry comprises a solvent in addition to the various electrode components that are to form the electrode layer, such as electrode active materials, binding agents and conductive agents. In some embodiments, the solvent of the electrode slurry is an aqueous solvent. In some embodiments, the aqueous solvent is water. In certain embodiments, the aqueous solvent in the electrode slurry further comprises a minor component in addition to water. In some embodiments, the volume ratio of water to the minor component is from about 51: 49 to about 99: 1.
[0163] Any water-miscible or volatile solvents, including all of the minor components of the solvent of the conductive layer slurry described above, can be used as the minor component of the aqueous solvent of the electrode slurry. When the aqueous solvent of the electrode slurry comprises a minor component in addition to water, said minor component may be the same as the minor component of the solvent of the conductive layer slurry, or they may be different or partially different. Some non-limiting examples of the minor component include alcohols, lower aliphatic ketones, lower alkyl acetates, and combinations thereof. The addition of a minor component may improve the processibility of the electrode slurry.
[0164] There are no particular limitations to the binding agent used in the electrode layer, although the binding agent should have desirable properties as a binder. For example, it is preferable that the binding agent can be dispersed well in the electrode slurry to ensure an even, smooth coating. When coated on the surface of the modified current collector, the electrode slurry comprising the binding agent should not be able to dissolve the conductive layer of the modified current collector. In some embodiments, more than one binding agent is used in the electrode layer, as long as they do not dissolve the conductive layer of the modified current collector. In some embodiments, the binding agent is water-soluble.
[0165] In some embodiments, the binding agent in the electrode layer comprises a polymer. In some embodiments, the binder polymer in the electrode layer is a copolymer. In other embodiments, the binder polymer in the electrode layer is a homopolymer.
[0166] In certain embodiments, the binding agent in the electrode layer comprises styrene-butadiene rubber (SBR) , carboxymethyl cellulose (CMC) , polyacrylic acid (PAA) , polyacrylonitrile (PAN) , polyacrylamide (PAM) , acrylic acid-acrylonitrile-acrylamide copolymer, latex, a salt of alginic acid, polyvinylidene fluoride (PVDF) , poly (vinylidene fluoride) -hexafluoropropene (PVDF-HFP) , polytetrafluoroethylene (PTFE) , polystyrene, poly (vinyl alcohol) (PVA) , poly (vinyl acetate) , polyisoprene, polyaniline, polyethylene, polyimide, polyurethane, polyvinyl butyral, polyvinyl pyrrolidone (PVP) , gelatin, chitosan, starch, agar-agar, xanthan gum, gum arabic, gellan gum, guar gum, gum karaya, tara gum, gum tragacanth, casein, amylose, pectin, PEDOT: PSS, carrageenans, or a combination thereof. In certain embodiments, the salt of alginic acid comprises a cation selected from the group consisting of Na, Li, K, Ca, NH4, Mg, Al, and combinations thereof. In certain embodiments, the binding agent in the electrode layer does not comprise styrene-butadiene rubber, carboxymethyl cellulose, polyacrylic acid, polyacrylonitrile, polyacrylamide, acrylic acid-acrylonitrile-acrylamide copolymer, latex, a salt of alginic acid, polyvinylidene fluoride, poly (vinylidene fluoride) -hexafluoropropene, polytetrafluoroethylene, polystyrene, poly (vinyl alcohol) , poly (vinyl acetate) , polyisoprene, polyaniline, polyethylene, polyimide, polyurethane, polyvinyl butyral, polyvinyl pyrrolidone, gelatin, chitosan, starch, agar-agar, xanthan gum, gum arabic, gellan gum, guar gum, gum karaya, tara gum, gum tragacanth, casein, amylose, pectin, PEDOT: PSS, or carrageenans. In certain embodiments, the binding agent in the electrode layer does not comprise a fluorine-containing polymer such as PVDF, PVDF-HFP or PTFE.
[0167] In some embodiments, the binding agent in the electrode layer comprises one or more functional groups containing a halogen, O, N, S, or a combination thereof. Some non-limiting examples of suitable functional groups include alkoxy, aryloxy, nitro, thiol, alkylthio, imine, cyano, amide, amino (primary, secondary or tertiary) , carboxyl, epoxy, ketone, aldehyde, ester, hydroxyl, halo (fluoro, chloro, bromo, or iodo) , and combinations thereof. In some embodiments, the functional group is or comprises carboxylic acid (i.e., -COOH) , carboxylic acid salt, sulfonic acid, sulfonic acid salt, sulfuric acid, sulfuric acid salt, phosphonic acid, phosphonic acid salt, phosphoric acid, phosphoric acid salt, nitric acid, nitric acid salt, amide, hydroxyl, nitrile, ester, epoxy, or -NH2.
[0168] In some embodiments, the binding agent has structural units in the same manner as the stabilizing agent of the conductive layer. In certain embodiments, the composition of the binding agent can be the same as, different to or partially different to the composition of the stabilizing agent.
[0169] In some embodiments, the electrode layer additionally comprises a conductive agent. The presence of a conductive agent enhances the electrically-conducting properties of the electrode layer in an electrode. Therefore, it may be advantageous for the electrode layer to comprise a conductive agent. Any suitable material can act as a conductive agent. Any embodiments of conductive material suitable for use in the conductive layer of a modified current collector of the present invention are also suitable for use as conductive agent in the electrode layer. In other embodiments, the conductive agent is not a conductive material used in the conductive layer of a modified current collector. The conductive agent used in the electrode layer and the conductive material used in the conductive layer of a modified current collector may be the same, different, or partially different.
[0170] In some embodiments, the conductive agent comprises a conductive polymer selected from the group consisting of polypyrrole, polyaniline, polyacetylene, polyphenylene sulfide (PPS) , polyphenylene vinylene (PPV) , poly (3, 4-ethylenedioxythiophene) (PEDOT) , polythiophene, and combinations thereof. In some embodiments, the conductive polymer plays two roles simultaneously, not only as a conductive agent but also as a binder. In other embodiments, the conductive agent does not comprise a conductive polymer.
[0171] In some embodiments, the proportion of electrode active material in the electrode layer is from about 60%to about 99%, from about 70%to about 99%, from about 75%to about 99%, from about 80%to about 99%, from about 85%to about 99%, from about 90%to about 99%, from about 60%to about 95%, from about 65%to about 95%, from about 70%to about 95%, from about 75%to about 95%, from about 80%to about 95%, from about 85%to about 95%, from about 60%to about 90%, from about 65%to about 90%, from about 70%to about 90%, from about 75%to about 90%, from about 80%to about 90%, from about 60%to about 85%, from about 65%to about 85%, from about 70%to about 85%, from about 75%to about 85%, from about 60%to about 80%, from about 65%to about 80%, or from about 70%to about 80%by weight, based on the total weight of the electrode layer.
[0172] In some embodiments, the proportion of electrode active material in the electrode layer is less than 99%, less than 95%, less than 90%, less than 85%, less than 80%, less than 75%, less than 70%, or less than 65%by weight, based on the total weight of the electrode layer. In some embodiments, the proportion of electrode active material in the electrode layer is more than 60%, more than 65%, more than 70%, more than 75%, more than 80%, more than 85%, more than 90%, or more than 95%by weight, based on the total weight of the electrode layer.
