Negative current collector and metal battery including the same

Abstract

The present invention relates to a negative electrode current collector and a metal battery, more particularly to a negative electrode current collector including a two-dimensional material layer having an atomic thickness formed on at least a portion of at least one surface of a current collector substrate, and a metal layer formed on at least a portion of the two-dimensional material layer, and a metal battery including the same. The present invention may further provide a method for manufacturing the negative electrode current collector.

Description

Technical Field

[0001] The present invention relates to a negative electrode current collector and a metal battery including the same.

Background Art

[0002] Among various secondary batteries, lithium secondary batteries are the most excellent in terms of energy density and output characteristics and are widely commercialized. While the demand in electric vehicles and large-capacity power storage devices is increasing, the development of high-energy batteries to meet this demand is required. There is an analysis result that a lithium metal negative electrode must be applied to achieve an energy density of 400 Wh / kg or more, and for the purpose of improving the energy density of secondary batteries, technical development using lithium metal as a negative electrode is actively underway.

[0003] A lithium metal battery is a secondary battery that uses lithium metal having a high capacity and a low reduction potential as a negative electrode, and has been researched and developed in various forms such as lithium-air batteries and lithium-sulfur batteries, and has attracted attention as a next-generation energy battery system with high energy density.

[0004] When using lithium metal as a negative electrode, a lithium layer with a dendrite structure is formed during the process of depositing lithium metal on the surface of the current collector. When lithium dendrites grow due to such a non-uniform lithium layer, it not only causes a short-circuit phenomenon but also may form Dead Li that does not contribute to the capacity. In addition, such a lithium layer with a dendrite structure causes a phenomenon in which the capacity and output characteristics of the battery decrease, making it difficult to commercialize lithium metal batteries.

[0005] In order to solve such problems, the development of a technology for forming a uniform lithium layer on the surface of the current collector is increasing, but it is technically difficult to control uniform lithium nucleation due to the high nucleation overpotential on the surface of the conventional current collector.

Summary of the Invention

Problems to be Solved by the Invention

[0006] In order to solve the above-mentioned problems, the present invention provides a negative electrode current collector modified to a metal-affinitive surface capable of forming a uniform and dense metal layer.

[0007] The present invention provides a metal battery capable of realizing a high energy density of a metal substrate including the negative electrode current collector according to the present invention.

[0008] The present invention provides a method for manufacturing the negative electrode current collector according to the present invention.

[0009] However, the problems to be solved by the present invention are not limited to those mentioned above, and other unmentioned problems can be clearly understood by those skilled in the art from the following description.

Means for Solving the Problems

[0010] According to an embodiment of the present invention, it relates to a negative electrode current collector including a current collector substrate, a two-dimensional material layer with an atomic thickness formed on at least a part of at least one surface of the current collector substrate, and a metal layer formed on at least a part of the two-dimensional material layer.

[0011] According to an embodiment of the present invention, the current collector substrate can include at least one or more selected from the group consisting of Ni, Cu, Ti, V, Cr, Mn, Fe, Co, Zn, Mo, W, Ag, Au, Ru, Pt, Ir, Li, Al, Sn, Bi, Sb, and alloys thereof, fired carbon, and stainless steel.

[0012] According to an embodiment of the present invention, the current collector substrate can include a first component including Cu, Ni, Ti, stainless steel, or Al, and a second component (excluding the same elements as the first component) including at least one or more selected from the group consisting of Ni, Cu, Ti, V, Cr, Mn, Fe, Co, Zn, Mo, W, Ag, Au, Ru, Pt, Ir, Li, Al, Sn, Bi, Sb, and alloys thereof.

[0013] According to one embodiment of the present invention, the current collector substrate may be a foil having a thickness of 5 μm to 100 μm.

[0014] According to one embodiment of the present invention, the two-dimensional material may include at least one or more of graphene, hexagonal boron nitride, and transition metal compounds.

