Negative electrode current collector and metal battery including same

Abstract

The present invention relates to a negative electrode current collector and a metal battery including the same, and more specifically, to a negative electrode current collector including a current collector substrate, an amorphous boron nitride layer formed on at least a portion of at least one surface of the current collector substrate, and a metal-containing layer formed on at least a portion of the amorphous boron nitride layer, and a metal battery including the same.

Description

[Technical Field]

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

[0002] Lithium secondary batteries are widely used commercially due to their excellent energy density and output characteristics among various secondary batteries. As demand for electric vehicles and large-capacity power storage devices increases, the development of high-energy batteries is required to meet these demands. Analysis has shown that lithium metal anodes are required to achieve energy densities of 400 Wh / kg or more. Therefore, active research is being conducted into the use of lithium metal as anodes in order to improve the energy density of secondary batteries.

[0003] Lithium metal batteries are secondary batteries that use lithium metal, which has high capacity and low reduction potential, as a negative electrode. Various types of lithium metal batteries, such as lithium-air batteries and lithium-sulfur batteries, have been developed and developed, and are attracting attention as next-generation energy battery systems with high energy density.

[0004] When lithium metal is used as the negative electrode, a lithium layer with a dendrite structure is formed during the deposition of lithium metal on the surface of the current collector. When lithium dendrites grow due to this uneven lithium layer, it can not only cause short circuits but also form dead lithium that does not contribute to capacity. Furthermore, this lithium layer with a dendrite structure can cause a decrease in the capacity and output characteristics of the battery, making it difficult to commercialize lithium metal batteries.

[0005] To solve this problem, technological developments have been made to form a uniform lithium layer on the surface of the current collector. However, conventional techniques have technical difficulties in controlling uniform lithium nucleation due to the high nucleation overpotential on the current collector surface. Summary of the Invention [Problem to be solved by the invention]

[0006] In order to solve the above-mentioned problems, the present invention provides a negative electrode current collector whose surface is modified with a metal-affinitive material that allows the formation of a uniform and dense metal-containing layer.

[0007] The present invention provides a metal battery that includes the negative electrode current collector according to the present invention and that can achieve high energy density.

[0008] The present invention provides a method for manufacturing a negative electrode current collector by surface treatment with a metal-affinitive material at an atomic thickness.

[0009] However, the problems that the present invention aims to solve are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description. [Means for solving the problem]

[0010] One embodiment of the present invention relates to a negative electrode current collector including a current collector substrate, an amorphous boron nitride layer formed on at least a portion of at least one surface of the current collector substrate, and a metal-containing layer formed on at least a portion of the amorphous boron nitride layer.

[0011] According to one embodiment of the present invention, the current collector substrate may include at least one 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, sintered carbon, and stainless steel.

[0012] According to one 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 including at least one 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 in the first component).

[0013] According to one embodiment of the present invention, the amorphous boron nitride layer may have a thickness of 10 nm or less.

[0014] According to one embodiment of the present invention, the amorphous boron nitride layer may have a thickness of 0.1 nm to 1 nm.

[0015] According to one embodiment of the present invention, the amorphous boron nitride layer may have an atomic thickness.

[0016] According to one embodiment of the present invention, the metal-containing layer is directly grown on the amorphous boron nitride layer by evaporation, and the metal-containing layer may be directly grown by electrodeposition.

[0017] According to one embodiment of the present invention, the metal-containing layer comprises at least one metal 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 the metal-containing layer comprises the metal. sulfide The material may include at least one selected from the group consisting of a halide, an oxide, an intermetallic compound, and an alloy.

[0018] According to one embodiment of the present invention, the metal-containing layer is free of a metal-containing dendrite structure, and the metal-containing layer may be a planar film.

[0019] According to one embodiment of the present invention, the metal-containing layer may have a thickness of 1 nm to 100 μm.

[0020] According to one embodiment of the present invention, the metal-containing layer may include lithium metal, lithium sulfide, lithium halide, a lithium alloy, or two thereof.

[0021] According to one embodiment of the present invention, the lithium alloy may include lithium and at least one 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).

[0022] One embodiment of the present invention relates to a metal battery including an anode part, a cathode part, and an electrolyte between the anode part and the cathode part, wherein the anode part includes an anode current collector, and the anode current collector includes a current collector substrate, an amorphous boron nitride layer formed on at least a portion of at least one surface of the current collector substrate, and a metal-containing layer formed on at least a portion of the amorphous boron nitride layer.

[0023] According to one embodiment of the present invention, the electrolyte may include a liquid electrolyte, a solid electrolyte, or a combination of the two.

[0024] According to an embodiment of the present invention, the negative electrode current collector may be a non-negative electrode current collector in which an electrolyte is in contact with the metal-containing layer.