[0173] In some embodiments, the proportion of binding agent and conductive agent in the electrode layer is each independently from about 1%to about 20%, from about 2%to about 20%, from about 3%to about 20%, from about 4%to about 20%, from about 5%to about 20%, from about 6%to about 20%, from about 7%to about 20%, from about 8%to about 20%, from about 9%to about 20%, from about 10%to about 20%, from about 15%to about 20%, from about 1%to about 15%, from about 2%to about 15%, from about 3%to about 15%, from about 4%to about 15%, from about 5%to about 15%, from about 6%to about 15%, from about 7%to about 15%, from about 8%to about 15%, from about 9%to about 15%, from about 10%to about 15%, from about 1%to about 10%, from about 2%to about 10%, from about 3%to about 10%, from about 4%to about 10%, from about 5%to about 10%, from about 1%to about 5%, from about 2%to about 5%, or from about 3%to about 5%by weight, based on the total weight of the electrode layer.
[0174] In some embodiments, the proportion of binding agent and conductive agent in the electrode layer is each independently less than 20%, less than 19%, less than 18%, less than 17%, less than 16%, less than 15%, less than 14%, less than 13%, less than 12%, less than 11%, less than 10%, less than 9%, less than 8%, less than 7%, or less than 6%by weight, based on the total weight of the electrode layer. In some embodiments, the proportion of binding agent and conductive agent in the electrode layer is each independently more than 1%, more than 2%, more than 3%, more than 4%, more than 5%, more than 6%, more than 7%, more than 8%, more than 9%, more than 10%, more than 11%, more than 12%, more than 13%, more than 14%, or more than 15%by weight, based on the total weight of the electrode layer.
[0175] In some embodiments, the electrode layer of an electrode may additionally comprise other additives for enhancing electrode properties. In some embodiments, the additives may include surfactants, dispersants and flexibility-enhancing additives, salts, ion conductive polymers, and inorganic solid-state electrolytes.
[0176] In some embodiments, the solid content of the electrode slurry is from about 40%to about 80%, from about 40%to about 75%, from about 40%to about 70%, from about 40%to about 65%, from about 40%to about 60%, from about 40%to about 55%, from about 45%to about 80%, from about 45%to about 75%, from about 45%to about 70%, from about 45%to about 65%, from about 45%to about 60%, from about 50%to about 80%, from about 50%to about 75%, from about 50%to about 70%, from about 50%to about 65%, from about 55%to about 80%, from about 55%to about 75%, from about 55%to about 70%, from about 60%to about 80%, from about 60%to about 75%, from about 65%to about 80%, from about 65%to about 75%, or from about 70%to about 80%by weight, based on the total weight of the electrode slurry.
[0177] In some embodiments, the solid content of the electrode slurry is less than 80%, less than 75%, less than 70%, less than 65%, less than 60%, less than 55%, or less than 50%by weight, based on the total weight of the electrode slurry. In some embodiments, the solid content of the electrode slurry is more than 40%, more than 45%, more than 50%, more than 55%, more than 60%, more than 65%, or more than 70%by weight, based on the total weight of the electrode slurry.
[0178] There are no particular limitations on the method used to produce an electrode slurry from the various electrode components, except that all electrode components should be mixed to form a homogeneous electrode slurry, for example through mixing in a homogenizer. The method and conditions of the homogenization process of the electrode slurry can be the same as, different to or partially different to those of the homogenization of the conductive layer slurry.
[0179] In some embodiments, after homogenization of an electrode slurry, the electrode slurry can be coated onto one side or both sides of a modified current collector of the present invention to form an electrode layer. The method and conditions of the coating process of the electrode slurry can be the same as, different to or partially different to those of the coating process of the conductive layer slurry.
[0180] In some embodiments, following the coating of the electrode slurry onto a modified current collector of the present invention, the coating is dried. Any equipment that can dry the coating in order to affix the electrode layer onto the modified current collector can be used herein.
[0181] There are no particular limitations to the conditions used for drying, except that the drying conditions should be sufficient to ensure that the electrode layer adheres strongly to the modified current collector. However, drying the electrode slurry at temperatures above 100 ℃ may result in undesirable deformation of the electrode, thus affecting the performance of the resultant electrode. In some embodiments, the resultant electrode is compressed mechanically following drying of the film in order to increase the density of the electrode.
[0182] In certain embodiments, the thickness of the electrode layer is from about 5 μm to about 90 μm, from about 5 μm to about 50 μm, from about 5 μm to about 25 μm, from about 10 μm to about 90 μm, from about 10 μm to about 50 μm, from about 10 μm to about 30 μm, from about 15 μm to about 90 μm, from about 20 μm to about 90 μm, from about 25 μm to about 90 μm, from about 25 μm to about 80 μm, from about 25 μm to about 70 μm, from about 25 μm to about 50 μm, from about 30 μm to about 90 μm, or from about 30 μm to about 80 μm. In some embodiments, the thickness of the electrode layer is more than 5 μm, more than 10 μm, more than 15 μm, more than 20 μm, more than 25 μm, more than 30 μm, more than 40 μm, more than 50 μm, more than 60 μm, more than 70 μm, or more than 80 μm. In some embodiments, the thickness of the electrode layer is less than 90 μm, less than 80 μm, less than 70 μm, less than 60 μm, less than 50 μm, less than 40 μm, less than 30 μm, less than 25 μm, less than 20 μm, less than 15 μm, or less than 10 μm.
[0183] In some embodiments, the surface density of the electrode layer is from about 1 mg / cm2 to about 50 mg / cm2, from about 2.5 mg / cm2 to about 50 mg / cm2, from about 5 mg / cm2 to about 50 mg / cm2, from about 10 mg / cm2 to about 50 mg / cm2, from about 15 mg / cm2 to about 50 mg / cm2, from about 20 mg / cm2 to about 50 mg / cm2, from about 30 mg / cm2 to about 50 mg / cm2, from about 1 mg / cm2 to about 30 mg / cm2, from about 2.5 mg / cm2 to about 30 mg / cm2, from about 5 mg / cm2 to about 30 mg / cm2, from about 10 mg / cm2 to about 30 mg / cm2, from about 15 mg / cm2 to about 30 mg / cm2, from about 20 mg / cm2 to about 30 mg / cm2, from about 1 mg / cm2 to about 20 mg / cm2, from about 2.5 mg / cm2 to about 20 mg / cm2, from about 5 mg / cm2 to about 20 mg / cm2, from about 10 mg / cm2 to about 20 mg / cm2, from about 1 mg / cm2 to about 15 mg / cm2, from about 2.5 mg / cm2 to about 15 mg / cm2, from about 5 mg / cm2 to about 15 mg / cm2, or from about 10 mg / cm2 to about 15 mg / cm2.
[0184] In some embodiments, the surface density of the electrode layer is less than 50 mg / cm2, less than 40 mg / cm2, less than 30 mg / cm2, less than 20 mg / cm2, less than 15 mg / cm2, less than 10 mg / cm2, less than 5 mg / cm2, or less than 2.5 mg / cm2. In some embodiments, the surface density of the electrode layer is more than 1 mg / cm2, more than 2.5 mg / cm2, more than 5 mg / cm2, more than 10 mg / cm2, more than 15 mg / cm2, more than 20 mg / cm2, more than 30 mg / cm2, or more than 40 mg / cm2.