[0015] According to one embodiment of the present invention, the thickness of the two-dimensional material layer may be 0.4 nm to 10 nm.

[0016] According to one embodiment of the present invention, the metal layer is directly grown on the two-dimensional material layer by vapor deposition, and the metal layer can be directly grown by electroplating.

[0017] According to one embodiment of the present invention, the metal layer may include at least one or more selected from the group consisting of lithium (Li), sodium (Na), aluminum (Al), calcium (Ca), silver (Ag), gold (Au), sodium (Na), zinc (Zn), magnesium (Mg), and potassium (K), sulfides containing the metal, halides, oxides, intermetallic compounds, and alloys. According to one embodiment of the present invention, the metal layer is free of a metal-containing dendrite structure, and the metal layer may be a planar film.

[0018] According to one embodiment of the present invention, the thickness of the metal layer may be 1 nm to 100 μm.

[0019] According to one embodiment of the present invention, the metal layer may include lithium metal, lithium sulfide, lithium halide, a lithium alloy, or two of them.

[0020] According to an embodiment of the present invention, the lithium alloy can include lithium and at least one or more selected from the group consisting of sodium (Na), aluminum (Al), calcium (Ca), silver (Ag), gold (Au), sodium (Na), zinc (Zn), magnesium (Mg), and potassium (K).

[0021] According to an embodiment of the present invention, a metal battery is provided that includes a negative electrode portion, a positive electrode portion, and an electrolyte between the negative electrode portion and the positive electrode portion. The negative electrode portion includes a negative electrode current collector, and the negative electrode current collector includes a current collector substrate, a two-dimensional material layer with an atomic thickness formed on at least a part of at least one surface of the current collector substrate, and a metal layer formed on at least a part of the two-dimensional material layer.

[0022] According to an embodiment of the present invention, the electrolyte can include a liquid electrolyte, a solid electrolyte, or both of them.

[0023] According to an embodiment of the present invention, the negative electrode current collector may be a non-negative electrode-facing current collector in contact with the electrolyte on the metal layer.

[0024] According to an embodiment of the present invention, a method for manufacturing a negative electrode current collector is provided that includes the steps of preparing a current collector substrate, forming a two-dimensional material layer with an atomic thickness on at least a part of at least one surface of the current collector substrate, and forming a metal layer on at least a part of the two-dimensional material layer.

[0025] According to an embodiment of the present invention, the step of forming the two-dimensional material layer can include the step of transferring the two-dimensional material layer onto the current collector.

[0026] According to an embodiment of the present invention, the step of forming the two-dimensional material layer can include the step of directly growing the two-dimensional material layer on the current collector by a vapor deposition method.

[0027] According to an embodiment of the present invention, in the step of forming the metal layer, the metal layer can be directly grown on the two-dimensional material layer by vapor deposition.

Effects of the Invention

[0028] In the present invention, on the surface of the current collector adopting the negative electrode structure, a metal layer, for example, a flat and dense structure metal layer such as a lithium layer with a reduced nucleation overvoltage of a metal such as lithium and suppressed dendrite structure on the surface of the current collector is formed. Such a flat and dense structure metal layer can be applied to a metal negative electrode, for example, a lithium metal negative electrode. Further, it is possible to prevent the reduction of the capacity and output characteristics, improve the certain energy density and stability, and realize a high-energy metal battery, for example, a lithium metal battery.

[0029] Moreover, the present invention can provide a current collector for a non-negative electrode direction with a two-dimensional material having an atomic thickness and a planar shape and capable of adsorbing metal atoms, and a surface-treated metal layer formed uniformly and densely, and a metal battery, for example, a lithium metal battery applying the current collector for a non-negative electrode direction.