[0025] According to one embodiment of the present invention, the metal battery may be a lithium metal battery.

[0026] One embodiment of the present invention relates to a method for manufacturing a negative electrode current collector, including the steps of: providing a current collector substrate; forming an amorphous boron nitride layer on at least a portion of at least one surface of the current collector substrate; and forming a metal-containing layer on at least a portion of the amorphous boron nitride layer.

[0027] According to one embodiment of the present invention, the step of forming the amorphous boron nitride layer comprises:

[0028] and transferring an amorphous boron nitride layer onto the current collector, wherein the amorphous boron nitride layer may have a thickness of 10 nm or less.

[0029] According to one embodiment of the present invention, the step of forming the amorphous boron nitride layer includes the step of directly growing amorphous boron nitride on the current collector by a vapor deposition method;

[0030] The amorphous boron nitride layer may have a thickness of 10 nm or less.

[0031] According to an embodiment of the present invention, the step of forming the metal-containing layer may include growing the metal-containing layer directly on the amorphous boron nitride layer by a deposition method. [Effects of the Invention]

[0032] The present invention provides an anode current collector having a certain energy density and stability, by modifying the surface of the anode current collector with a metal-affinitive material formed thereon, thereby suppressing the formation of a dendrite structure even when a metal is vapor-deposited on the current collector, and a lithium metal battery including the same and a method for manufacturing the same. [Brief explanation of the drawings]

[0033] [Figure 1A] FIG. 1 shows a scanning electron microscope image of the surface of a lithium metal layer deposited on a current collector according to one embodiment of the present invention, which shows the surface of a dendrite-structured lithium metal layer deposited on an existing Cu current collector that is not coated with amorphous boron nitride (thickness of amorphous boron nitride: 0 nm).

[0034] [Figure 1B] FIG. 1 shows a scanning electron microscope image of the surface of a lithium metal layer deposited on a current collector coated with amorphous boron nitride according to one embodiment of the present invention, which shows the extremely uniform surface of the lithium metal layer deposited on a Cu current collector coated with 1 nm thick amorphous boron nitride.

[0035] [Figure 1C] FIG. 1 shows a scanning electron microscope image of the surface of a lithium metal layer deposited on a current collector coated with amorphous boron nitride according to one embodiment of the present invention, which shows the surface of a uniform lithium metal layer deposited on a Cu current collector coated with amorphous boron nitride having a thickness of 3 nm.

[0036] [Figure 2A] 1 is an optical microscope image taken after transferring amorphous boron nitride grown on a Cu current collector to the surface of SiO2, according to one embodiment of the present invention.

[0037] [Figure 2B] 1 is a scanning electron microscope image taken after transferring amorphous boron nitride grown on a Cu current collector to the surface of SiO2, according to one embodiment of the present invention.

[0038] [Figure 3]

[0023] Figure 1 shows the results of Raman spectroscopy measurements showing the absence of crystallinity of amorphous boron nitride at various locations measured within an amorphous boron nitride film, in accordance with one embodiment of the present invention, and the locations where Raman spectroscopy was measured are shown in an optical image of the amorphous boron nitride film.

[0039] [Figure 4] According to one embodiment of the present invention, atomic force microscope data are shown that confirm the change in thickness of coated amorphous boron nitride depending on deposition time. (a) Coating surface of amorphous boron nitride deposited by PECVD for 30 minutes and coating thickness of 1.40 nm, (b) Coating surface of amorphous boron nitride deposited by PECVD for 40 minutes and coating thickness of 1.79 nm, and (c) Coating surface of amorphous boron nitride deposited by PECVD for 60 minutes and coating thickness of 2.73 nm.

[0040] [Figure 5A]1 shows a B1s spectrum measured by X-ray photoelectron spectroscopy of an amorphous boron nitride thin film deposited on a Cu current collector according to one embodiment of the present invention.

[0041] [Figure 5B] 1 shows the N1s spectrum measured by X-ray photoelectron spectroscopy of an amorphous boron nitride thin film deposited on a Cu current collector, according to one embodiment of the present invention.

[0042] [Figure 5C] 1 shows a Cu 2p spectrum measured by X-ray photoelectron spectroscopy of an amorphous boron nitride thin film deposited on a Cu current collector, according to one embodiment of the present invention.

[0043] [Figure 6] 1 shows the results of absorption spectroscopy measurements of amorphous boron nitride thin films deposited by PECVD, according to one embodiment of the present invention.