[0185] In an electrode comprising a modified current collector of the present invention, the electrode layer exhibits strong adhesion to the modified current collector. It is important for the electrode layer to have a high peeling strength with respect to the modified current collector, as this prevents delamination or separation of the electrode, which would greatly impact the mechanical stability of the electrode and the cyclability of a battery comprising the electrode. Therefore, the electrodes should have sufficient peeling strength to withstand the rigors of battery manufacture.
[0186] In some embodiments, the peeling strength between the electrode layer and the modified current collector is in the range of from about 1.0 N / cm to about 8.0 N / cm, from about 1.0 N / cm to about 6.0 N / cm, from about 1.0 N / cm to about 5.0 N / cm, from about 1.0 N / cm to about 4.0 N / cm, from about 1.0 N / cm to about 3.0 N / cm, from about 1.0 N / cm to about 2.0 N / cm, from about 2.0 N / cm to about 8.0 N / cm, from about 2.0 N / cm to about 6.0 N / cm, from about 2.0 N / cm to about 5.0 N / cm, from about 2.0 N / cm to about 3.0 N / cm, from about 3.0 N / cm to about 8.0 N / cm, from about 3.0 N / cm to about 6.0 N / cm, or from about 4.0 N / cm to about 6.0 N / cm.
[0187] In some embodiments, the peeling strength between the electrode layer and the modified current collector is more than 1.0 N / cm, more than 1.5 N / cm, more than 2.0 N / cm, more than 2.5 N / cm, more than 3.0 N / cm, more than 3.5 N / cm, more than 4.0 N / cm, more than 4.5 N / cm, more than 5.0 N / cm, more than 5.5 N / cm, more than 6.0 N / cm, more than 6.5 N / cm, or more than 7.0 N / cm. In some embodiments, the peeling strength between the electrode layer and the modified current collector is less than 8.0 N / cm, less than 7.5 N / cm, less than 7.0 N / cm, less than 6.5 N / cm, less than 6.0 N / cm, less than 5.5 N / cm, less than 5.0 N / cm, less than 4.5 N / cm, less than 4.0 N / cm, less than 3.5 N / cm, less than 3.0 N / cm, less than 2.5 N / cm, less than 2.0 N / cm, or less than 1.5 N / cm.
[0188] In some embodiments, once an electrode comprising a modified current collector is formed, the electrode can be assembled with an electrode of opposite polarity and an electrolyte to form a battery.
[0189] In some embodiments, the electrolyte is a liquid electrolyte. Such a liquid electrolyte comprises an electrolyte solvent and a salt. In some embodiments, the electrolyte solvent is water; the liquid electrolyte is then an aqueous electrolyte. In other embodiments, the electrolyte solvent is a liquid composed of one or more organic solvents; the liquid electrolyte is then a non-aqueous electrolyte. In some embodiments, each organic solvent is selected from a carbonate-based, ester-based, ether-based or other aprotic solvent. Some non-limiting examples of the carbonate-based solvent include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, and combinations thereof. Some non-limiting examples of the ester-based solvent include methyl acetate, methyl propanoate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate, and combinations thereof. Some non-limiting examples of the ether-based solvent include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and combinations thereof. Some non-limiting examples of the other aprotic solvent include methyl bromide, ethyl bromide, methyl formate, acetonitrile, dimethyl sulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, and combinations thereof.
[0190] In some embodiments, the liquid electrolyte is for a conventional lithium-ion battery. The salt in the liquid electrolyte is then a lithium salt. In some embodiments, the lithium salt is selected from the group consisting of LiPF6, LiBO2, LiBF4, LiSbF6, LiAsF6, LiAlCl4, LiClO4, LiCl, LiI, LiNO3, LiB (C2O4) 2, LiSO3CF3, LiN (SO2F) 2, LiN (SO2CF3) 2, LiN (SO2CF2CF3) 2, LiC2H3O2, and combinations thereof.
[0191] In some embodiments, the liquid electrolyte is for a conventional sodium-ion battery. The salt in the liquid electrolyte is then a sodium salt. In some embodiments, the sodium salt is the sodium analogue of the lithium salts discussed above, with the lithium replaced by sodium. Such sodium salts include NaPF6, NaBF4, NaN (SO2CF3) 2, NaN (SO2F) 2, NaClO4, NaSO3CF3, and combinations thereof. In some embodiments, the salt present in the liquid electrolyte for a conventional sodium-ion battery is one or more of NaMFx; wherein each x=4 or 6; and wherein each M is selected from the group consisting of Al3+, B3+, Ga3+, In3+, Sc3+, Y3+, La3+, P5+, As5+, and combinations thereof.
[0192] In some embodiments, the electrolyte is a solid-state electrolyte. In some embodiments, the solid-state electrolyte is a polymer electrolyte. Such a polymer electrolyte comprises an ion-conductive polymer as well as a salt. Some non-limiting examples of the ion-conductive polymer include polyether, polycarbonate, polyacrylate, polysiloxane, polyphosphazene, polyethylene derivative, alkylene oxide derivative, phosphate polymer, poly-lysine, polyester sulfide, polyvinyl alcohol, and polyvinylidene fluoride. In some embodiments, the ion-conductive polymer is selected from the group consisting of polyacrylonitrile (PAN) , polyethylene carbonate (PEC) , polyacrylamide (PAM) , polyethylene glycol (PEG) , polyethylene oxide (PEO) , polyhydroxyethylmethacrylate (P (HEMA) ) , polyphosphonate (PPh) , polysiloxane, polyamide (PA) , polydilactone, polydiester, polyphasphazene (PPHOS) , polyurethane (PU) , copolymers thereof, and combinations thereof. Some non-limiting examples of the salt present in the polymer electrolyte include the lithium and sodium salts mentioned above for the liquid electrolyte.
[0193] In some embodiments, the solid-state electrolyte is an inorganic solid-state electrolyte. Any known inorganic solid-state electrolyte can be used. Some non-limiting examples include sulfides, lithium superionic conductor (LISICON) type compounds, lithium lanthanum titanate (LLTO) type compounds, and perovskite compounds.
[0194] In some embodiments, the solid-state electrolyte is a gel electrolyte. Such a gel electrolyte comprises a polymer electrolyte and an electrolyte solvent.
[0195] Due to the presence of a conductive layer in a modified current collector of the present invention, batteries comprising electrodes that use the modified current collector exhibit exceptional electrochemical performance. Compared to a conventional current collector, a modified current collector of the present invention brings about considerable improvement to the electrode, such improvement being made possible by the contribution of each individual component present in the conductive layer of the modified current collector. In particular, the conductive material decreases the interfacial resistance between the modified current collector and the electrode layer, thereby reducing inherent capacity losses that arise from the internal resistance of the electrodes in a battery. The conductive layer also acts as a physical barrier to prevent corrosion of the substrate. The binder material not only provides more effective binding force between the conductive material particles themselves and between the conductive material particles and the substrate, but also improves the mechanical strength of the electrode as a whole. Furthermore, the binder material within the conductive layer still maintains excellent binding properties even if an aqueous electrode slurry is applied on the conductive layer, preventing the conductive layer from disintegrating or delaminating from the substrate.