Brief Description of the Drawings

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MODE FOR CARRYING OUT THE INVENTION

[0031] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the present invention, when it is determined that a specific description of related known functions or configurations would unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. Also, the terms used in this specification are used as terms for appropriately expressing preferred embodiments of the present invention, and these may vary depending on the intention of the user, operator, or the convention in the field to which the present invention belongs. Therefore, the definitions of these terms should be made based on the content throughout this specification. The same reference numerals presented in each drawing indicate the same members.

[0032] Throughout the specification, when any member is located "above" a different member, this includes not only the case where any member is in contact with another member, but also the case where there are additional members between the two members.

[0033] Throughout the specification, when any part "includes" any component, this means that it does not exclude other components, but may further include other components.

[0034] The present invention relates to the project of "Material Chemistry Laboratory of Two-Dimensional Van der Waals Structures (Detail Project Number: 2019R1A4A1027934, Project Specific Number: 1711108505, Project Name: Group Research Support (R&D), Project Management (Specialty) Agency Name: National Research Foundation of Korea, Research Period: March 1, 2020 ~ February 28, 2021)" supported by the Ministry of Science and Technology Information and Communication.

[0035] Hereinafter, the negative electrode current collector, metal battery, and method for manufacturing the negative electrode current collector of the present invention will be specifically described with reference to embodiments and drawings. However, the present invention is not limited to such embodiments and drawings.

[0036] The present invention relates to a negative electrode current collector. The negative electrode current collector according to an embodiment of the present invention is modified with a two-dimensional material to have a metal-affinitive surface, for example, a lithium-affinitive surface. By modifying the surface of the negative electrode current collector to be metal-affinitive, a dense and flat metal layer, for example, a lithium metal layer, can be formed on the surface of the current collector even without a dendrite structure. After the deposition of the metal layer, the formation of a metal with a dendrite structure is suppressed, and a certain energy density and stability are exhibited.

[0037] According to an embodiment of the present invention, the negative electrode current collector may include a current collector substrate, a two-dimensional material layer, and a metal layer.

[0038] According to an embodiment of the present invention, the current collector substrate may include at least one or more selected from the group consisting of Ni, Cu, Ti, V, Cr, Mn, Fe, Co, Zn, Mo, W, Ag, Au, Ru, Pt, Ir, Li, Al, Sn, Bi, Sb, and alloys thereof; fired carbon; and stainless steel. For example, a first component including Cu, Ni, Ti, stainless steel, or Al; and a second component including at least one or more selected from the group consisting of Ni, Cu, Ti, V, Cr, Mn, Fe, Co, Zn, Mo, W, Ag, Au, Ru, Pt, Ir, Li, Al, Sn, Bi, Sb, and alloys thereof (excluding the same elements as the first component) may be included. The second component does not include the same elements as the first component, and the current collector substrate can be formed in the form of a mixture, coating, alloy, composite, etc. mixed with the first component.

[0039] As an example of the present invention, the current collector substrate may be a foil, thin film, film, or sheet, and may include a thickness of 5 μm to 100 μm. If it is included within the thickness range, electron transfer is advantageous due to the high electrical conductivity of the current collector substrate, and it can be utilized as a current collector for a lithium metal battery with a high energy density through lithium-affinitive surface modification.

[0040] According to an embodiment of the present invention, the two-dimensional material layer modifies the current collector substrate to a lithium-affinity surface, thereby reducing the nucleation overpotential on the surface of the current collector, realizing uniform metal, for example, lithium nucleation, and forming a uniform and flat metal deposition film, for example, a lithium deposition film.

[0041] As an example of the present invention, the two-dimensional material layer is formed at least in part on at least one surface of the current collector substrate, formed with an atomic thickness, and contains at least one or more of graphene, hexagonal boron nitride, and transition metal compounds. Preferably, it may be hexagonal boron nitride. The two-dimensional material layer can control the metal affinity of the metal layer. That is, referring to FIG. 1, hexagonal boron nitride controls the lithium affinity through the introduction of a single layer of hexagonal boron nitride. When a single layer of hexagonal boron nitride with few defects is introduced on the current collector substrate, electron transfer is possible from the current collector substrate. Therefore, lithium deposition can be directly performed with hexagonal boron nitride. In addition, there are few defects on the current collector substrate, and boron and nitrogen with different electronegativities are extremely regularly arranged, enabling uniform metal deposition, for example, lithium metal deposition. The polarity difference of hexagonal boron nitride can easily deposit lithium, thereby inducing uniform lithium nucleation.

[0042] As an example of the present invention, the thickness of the two-dimensional material layer is 0.4 nm to 10 nm. If it is within this range, the adsorption of lithium atoms is advantageous, the electron conductivity in the vertical direction from the current collector substrate can be adjusted, the deposition rate of the metal layer, for example, the lithium metal layer, can be adjusted, and a uniform lithium metal layer can be formed.

[0043] According to an embodiment of the present invention, the metal layer is formed on at least a part of the two-dimensional material layer and is directly grown on the two-dimensional material layer by a vapor deposition method. Referring to FIG. 1, on the two-dimensional material layer, the lithium metal layer has a greatly reduced lithium nucleation resistance, suppressing the dendritic lithium vapor deposition and enabling uniform lithium metal vapor deposition. Uniform lithium nucleation can occur at the atomic unit and face-to-face level, and a face-to-face lithium metal layer can be formed. Further, the lithium metal layer is deposited in a uniform and compact form, suppressing side reactions and capable of suppressing the formation and growth of lithium dendrites at high currents.

[0044] As an example of the present invention, the metal layer is directly grown on the surface of the current collector modified by the two-dimensional material layer, reducing the nucleation overvoltage of the metal, and forming a flat and dense metal layer structure with suppressed dendritic structure on the surface of the current collector. That is, it is formed into a metal layer of a flat film with a compact and flat structure, and can improve a certain energy density and stability. Further, the metal layer may suppress the formation of a metal dendrite structure, slightly contain it, or hardly contain it, or be free of the metal dendrite structure. The metal layer is formed from a uniform and compact film, suppressing side reactions at high currents and suppressing the formation of dendrites during the driving of the battery. For example, the lifespan of a lithium metal battery with h-BN introduced is improved by 3 times compared to the lifespan of an existing lithium metal battery without h-BN introduced.

[0045] As an example of the present invention, the metal layer may include at least one or more metals selected from the group consisting of lithium (Li), sodium (Na), aluminum (Al), calcium (Ca), silver (Ag), gold (Au), sodium (Na), zinc (Zn), magnesium (Mg), and potassium (K); and at least one or more selected from the group consisting of the metal (or metal element) - containing compound, the metal (or metal element) - containing intermetallic compound, and the alloy. For example, the metal (or metal element) - containing compound may be a sulfide, a halide, an oxide, or the like.

[0046] As an example of the present invention, the metal layer is a lithium metal layer, and the lithium metal layer may contain at least one or more selected from the group consisting of lithium metal, lithium-containing compounds, lithium-containing intermetallic compounds, and lithium alloys.

[0047] The lithium-containing compounds are sulfides, halides, oxides, etc., and for example, lithium sulfide (e.g., LiS), lithium halide (e.g., LiF), lithium oxide (e.g., LiO2), etc. may be used.

[0048] The lithium alloy and the intermetallic compound may contain, for example, lithium; and at least one or more selected from the group consisting of sodium (Na), aluminum (Al), calcium (Ca), silver (Ag), gold (Au), sodium (Na), zinc (Zn), magnesium (Mg), and potassium (K).

[0049] In addition, the lithium metal layer may further contain at least one or more metals (or elements) selected from the group consisting of sodium (Na), aluminum (Al), calcium (Ca), silver (Ag), gold (Au), sodium (Na), zinc (Zn), magnesium (Mg), and potassium (K).