[0196] The following examples are presented to exemplify embodiments of the invention but are not intended to limit the invention to the specific embodiments set forth. Unless indicated to the contrary, all parts and percentages are by weight. All numerical values are approximate. When numerical ranges are given, it should be understood that embodiments outside the stated ranges may still fall within the scope of the invention. Specific details described in each example should not be construed as necessary features of the invention.
[0197] EXAMPLES
[0198] The interfacial resistance of the cathode was measured using an electrode resistance measurement system (RM2610, HIOKI) .
[0199] The adhesive strengths of the binder materials when dried were measured by a tensile testing machine (DZ-106A, obtained from Dongguan Zonhow Test Equipment Co. Ltd., China) . This test measures the average force required to peel a layer of dried binder material from an aluminum substrate at 180° angle in Newtons. The mean roughness depth (Rz) of the substrate is 2 μm. A binder material solution was coated on the substrate and dried to obtain a dried binder layer of thickness 10 μm to 12 μm. The coated substrate was then placed in an environment of constant temperature of 25 ℃ and humidity of 50%to 60%for 30 minutes. A strip of adhesion tape (3M; US; model no. 810) with a width of 18 mm and a length of 20 mm was attached onto the surface of the dried binder layer. The coated substrate was clipped onto the testing machine and the tape was folded back on itself at 180 degrees, and placed in a moveable jaw and pulled at room temperature and a peel rate of 300 mm per minute. The maximum stripping force measured was taken as the adhesive strength. Measurements were repeated three times to find the average value.
[0200] Example 1
[0201] A) Preparation of Binder Material Solution
[0202] 0.94 g of sodium lauryl polyoxyethylene ether sulfate (SLES) and 0.41 g of polyoxyethylene nonylphenol ether (NP-9) were added into a round-bottomed flask containing 101.14 g of de-ionized water while stirring with an overhead stirrer (R20, IKA) . This mixture was stirred at a speed of 200 rpm for 5 minutes at 25 ℃ to obtain a first mixture.
[0203] 3.63 g of 2-ethylhexyl acrylate (EHA; monomer of structural unit (b) ) and 8.71 g of methyl methacrylate (MMA; monomer of structural unit (c) ) were added into the first mixture. This mixture was stirred at 500 rpm for 25 minutes at 25 ℃, then at 200 rpm for 5 minutes at 80 ℃ to obtain a second mixture.
[0204] 0.17 g of water-soluble free radical initiator (ammonium persulfate, APS; obtained from Aladdin Industries Corporation, China) was dissolved in 6.57 g of DI water. The APS solution was added into the second mixture. This mixture was stirred at 200 rpm for 30 minutes at 80 ℃ to obtain a third mixture.
[0205] A pre-emulsion was prepared separately. 1.62 g of SLES and 0.81 g of NP-9 were dispersed in 74.17 g of DI water at a speed of 200 rpm for 5 minutes at 25 ℃. Then, 52.46 g of 2- (perfluorohexyl) ethyl methacrylate (PFHEM; monomer of structural unit (a) ) , 69.06 g of EHA, 34.84 g of MMA, 2.18 g and 2.16 g of methacrylic acid and acrylamide respectively (MAA and AM respectively; together, monomers of structural unit (d) ) , and 1.14 g of 1, 6-hexanediol diacrylate (HDDA; monomer of structural unit (e) ) were added. Following the addition of the monomers, the mixture was further stirred at a speed of 200 rpm for 30 minutes at 25 ℃ to form the pre-emulsion. The pre-emulsion was added dropwise to the third mixture. This addition took about 2.5 hours.
[0206] At the same time as the preparation of the pre-emulsion, an initiator solution was prepared. 0.27 g of APS and 0.34 g of reducing agent (sodium bicarbonate) were dissolved in 44.2 g of DI water. This mixture was stirred at 200 rpm for 30 minutes at 25 ℃ to obtain the initiator solution. 30 minutes after the pre-emulsion was first added into the third mixture, the initiator solution was also added dropwise to the third mixture. This addition took about 2 hours, after which the fourth mixture is formed.
[0207] The fourth mixture was stirred at 200 rpm for 60 minutes at 80 ℃, then further at 150 rpm for 60 minutes at 85 ℃ to obtain a fifth mixture. After the complete reaction, the temperature of the fifth mixture was lowered to 25 ℃. 1.09 g of sodium hydroxide (NaOH) was dissolved in 25.0 g of DI water. Thereafter, all of the sodium hydroxide solution was added dropwise into the fifth mixture for 1 h to adjust pH to 7.6 to form the sixth mixture. The sixth mixture was filtered using 200 μm nylon mesh to form the binder material solution. The solid content of the binder material solution is 41.3 wt. %.
[0208] B) Preparation of Stabilizing Agent Solution
[0209] 11.90 g of NaOH was added into a round-bottom flask containing 380 g of distilled water. The sodium hydroxide solution was stirred at 80 rpm for 30 mins to obtain a first suspension.
[0210] 24.78 g of acrylic acid was added into the first suspension. The mixture was further stirred at 80 rpm for 30 mins to obtain a second suspension.
[0211] 7.19 g of acrylamide (AM) was dissolved in 10 g of DI water to form an AM solution. Thereafter, all of the AM solution was added into the second suspension. The mixture was further heated to 55 ℃ and stirred at 80 rpm for 45 mins to obtain a third suspension.
[0212] 30.06 g of acrylonitrile (AN) was added into the third suspension. The mixture was further stirred at 80 rpm for 10 mins to obtain a fourth suspension.
[0213] Furthermore, 0.015 g of APS was dissolved in 3 g of DI water and 0.0075 g of reducing agent (sodium bisulfite; obtained from Tianjin Damao Chemical Reagent Factory, China) was dissolved in 1.5 g of DI water. All of the APS solution and the sodium bisulfite solution were added into the fourth suspension. The mixture was stirred at 200 rpm for 24 h at 55 ℃ to obtain a fifth suspension.
[0214] After the complete reaction, the temperature of the fifth suspension was lowered to 25 ℃. 3.72 g of NaOH was dissolved in 400 g of DI water. Thereafter, all of the NaOH solution was added dropwise into the fifth suspension to adjust pH to 7.3 to form the stabilizing agent solution. The solid content of the stabilizing agent solution is 8.31 wt. %.
[0215] C) Preparation of Conductive Layer Slurry
[0216] 6.02 g of the stabilizing agent solution was added into 230.52 g of DI water. After the addition, this mixture was stirred for about 15 mins at 25 ℃ at a speed of 1,200 rpm to form a first mixture.
[0217] 54.5 g of graphite powder (obtained from Timcal Ltd, Bodio, Switzerland) was added into the first mixture. After the addition, the mixture was stirred for about 3 hours at 25 ℃ at a speed of 1,200 rpm to form a second mixture.
[0218] 108.96 g of the binder material solution was added into the second mixture. After the addition, this mixture was stirred for about 60 minutes at 25 ℃ at a speed of 800 rpm to form the conductive layer slurry. The solid content of the conductive layer slurry is 25 wt. %.