[0050] As an example of the present invention, the thickness of the metal layer is 1 nm to 100 μm; 10 nm to 50 μm; or 1 μm to 40 μm; or 10 μm to 35 μm, or may be atomic thickness. It can be included within the thickness range or form a thinner thickness within the range to increase the energy density per cell unit.

[0051] The present invention relates to a metal battery. According to an embodiment of the present invention, the lithium metal battery may include a negative electrode portion; a positive electrode portion; and an electrolyte between the negative electrode portion and the positive electrode portion. The lithium metal battery applies the negative electrode current collector according to the present invention and exhibits high energy density, high safety, and long life characteristics.

[0052] According to an embodiment of the present invention, the metal battery may be a metal battery based on lithium (Li), sodium (Na), aluminum (Al), calcium (Ca), silver (Ag), gold (Au), sodium (Na), zinc (Zn), magnesium (Mg), or potassium (K).

[0053] According to an embodiment of the present invention, the negative electrode includes the negative electrode current collector according to the present invention, and the negative electrode current collector may be a current collector without a negative electrode by applying the metal layer.

[0054] According to an embodiment of the present invention, the electrolyte includes an electrolyte applicable to a metal battery known in the technical field of the present invention, and is formed between the metal layer of the cathode current collector and the positive electrode, and may include a liquid electrolyte, a solid electrolyte, or two of them. A separator is further included between the electrolyte and the positive electrode, and the separator includes a liquid electrolyte, a solid electrolyte, or two of them, and can be applied as a function of the electrolyte.

[0055] As an example of the present invention, the electrolyte may form a non-aqueous metal battery in contact with the metal layer, for example, a non-aqueous lithium metal battery.

[0056] According to an embodiment of the present invention, the positive electrode may be applied without limitation as long as it is applicable to a metal battery known in the technical field of the present invention, and may be a high-capacity positive electrode such as an oxide or a sulfide. The positive electrode may further include a positive electrode current collector.

[0057] As an example of the present invention, the metal battery is operated and driven by introducing a configuration known in the technical field of the present invention without departing from the object and scope of the present invention, and is not specifically mentioned in this specification.

[0058] The present invention relates to a method for manufacturing a negative electrode current collector according to the present invention. According to an embodiment of the present invention, the manufacturing method is to modify the surface of the current collector substrate in a lithium-affinitive manner with a two-dimensional material, and directly grow a metal layer on the current collector to form a lithium metal film that is uniform, dense, and suppresses the generation of a dendrite structure.

[0059] According to an embodiment of the present invention, the manufacturing method includes a step of preparing a current collector substrate, a step of forming a two-dimensional material layer with an atomic thickness on at least a part of at least one surface of the current collector substrate, and a step of forming a metal layer on at least a part of the two-dimensional material layer.

[0060] According to an embodiment of the present invention, the step of forming the two-dimensional material layer can be formed by a physical method or a chemical method.

[0061] For example, the physical method may include a step of transferring a two-dimensional material layer onto the current collector. The two-dimensional material grown on a separate substrate can be peeled off by an electrical peeling method and transferred onto the current collector substrate. The transfer step applies a two-dimensional material (or film) and its transfer method known in the technical field of the present invention, but is not specifically mentioned herein.

[0062] For example, the electrochemical method may include a step of directly growing a two-dimensional material layer on the current collector by a vapor deposition method. The two-dimensional material can be directly grown on the current collector substrate by chemical vapor deposition (CVD). The electrochemical method may further use atomic layer deposition (ALD), plasma atomic layer deposition method, plasma enhanced chemical vapor deposition (PECVD), etc.

[0063] According to an embodiment of the present invention, the step of forming the metal layer can be directly grown on the current collector substrate surface-modified on the two-dimensional material layer by directly growing a metal layer on the two-dimensional material layer by a vapor deposition method, such as electrochemical deposition, physical adsorption (e.g., press, etc.), alloying (e.g., melting and alloying reaction like "melting & alloy").

[0064] The present invention can provide a method for manufacturing a metal battery that introduces or utilizes a negative electrode current collector according to the present invention or a method for manufacturing the negative electrode current collector. For example, it may include the steps of preparing the negative electrode current collector, preparing an electrolyte and / or a separator, preparing a positive electrode, and arranging, connecting, bonding, attaching, and / or pressing the negative electrode current collector, the electrolyte and / or the separator, and the positive electrode in sequence.

[0065] The present invention will be described with reference to preferred embodiments of the present invention. However, the present invention is not limited thereto, and the present invention can be variously modified and changed within the scope not departing from the idea and scope of the present invention described in the following claims, the detailed description of the invention, and the attached drawings.

Example

[0066] (Production Example 1) An h-BN Monolayer was manufactured and transferred onto a current collector.

[0067] (Production Example 2) Graphene Monolayer was directly grown and transferred onto a Cu foil to produce Graphene Monolayer / Cu.

[0068] (Production Example 3) h-BN was directly grown on a Cu foil by chemical vapor deposition to form h-BN Monolayer / Cu. The production examples manufactured graphene and h-BN with reference to a prior paper (Nano Lett. 2013, 13, 1834 - 1839).

[0069] (Production Example 4) Manufacture of an electrochemical cell composed of a lithium metal - negative electrode current collector A lithium metal layer with a desired thickness was deposited on the negative electrode current collector manufactured in Production Examples 1 to 3 through an electrochemical vapor deposition method on the two - dimensional material layer of the negative electrode current collector, and then a separator and an electrolyte were added. Electrolyte: 1M LiTFSI in 1,3 - dioxolane (DOL) / 1,2 - dimethyoxyethane (DME) = 1 / 1 (v / v)

[0070] The electrochemical properties and surface morphology of the current collectors produced in FIGS. 2A to 7 below were analyzed and shown.

[0071] FIGS. 2A, 2B and 2C show SEM images of the lithium metal vapor - deposited surface according to an embodiment of the present invention, and compare the morphologies of SEM images after Li Metal (0.1 mAh / cm 2 ) vapor deposition on Pristine Cu (FIG. 2A), h - BN Monolayer / Cu (FIG. 2B) and Graphene Monolayer / Cu (FIG. 2C). It can be confirmed that the most uniform Li Metal Deposition was performed on h - BN Monolayer / Cu.

[0072] That is, the image of the lithium layer formed on the Cu current collector is different from that having a dendrite structure. In contrast, the image of the lithium layer formed on the hexagonal boron nitride / Cu current collector has no dendrite structure, which confirms that a dense and flat lithium layer was formed on the surface of the current collector.

[0073] Measurement conditions Electrolyte: 1M LiTFSI in 1,3 - dioxolane (DOL) / 1,2 - dimethyoxyethane (DME) (5 / 5, v / v)+2 wt% LiNO3 Current Density: 10 μA / cm 2

[0074] FIG. 3 shows the measurement results of the nucleation overpotential of the current collector according to an embodiment of the present invention, and compares the results before and after the introduction of the h - BN layer on the current collector and the type of the current collector.

[0075] The overpotentials with and without h-BN introduction for each type of current collector (Cu, Ni, SUS) were compared, and it was confirmed that the nucleation overpotential after h-BN introduction decreases regardless of the type of current collector.

[0076] Measurement conditions For the Cu current collector, directly grown h-BN was used, and for the Ni & SUS current collectors, transferred h-BN was used. Electrolyte: 1M LiTFSI in DOL / DME (5 / 5, v / v) + 2 wt% LiNO3 Current density: 10 μA / cm 2

[0077] Figures 4A and 4B show the measurement results of the nucleation overpotential of the current collector according to an embodiment of the present invention, and compare the results according to the types of two-dimensional materials (h-BN and Graphene). The current collector with h-BN Monolayer introduced shows a lower nucleation overpotential than Graphene Monolayer, which can induce an increase in Li Binding Energy.