[0219] D) Preparation of Modified Current Collector
[0220] An aluminum foil having a thickness of 16 μm was used as a substrate. The conductive layer slurry was coated onto both sides of the substrate using a doctor blade coater with a gap width of 8 μm. The coated slurry of 4.5 μm on the aluminum foil was dried to form a conductive layer using an electrically heated oven at 85 ℃. The drying time was about 30 mins.
[0221] E) Preparation of Binding Agent Solution
[0222] A binding agent solution was prepared in the same manner as that of the stabilizing agent solution, except that 18.15 g of NaOH was added in the preparation of the first suspension, 36.04 g of acrylic acid was added in the preparation of the second suspension, 19.04 g of acrylamide was added in the preparation of the third suspension and 12.92 g of acrylonitrile was added in the preparation of the fourth suspension. The solid content of the binding agent solution is 9.00 wt. %.
[0223] F) Preparation of Positive Electrode
[0224] A first mixture was prepared by dispersing 12 g of conductive agent (Super P; obtained from Timcal Ltd, Bodio, Switzerland) and 100 g of the binding agent solution (9.00 wt. %solid content) in 74 g of deionized water while stirring with an overhead stirrer (R20, IKA) . After the addition, the first mixture was further stirred for about 30 mins at 25 ℃ at a speed of 1,200 rpm.
[0225] Thereafter, a second mixture was prepared by adding 276 g of NMC811 (obtained from Shandong Tianjiao New Energy Co., Ltd, China) to the first mixture at 25 ℃ while stirring with an overhead stirrer. Then, the second mixture was degassed under a pressure of about 10 kPa for 1 hour. The second mixture was further stirred for about 60 mins at 25 ℃ at a speed of 1,200 rpm to form a homogenized cathode slurry.
[0226] The homogenized cathode slurry was coated onto both sides of the surface of the modified current collector prepared above using a doctor blade coater with a gap width of 120 μm.The coated slurry of 80 μm on the modified current collector was dried to form a cathode layer using an electrically heated oven at 70 ℃. The drying time was about 10 mins. The electrode was then pressed to decrease the thickness of the cathode layer to 23 μm. The surface density of the cathode layer on the modified current collector is 7.00 mg / cm2.
[0227] G) Assembly of Coin Cell
[0228] The electrochemical performance of the cathode prepared above was tested in a CR2032 coin-type Li cell assembled in an argon-filled glove box. The cathode was cut into disc-form shapes for coin-type cell assembly. A lithium metal foil having a thickness of 500 μm was used as an anode. The cathode and anode were kept apart by a separator. The separator was a ceramic coated microporous membrane made of nonwoven fabric (MPM, Japan) , which had a thickness of about 25 μm. The electrode assembly was then dried in a box-type resistance oven under vacuum (DZF-6020, obtained from Shenzhen Kejing Star Technology Co. Ltd., China) at 105 ℃ for about 16 hours.
[0229] An electrolyte was then injected into the case holding the packed electrodes under a high-purity argon atmosphere with a moisture and oxygen content of less than 3 ppm respectively. The electrolyte was a solution of LiPF6 (1 M) in a mixture of ethylene carbonate (EC) , ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) at a volume ratio of 1: 1: 1. After electrolyte filling, the coin cell was mechanically pressed using a punch tooling with a standard circular shape.
[0230] H) Electrochemical Measurements
[0231] The coin cell was analyzed in a constant current mode using a multi-channel battery tester (BTS-4008-5V10mA, obtained from Neware Electronics Co. Ltd, China) . After 1 cycle at C / 20 was completed, they were charged and discharged at a rate of C / 2. The charging / discharging cycling tests of the cells were performed between 3.0 and 4.3 V at a current density of C / 2 at 25 ℃ to obtain the discharge capacity. The electrochemical performance of the coin cell of Example 1 was measured and is shown in Table 1 below.
[0232] Preparation of Binder Material Solutions of Examples 2-3 and 9-15, Comparative Examples 1 and 5-6
[0233] The binder material solutions of Examples 2-3 and 9-15, and Comparative Examples 1 and 5-6 were prepared in the same manner as in Example 1.
[0234] Preparation of Binder Material Solution of Example 4
[0235] The binder material solution of Example 4 was prepared in the same manner as in Example 1, except that 5.31 g of EHA and 4.66 g of MMA were added to form the second mixture, and 1.62 g of SLES, 0.81 g of NP-9, 74.17 g of DI water, 61.20 g of PFHEM, 100.94 g of EHA, 18.63 g of MMA, 2.18 g of MAA, 2.16 g of AM and 1.14 g of HDDA were added in the formation of the pre-emulsion. The solid content of the binder material solution is 44.5 wt. %.
[0236] Preparation of Binder Material Solution of Example 5
[0237] The binder material solution of Example 5 was prepared in the same manner as in Example 1, except that 2.14 g of EHA and 11.54 g of MMA were added to form the second mixture, and 1.62 g of SLES, 0.81 g of NP-9, 74.17 g of DI water, 61.20 g of PFHEM, 40.73 g of EHA, 46.18 g of MMA, 2.18 g of MAA, 2.16 g of AM and 1.14 g of HDDA were added in the formation of the pre-emulsion. The solid content of the binder material solution is 40.4 wt. %.
[0238] Preparation of Binder Material Solution of Example 6
[0239] The binder material solution of Example 6 was prepared in the same manner as in Example 1, except that 3.82 g of EHA and 9.32 g of MMA were added to form the second mixture, and 1.62 g of SLES, 0.81 g of NP-9, 74.17 g of DI water, 30.60 g of PFHEM, 72.60 g of EHA, 37.27 g of MMA, 2.18 g of MAA, 2.16 g of AM and 1.14 g of HDDA were added in the formation of the pre-emulsion. The solid content of the binder material solution is 39.5 wt. %.
[0240] Preparation of Binder Material Solution of Example 7
[0241] The binder material solution of Example 7 was prepared in the same manner as in Example 1, except that 3.08 g of EHA and 6.89 g of MMA were added to form the second mixture, and 1.62 g of SLES, 0.81 g of NP-9, 74.17 g of DI water, 118.03 g of PFHEM, 58.44 g of EHA, 27.55 g of MMA, 2.18 g of MAA, 2.16 g of AM and 1.14 g of HDDA were added in the formation of the pre-emulsion. The solid content of the binder material solution is 46.9 wt. %.
[0242] Preparation of Binder Material Solution of Example 8
[0243] The binder material solution of Example 8 was prepared in the same manner as in Example 1, except that 1.62 g of SLES, 0.81 g of NP-9, 74.17 g of DI water, 52.46 g of PFHEM, 69.06 g of EHA, 34.84 g of MMA, 2.61 g of MAA, 2.16 g of AM and no HDDA were added in the formation of the pre-emulsion; and 1.29 g of NaOH was dissolved in 30.0 g of DI water to form the sodium hydroxide solution which was used to form the sixth mixture. The solid content of the binder material solution is 40.8 wt. %.
[0244] Preparation of Binder Material Solution of Example 16
[0245] The binder material solution of Example 16 was prepared in the same manner as in Example 1, except that 52.46 g of PFHEM was replaced with 18.70 g of 2, 2, 2-trifluoroethyl acrylate (TFEA) in the formation of the pre-emulsion. The solid content of the binder material solution is 36.3 wt. %.