[0078] Measurement conditions Current collectors: Pristine Cu, h-BN Monolayer / Cu, Graphene Monolayer / Cu (a) The voltage profiles during Li deposition on Cu, h-BN / Cu, and graphene / Cu were compared at a current density of 0.01 mA cm -2 (Figure 4A). (b) The Relative Li nucleation overpotentials of the three electrodes were measured at different current densities (0.01, 0.10, 0.50, and 1.0 mA cm -2 ) (Figure 4B).

[0079] Figure 5 shows the CE Test results of the current collector according to an embodiment of the present invention. h-BN Monolayer / Cu exhibits the best life characteristics. The CE of h-BN Monolayer / Cu is maintained constantly, indicating that the reversible reaction of Li is constant and the battery can maintain a constant performance even during repeated charge and discharge.

[0080] Measurement conditions Current collector: Pristine Cu, h-BN Monolayer / Cu, Graphene Monolayer / Cu Electrolyte: 1 M LiTFSI in DOL / DME(5 / 5, v / v) + 2wt% LiNO3

[0081] Figure 6 shows the full cell C-rate measurement results according to an embodiment of the present invention. The full cell C-rate characteristics (NP Ratio = 1) with and without the introduction of h-BN Monolayer are compared. C-rate represents the charge and discharge rate. In Figure 6, when h-BN Monolayer is introduced, it shows that the battery can maintain a constant performance during various charge and discharges. That is, it is confirmed that the Rate characteristics are improved when h-BN Monolayer is introduced, and stable metal utilization is possible even at high rates.

[0082] Measurement conditions Current collector: Pristine Cu and h-BN Monolayer / Cu Electrolyte: 1 M LiPF6 in EC / DEC(5 / 5, v / v) + 10wt% FEC + 1wt% VC Charge Current Density: 0.1C

[0083] Figure 7 shows the measurement results of the full cell Cycle characteristics according to an embodiment of the present invention, and compares the full cell C-rate characteristics (NP Ratio = 1) with and without the introduction of h-BN Monolayer (Pristine Cu and h-BN Monolayer / Cu). It is confirmed that when h-BN Monolayer is introduced, the Rate characteristics are improved and stable metal utilization is possible even at high rates.

[0084] Measurement conditions Current collector: Pristine Cu and h-BN Monolayer / Cu Electrolyte: 1M LiPF6 in EC / DEC (5 / 5, v / v) + 10wt% FEC + 1wt% VC Charge / Discharge Current Densities: 0.1C / 0.2C

[0085] The present invention can not only reduce the lithium nucleation resistance through improving the lithium affinity on the surface of the current collector, suppress the lithium deposition of the lithium dendrite structure, but also provide a negative electrode current collector capable of uniform lithium deposition and uniform lithium deposition even at a high current density. Further, the negative electrode current collector may be utilized as a current collector for a non-aqueous negative electrode of a lithium metal battery with a high energy density.

[0086] As described above, although the embodiments are described by way of limited embodiments and drawings, those having ordinary knowledge in the art can make various modifications and variations from the above description. For example, the described technology may be executed in a different order from the described method, and / or the described components may be combined or combined in a different form from the described method, or replaced or substituted by other components or equivalents to achieve appropriate results. Therefore, the scope of the present invention is not defined by the disclosed embodiments, but is defined by the claims and equivalents thereof.

Claims

1. A current collector substrate, a two-dimensional material layer with atomic thickness formed on at least a part of at least one surface of the current collector substrate, a metal layer formed on at least a part of the two-dimensional material layer, comprising: the metal layer contains at least one or more selected from the group consisting of lithium metal, lithium sulfide, lithium halide, and lithium alloy, the metal layer is a vapor deposition layer or a pressure bonding layer formed on the two-dimensional material layer, a negative electrode current collector.

2. The current collector substrate contains at least one or more selected from the group consisting of Ni, Cu, Ti, V, Cr, Mn, Fe, Co, Zn, Mo, W, Ag, Au, Ru, Pt, Ir, Li, Al, Sn, Bi, Sb and their alloys, fired carbon, and stainless steel. The negative electrode current collector according to Claim 1.

3. The current collector substrate contains a first component including Cu, Ni, Ti, stainless steel or Al, and a second component (excluding the same elements as the first component) containing at least one or more selected from the group consisting of Ni, Cu, Ti, V, Cr, Mn, Fe, Co, Zn, Mo, W, Ag, Au, Ru, Pt, Ir, Li, Al, Sn, Bi, Sb and their alloys. The negative electrode current collector according to Claim 1.

4. The current collector substrate is a foil having a thickness of 5 μm to 100 μm. The negative electrode current collector according to Claim 1.

5. The two-dimensional material layer contains at least one or more of graphene, hexagonal boron nitride, and transition metal compounds. The negative electrode current collector according to Claim 1.

6. The thickness of the two-dimensional material layer is 0.4 nm to 10 nm. The negative electrode current collector according to Claim 1.

7. The metal layer is directly grown on the two-dimensional material layer by vapor deposition, The metal layer is directly grown by electrodeposition. The negative electrode current collector according to Claim 1.

8. The metal layer is free of metal-containing dendrite structures, The metal layer is a planar film. The negative electrode current collector according to Claim 1.

9. The thickness of the metal layer is 1 nm to 100 μm. The negative electrode current collector according to Claim 1.

10. The lithium alloy-containing negative electrode current collector according to claim 1, wherein the lithium alloy contains lithium and at least one or more selected from the group consisting of sodium (Na), aluminum (Al), calcium (Ca), silver (Ag), gold (Au), sodium (Na), zinc (Zn), magnesium (Mg), and potassium (K).

11. A negative electrode part, A positive electrode part, An electrolyte between the negative electrode part and the positive electrode part, Comprising, The negative electrode part includes a negative electrode current collector, The negative electrode current collector is, A current collector substrate, A two-dimensional material layer with an atomic thickness formed on at least a part of at least one surface of the current collector substrate, A metal layer formed on at least a part of the two-dimensional material layer, Comprising, The metal layer includes lithium metal, lithium sulfide, lithium halide, a lithium alloy, or both, The metal layer is a vapor deposition layer or a pressure bonding layer formed on the two-dimensional material layer, a metal battery.

12. The metal battery according to claim 11, wherein the electrolyte includes a liquid electrolyte, a solid electrolyte, or two of them.

13. The metal battery according to claim 11, wherein the negative electrode current collector is a current collector facing the non-negative electrode side where the electrolyte contacts on the metal layer.

14. The metal battery according to claim 11, wherein the metal battery is a lithium metal battery.

15. A method for manufacturing the negative electrode current collector according to claim 1, comprising: Preparing the current collector substrate; Forming a two-dimensional material layer with an atomic thickness on at least a part of at least one surface of the current collector substrate; Forming the metal layer on at least a part of the two-dimensional material layer; Comprising, The step of forming the metal layer includes vapor depositing the metal layer on the two-dimensional material layer or pressure bonding the metal layer, a method for manufacturing a negative electrode current collector.

16. The method for manufacturing a negative electrode current collector according to claim 15, wherein the step of forming the two-dimensional material layer includes transferring the two-dimensional material layer onto the current collector substrate.

17. The method for manufacturing a negative electrode current collector according to claim 15, wherein the step of forming the two-dimensional material layer includes directly growing the two-dimensional material layer on the current collector substrate by a vapor deposition method.

18. The method for manufacturing a negative electrode current collector according to claim 15, wherein the step of forming the metal layer includes directly growing the metal layer on the two-dimensional material layer by a vapor deposition method.

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