[0246] Preparation of Binder Material Solution of Example 17
[0247] The binder material solution of Example 17 was prepared in the same manner as in Example 1, except that 3.63 g of EHA was replaced with 1.97 g of ethyl acrylate (EA) in the formation of the second mixture; and 69.06 g of EHA was replaced with 37.52 g of EA in the formation of the pre-emulsion. The solid content of the binder material solution is 36.6 wt. %.
[0248] Preparation of Binder Material Solution of Example 18
[0249] The binder material solution of Example 18 was prepared in the same manner as in Example 1, except that 8.71 g of MMA was replaced with 11.32 g of 2-hydroxypropyl acrylate (2-HPA) in the formation of the second mixture; and 34.84 g of MMA was replaced with 45.28 g of 2-HPA in the formation of the pre-emulsion. The solid content of the binder material solution is 43.0 wt. %.
[0250] Preparation of Binder Material Solution of Comparative Example 2
[0251] The binder material solution of Comparative Example 2 was prepared in the same manner as in Example 1, except that 2.24 g of EHA and 6.08 g of MMA were added to form the second mixture, and 1.62 g of SLES, 0.81 g of NP-9, 74.17 g of DI water, 174.86 g of PFHEM, 42.50 g of EHA, 24.30 g of MMA, 2.18 g of MAA, 2.16 g of AM and 1.14 g of HDDA were added in the formation of the pre-emulsion. The solid content of the binder material solution is 50.8 wt. %.
[0252] Preparation of Binder Material Solution of Comparative Example 3
[0253] The binder material solution of Comparative Example 3 was prepared in the same manner as in Example 1, except that 5.78 g of EHA and 4.05 g of MMA were added to form the second mixture, and 1.62 g of SLES, 0.81 g of NP-9, 74.17 g of DI water, 52.46 g of PFHEM, 109.79 g of EHA, 16.20 g of MMA, 2.18 g of MAA, 2.16 g of AM and 1.14 g of HDDA were added in the formation of the pre-emulsion. The solid content of the binder material solution is 43.9 wt. %.
[0254] Preparation of Binder Material Solution of Comparative Example 4
[0255] The binder material solution of Comparative Example 4 was prepared in the same manner as in Example 1, except that 1.86 g of EHA and 14.18 g of MMA were added to form the second mixture, and 1.62 g of SLES, 0.81 g of NP-9, 74.17 g of DI water, 17.49 g of PFHEM, 35.42 g of EHA, 56.71 g of MMA, 2.18 g of MAA, 2.16 g of AM and 1.14 g of HDDA were added in the formation of the pre-emulsion. The solid content of the binder material solution is 35.0 wt. %.
[0256] Preparation of Stabilizing Agent Solution of Example 2
[0257] The binding agent solution of Example 1 was used as the stabilizing agent solution of Example 2.
[0258] Preparation of Stabilizing Agent Solution of Example 3
[0259] A stabilizing agent solution was prepared in the same manner as that of the stabilizing agent solution of Example 1, except that 7.45 g of NaOH was added in the preparation of the first suspension, 16.77 g of acrylic acid was added in the preparation of the second suspension and 35.95 g of acrylonitrile was added in the preparation of the fourth suspension. The solid content of the stabilizing agent solution is 8.07 wt. %.
[0260] Preparation of Stabilizing Agent Solutions of Examples 4-18 and Comparative Examples 2-6
[0261] The stabilizing agent solutions of Examples 4-18 and Comparative Examples 2-6 were prepared in the same manner as in Example 1.
[0262] Preparation of Conductive Layer Slurry of Example 2
[0263] The conductive layer slurry of Example 2 was prepared in the same manner as in Example 1, except that 5.56 g of the stabilizing agent solution was added into 230.99 g of DI water to form the first mixture.
[0264] Preparation of Conductive Layer Slurry of Example 3
[0265] The conductive layer slurry of Example 3 was prepared in the same manner as in Example 1, except that 6.20 g of the stabilizing agent solution was added into 230.35 g of DI water to form the first mixture.
[0266] Preparation of Conductive Layer Slurry of Example 4
[0267] The conductive layer slurry of Example 4 was prepared in the same manner as in Example 1, except that 6.02 g of the stabilizing agent solution was added into 238.36 g of DI water to form the first mixture, and 101.12 g of the binder material solution was added into the second mixture to form the conductive layer slurry.
[0268] Preparation of Conductive Layer Slurry of Example 5
[0269] The conductive layer slurry of Example 5 was prepared in the same manner as in Example 1, except that 6.02 g of the stabilizing agent solution was added into 228.10 g of DI water to form the first mixture, and 111.39 g of the binder material solution was added into the second mixture to form the conductive layer slurry.
[0270] Preparation of Conductive Layer Slurry of Example 6
[0271] The conductive layer slurry of Example 6 was prepared in the same manner as in Example 1, except that 6.02 g of the stabilizing agent solution was added into 225.56 g of DI water to form the first mixture, and 113.92 g of the binder material solution was added into the second mixture to form the conductive layer slurry.
[0272] Preparation of Conductive Layer Slurry of Example 7
[0273] The conductive layer slurry of Example 7 was prepared in the same manner as in Example 1, except that 6.02 g of the stabilizing agent solution was added into 243.53 g of DI water to form the first mixture, and 95.95 g of the binder material solution was added into the second mixture to form the conductive layer slurry.
[0274] Preparation of Conductive Layer Slurry of Example 8
[0275] The conductive layer slurry of Example 8 was prepared in the same manner as in Example 1, except that 6.02 g of the stabilizing agent solution was added into 229.19 g of DI water to form the first mixture, and 110.29 g of the binder material solution was added into the second mixture to form the conductive layer slurry.
[0276] Preparation of Conductive Layer Slurry of Example 9
[0277] The conductive layer slurry of Example 9 was prepared in the same manner as in Example 1, except that 54.5 g of carbon black (obtained from Timcal Ltd, Bodio, Switzerland) was used instead of 54.5 g of graphite powder in the formation of the second mixture.
[0278] Preparation of Conductive Layer Slurry of Example 10
[0279] The conductive layer slurry of Example 10 was prepared in the same manner as in Example 1, except that a mixture of 5.5 g of carbon black and 49 g of graphite powder was used instead of 54.5 g of graphite powder in the formation of the second mixture.
[0280] Preparation of Conductive Layer Slurry of Example 11
[0281] The conductive layer slurry of Example 11 was prepared in the same manner as in Example 1, except that a mixture of 5.5 g of vapor grown carbon nanofibers (VGCFs; obtained from Showa Denko K. K., Japan) and 49 g of graphite powder was used instead of 54.5 g of graphite powder in the formation of the second mixture.
[0282] Preparation of Conductive Layer Slurry of Example 12
[0283] The conductive layer slurry of Example 12 was prepared in the same manner as in Example 1, except that a mixture of 5.5 g of carbon nanotubes (CNTs; obtained from Jiangsu Cnano Technology Co. Ltd., China) and 49 g of graphite powder was used instead of 54.5 g of graphite powder in the formation of the second mixture.
[0284] Preparation of Conductive Layer Slurries of Examples 13-15
[0285] The conductive layer slurries of Examples 13-15 were prepared in the same manner as in Example 1.
[0286] Preparation of Conductive Layer Slurry of Example 16
[0287] The conductive layer slurry of Example 16 was prepared in the same manner as in Example 1, except that 6.02 g of the stabilizing agent solution was added into 215.52 g of DI water to form the first mixture, and 123.97 g of the binder material solution was added into the second mixture to form the conductive layer slurry.
[0288] Preparation of Conductive Layer Slurry of Example 17
[0289] The conductive layer slurry of Example 17 was prepared in the same manner as in Example 1, except that 6.02 g of the stabilizing agent solution was added into 216.53 g of DI water to form the first mixture, and 122.95 g of the binder material solution was added into the second mixture to form the conductive layer slurry.
[0290] Preparation of Conductive Layer Slurry of Example 18
[0291] The conductive layer slurry of Example 18 was prepared in the same manner as in Example 1, except that 6.02 g of the stabilizing agent solution was added into 234.83 g of DI water to form the first mixture, and 104.65 g of the binder material solution was added into the second mixture to form the conductive layer slurry.
[0292] Preparation of Conductive Layer Slurry of Comparative Example 1
[0293] 54.5 g of graphite powder was added into 236.04 g of DI water. After the addition, the mixture was stirred for about 3 hours at 25 ℃ at a speed of 1,200 rpm to form a first mixture.
[0294] 108.96 g of the binder material solution was added into the first mixture. After the addition, this mixture was stirred for about 60 minutes at 25 ℃ at a speed of 800 rpm to form the conductive layer slurry. The solid content of the conductive layer slurry is 25 wt. %.
[0295] Preparation of Conductive Layer Slurry of Comparative Example 2
[0296] The conductive layer slurry of Comparative Example 2 was prepared in the same manner as in Example 1, except that 6.02 g of the stabilizing agent solution was added into 250.90 g of DI water to form the first mixture, and 88.58 g of the binder material solution was added into the second mixture to form the conductive layer slurry.
[0297] Preparation of Conductive Layer Slurry of Comparative Example 3
[0298] The conductive layer slurry of Comparative Example 3 was prepared in the same manner as in Example 1, except that 6.02 g of the stabilizing agent solution was added into 236.98 g of DI water to form the first mixture, and 102.51 g of the binder material solution was added into the second mixture to form the conductive layer slurry.
[0299] Preparation of Conductive Layer Slurry of Comparative Example 4
[0300] The conductive layer slurry of Comparative Example 4 was prepared in the same manner as in Example 1, except that 6.02 g of the stabilizing agent solution was added into 210.91 g of DI water to form the first mixture, and 128.57 g of the binder material solution was added into the second mixture to form the conductive layer slurry.
[0301] Preparation of Conductive Layer Slurry of Comparative Example 5
[0302] The conductive layer slurry of Comparative Example 5 was prepared in the same manner as in Example 1, except that 163.30 g of the stabilizing agent solution was added into 86.31 g of DI water to form the first mixture. The solid content of the conductive layer slurry is 27.4 wt. %.
[0303] Preparation of Conductive Layer Slurry of Comparative Example 6
[0304] The conductive layer slurry of Comparative Example 6 was prepared in the same manner as in Example 1, except that 68.11 g of the stabilizing agent solution was added into 222.46 g of DI water to form the first mixture, and 25.71 g of the binder material solution was added into the second mixture to form a conductive layer slurry. The solid content of the conductive layer slurry is 19.1 wt. %.
[0305] Preparation of Modified Current Collectors of Examples 2-18 and Comparative Examples 2-4
[0306] The modified current collectors of Examples 2-18 and Comparative Examples 2-4 were prepared in the same manner as in Example 1.
[0307] Preparation of Modified Current Collectors of Comparative Examples 1 and 5-6
[0308] The same method used in Example 1 was also used in Comparative Examples 1 and 5-6 to attempt to prepare modified current collectors. However, a conductive layer could not be formed and therefore no further preparation and testing was carried out for each of the examples.
[0309] Preparation of Binding Agent Solutions of Examples 2-18 and Comparative Examples 2-4
[0310] The binding agent solutions of Examples 2-18 and Comparative Examples 2-4 were prepared in the same manner as in Example 1.
[0311] Preparation of Positive Electrodes of Examples 2-12 and 16-18, and Comparative Examples 2-4
[0312] The positive electrodes of Examples 2-12 and 16-18, and Comparative Examples 2-4 were prepared in the same manner as in Example 1.
[0313] Preparation of Positive Electrode of Example 13
[0314] The positive electrode was prepared in the same manner as in Example 1, except that 276 g of NMC811 was replaced with LiNi0.8Co0.15Al0.05O2 (NCA, obtained from Shandong Tianjiao New Energy Co., Ltd, China) of the same weight in the preparation of positive electrode.
[0315] Preparation of Positive Electrode of Example 14
[0316] The positive electrode was prepared in the same manner as in Example 1, except that 276 g of NMC811 was replaced with a core-shell cathode active material (C-S) comprising NMC532 as the core and Li0.95Ni0.53Mn0.29Co0.15Al0.03O2 as the shell of the same weight in the preparation of positive electrode.
[0317] Preparation of Positive Electrode of Example 15
[0318] The positive electrode was prepared in the same manner as in Example 1, except that 276 g of NMC811 was replaced with LiFePO4 (LFP; obtained from Shenzhen Dynanonic Co., Ltd., China) of the same weight in the preparation of positive electrode.
[0319] Assembly of Coin Cells of Examples 2-18 and Comparative Examples 2-4
[0320] The coin cells of Examples 2-18 and Comparative Examples 2-4 were assembled in the same manner as in Example 1.
[0321] Electrochemical Measurements of Examples 2-14 and 16-18, and Comparative Examples 2-4
[0322] The electrochemical performance of the coin cells of Examples 2-14 and 16-18, and Comparative Examples 2-4 was measured in the same manner as in Example 1 and the test results are shown in Table 1 below.
[0323] Electrochemical Measurements of Example 15
[0324] The electrochemical performance of the coin cell of Example 15 was measured in the same manner as in Example 1, except that the charging / discharging cycling tests of the cells were performed between 2.00 and 3.65 V at a current density of C / 2 at 25 ℃ to obtain the discharge capacity. The test results are shown in Table 1 below.
[0325] While the invention has been described with respect to a limited number of embodiments, the specific features of one embodiment should not be attributed to other embodiments of the invention. In some embodiments, the methods may include numerous steps not mentioned herein. In other embodiments, the methods do not include, or are substantially free of, any steps not enumerated herein. Variations and modifications from the described embodiments exist. The appended claims intend to cover all those modifications and variations as falling within the scope of the invention.
[0326]
Claims
1.A modified current collector for a secondary battery, comprising a substrate and a conductive layer applied on one side or both sides of the substrate, wherein the conductive layer comprises a conductive material and a binder material, wherein the binder material comprises a fluorine-containing copolymer, comprising a structural unit (a) , a structural unit (b) and a structural unit (c) .2.The modified current collector of claim 1, wherein the structural unit (a) is derived from a fluorine-containing acrylate or methacrylate monomer.3.The modified current collector of claim 2, wherein the fluorine-containing acrylate or methacrylate monomer is selected from the group consisting of 2, 2, 2-trifluoroethyl acrylate, 2, 2, 3, 3-tetrafluoropropyl acrylate, 2, 2, 3, 4, 4, 4-hexafluorobutyl acrylate, 1H, 1H, 9H-perfluorononyl acrylate, perfluoroethyl acrylate, perfluorobutyl acrylate, perfluorohexyl acrylate, perfluorooctyl acrylate, perfluorododecyl acrylate, trifluoromethyl acrylate, methyl 2, 2, 2- (trifluoroethyl) acrylate, methyl 2, 2, 3, 3- (tetrafluoropropyl) acrylate, methyl 2, 2, 3, 4, 4, 4- (hexafluorobutyl) acrylate, methyl 1H, 1H, 9H- (perfluorononyl) acrylate, methyl 1H,1H, 11H- (perfluoroundecyl) acrylate, methyl (perfluoroethyl) acrylate, methyl (perfluorobutyl) acrylate, methyl (perfluorohexyl) acrylate, methyl (perfluorooctyl) acrylate, methyl (perfluorodecyl) acrylate, methyl (perfluorododecyl) acrylate, methyl (trifluoromethyl) acrylate, (perfluorohexyl) ethyl methacrylate, (perfluorooctyl) ethyl methacrylate, 1H, 1H, 7H-perfluoroheptyl methacrylate, isomers thereof, and combinations thereof.4.The modified current collector of claim 1, wherein the structural unit (b) is derived from a monomer having a glass transition temperature below 0 ℃ and the structural unit (c) is derived from a monomer having a glass transition temperature of 0 ℃ or above; and wherein one or both of the structural units (b) and (c) are derived from an acrylate or methacrylate monomer.5.The modified current collector of claim 1, wherein the structural unit (b) is derived from a monomer selected from the group consisting of 2-ethylhexyl acrylate, 4-cyanobutyl acrylate, butyl acrylate, dodecyl acrylate, ethyl acrylate, pentyl acrylate, hexyl acrylate, isobutyl acrylate, isopropyl acrylate, isooctyl acrylate, decyl acrylate, propyl acrylate, sec-butyl acrylate, tetrahydrofurfuryl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, hexyl methacrylate, isodecyl methacrylate, octyl methacrylate, tetradecyl methacrylate, octadecyl methacrylate, isomers thereof, and combinations thereof.6.The modified current collector of claim 1, wherein the structural unit (c) is derived from a monomer selected from the group consisting of 2-cyanobutyl acrylate, 2-cyanoethyl acrylate, 3, 3, 5-trimethylcyclohexyl acrylate, benzyl acrylate, cyanomethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methyl acrylate, octadecyl acrylate, phenoxyethyl acrylate, tert-butyl acrylate, methyl cyanoacrylate, ethyl cyanoacrylate, butyl cyanoacrylate, hexadecyl acrylate, 1- (diethylamino) ethyl methacrylate, 1- (dimethylamino) ethyl methacrylate, 2- (tert-butylamino) ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-phenylethyl methacrylate, 4- (tert-butyl) cyclohexyl methacrylate, ethyl methacrylate, glycidyl methacrylate, hexadecyl methacrylate, isobornyl methacrylate, isobutyl methacrylate, isopropyl methacrylate, methyl methacrylate, neopentyl methacrylate, octadecyl methacrylate, pentyl methacrylate, phenyl methacrylate, propyl methacrylate, tetrahydrofurfuryl methacrylate, isomers thereof, and combinations thereof.7.The modified current collector of claim 1, wherein one or both of the structural units (b) and (c) are derived from a fluorine-free monomer.8.The modified current collector of claim 1, wherein the proportion of the structural unit (a) in the fluorine-containing copolymer is from about 3%to about 30%by mole, based on the total number of moles of monomeric units in the fluorine-containing copolymer.9.The modified current collector of claim 1, wherein the proportion of each of the structural unit (b) and the structural unit (c) in the fluorine-containing copolymer is independently from about 20%to about 60%by mole, based on the total number of moles of monomeric units in the fluorine-containing copolymer.10.The modified current collector of claim 1, wherein the fluorine-containing copolymer further comprises a structural unit (d) derived from a function-enhancing monomer, wherein the function-enhancing monomer is derived from an acid group-containing monomer, an amide group-containing monomer, a nitrile group-containing monomer, or combinations thereof; and wherein the fluorine-containing copolymer additionally comprises a structural unit (e) derived from a crosslinking monomer.11.The modified current collector of claim 10, wherein the proportion of the structural unit (d) in the fluorine-containing copolymer is from about 0.1%to about 10%by mole, based on the total number of moles of monomeric units in the fluorine-containing copolymer.12.The modified current collector of claim 1, wherein the weight-average molecular weight of the fluorine-containing copolymer is from about 200,000 g / mol to about 500,000 g / mol.13.The modified current collector of claim 1, wherein the thickness of the conductive layer is from about 0.5 μm to about 15 μm, and wherein the surface density of the conductive layer is from about 0.01 mg / cm2 to about 5 mg / cm2.14.A conductive layer slurry comprising the binder material of claim 1, a conductive material, an aqueous solvent and a stabilizing agent.15.The conductive layer slurry of claim 14, wherein the aqueous solvent is water or a mixture of water and a minor component selected from the group consisting of tetrahydrofuran, acetonitrile, dimethyl sulfoxide, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methanol, ethanol, isopropanol, n-propanol, tert-butanol, n-butanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, ethylene glycol, propylene glycol, glycerol, acetone, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isopropyl acetate, propyl acetate, butyl acetate, and combinations thereof.16.The conductive layer slurry of claim 14, wherein the stabilizing agent comprises a stabilizing copolymer comprising a structural unit (i) derived from an acid group-containing monomer, a structural unit (ii) derived from an amide group-containing monomer, and a structural unit (iii) derived from a nitrile group-containing monomer.17.The conductive layer slurry of claim 16, wherein, based on the total number of moles of monomeric units in the stabilizing copolymer, the proportion of the structural unit (i) in the stabilizing copolymer is from about 10%to about 70%by mole, the proportion of the structural unit (ii) in the stabilizing copolymer is from about 5%to about 40%by mole, and the proportion of the structural unit (iii) in the stabilizing copolymer is from about 15%to about 70%by mole.18.The conductive layer slurry of claim 14, wherein the proportion of the stabilizing agent in the conductive layer slurry is from about 0.1%to about 10%by weight, based on the solid content of the conductive layer slurry.19.The conductive layer slurry of claim 14, wherein the conductive layer slurry has a solid content of from about 1%to about 60%by weight, based on the total weight of the conductive layer slurry, and has a viscosity of from about 10 mPa·s to about 2,000 mPa·s.20.An electrode, comprising the modified current collector of claim 1 and an electrode layer, wherein the electrode layer is located on the surface of the conductive layer, and wherein the electrode layer comprises an electrode active material and a binding agent.
Citation Information
Patent Citations
Conductive adhesive composition, collector with adhesive layer, and electrochemical element electrode
CN103890124A
Current collector structure
CN104425051A
Multifunctional lithium battery current collector and preparation method thereof
CN108493455A
Modified current collector for secondary battery
WO2023097795A1
Cited By
Fluororubber sealing material with high battery electrolyte resistance and preparation method of fluororubber sealing material
CN121271114A
Highly resistant battery electrolyte fluororubber sealing material and its preparation method
CN121271114B