[0044] [Figure 7] FIG. 1 is a conceptual diagram comparing the nucleation overpotential of Cu and Ni current collectors and a Cu current collector on which an amorphous boron nitride layer is formed, through simulation, according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0045] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the present invention, if a detailed description of related known functions or configurations is deemed to unnecessarily obscure the gist of the present invention, such detailed description will be omitted. Furthermore, the terms used in this specification are used to appropriately express preferred embodiments of the present invention, and may vary depending on the intentions of users and operators, or the practices in the field to which the present invention pertains. Therefore, definitions of these terms should be based on the overall content of this specification. The same reference numerals shown in each drawing indicate the same elements.

[0046] Throughout this specification, when an element is said to be "on" another element, this includes not only when the element is in contact with a different element, but also when there is a further element between the two elements.

[0047] Throughout the specification, when any part is said to "comprise" any component, this does not mean that other components are excluded, but that other components may also be included.

[0048] Hereinafter, the negative electrode current collector, the metal battery, and the method for manufacturing the negative electrode current collector according to the present invention will be described in detail with reference to the embodiments and drawings, but the present invention is not limited to these embodiments and drawings.

[0049] The present invention relates to a negative electrode current collector. According to one embodiment of the present invention, the negative electrode current collector is formed by modifying the surface of the negative electrode current collector with amorphous boron nitride to have a metal-affinity surface, for example, a lithium-affinity surface. By modifying the surface of the negative electrode current collector to have a metal-affinity surface, a dense and flat metal-containing layer, for example, a lithium metal layer, can be formed on the surface of the current collector without suppressing or preventing the formation of a dendrite structure. Even after the deposition of the lithium metal layer, the formation of a dendrite structure can be suppressed, thereby providing a certain energy density and stability.

[0050] According to one embodiment of the present invention, the negative electrode current collector may include a current collector substrate; an amorphous boron nitride layer; and a metal-containing layer.

[0051] According to one embodiment of the present invention, the current collector substrate may include at least one 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; sintered carbon; and stainless steel. For example, the current collector substrate may include a first component including Cu, Ni, Ti, stainless steel, or Al; and a second component including at least one 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). The second component may not include the same elements as the first component, and the current collector substrate may be formed in the form of a mixture, coating, alloy, composite, or the like, mixed with the first component.

[0052] In one embodiment of the present invention, the current collector substrate may be a foil, thin film, film, or sheet, and may have a thickness of 5 μm to 100 μm. When the thickness falls within this range, the current collector substrate has high electrical conductivity, which facilitates electron transfer, and can be used as a current collector for high-energy-density lithium metal batteries due to its lithium-affinitive surface modification.

[0053] According to one embodiment of the present invention, the amorphous boron nitride layer modifies the surface of the current collector substrate to have a metal affinity, thereby reducing the nucleation overpotential on the current collector surface, thereby realizing uniform metal, e.g., lithium, nucleation and forming a metal deposition film, e.g., lithium metal deposition film, with a uniform and dense structure.

[0054] In one embodiment of the present invention, the amorphous boron nitride layer is formed on at least a portion of at least one surface of the current collector substrate, and can control the metal affinity of the metal-containing layer. That is, referring to Figure 7, a material modified with amorphous boron nitride has a reduced nucleation overpotential and improved lithium affinity, thereby reducing the resistance to lithium nucleation, suppressing the formation of lithium dendrites, and enabling uniform lithium deposition, as well as enabling uniform lithium (layer) deposition even at high current densities.

[0055] In one embodiment of the present invention, the thickness of the amorphous boron nitride layer may be 10 nm or less, 5 nm or less, 3 nm or less, 1 nm or less, or 0.1 nm to 1 nm, or may be an atomic thickness, for example, application of an atomic thickness favors adsorption of metal atoms, e.g., lithium atoms, and enables adjustment of electronic conductivity in a vertical direction from the substrate of the current collector, thereby adjusting the deposition rate of a metal-containing layer, e.g., a lithium metal layer, to form a uniform and dense lithium metal layer.

[0056] In one embodiment of the present invention, the amorphous boron nitride layer has a planar shape of the thickness range or atomic thickness mentioned above, which forms amorphous boron nitride of a thickness capable of adsorbing metal atoms.

[0057] According to one embodiment of the present invention, the metal-containing layer may be formed on at least a portion of the amorphous boron nitride layer and may be directly grown or transferred onto the amorphous boron nitride layer by a deposition method. For example, the lithium metal layer may be formed on the amorphous boron nitride layer because the resistance to lithium nucleation on the amorphous boron nitride layer is significantly reduced, suppressing lithium deposition in a dendrite structure, thereby enabling uniform lithium metal deposition and enabling uniform lithium nucleation at the atomic level and face-to-face, thereby allowing the formation of a large-area lithium metal layer. Furthermore, the lithium metal layer may be deposited in a uniform and compact form, suppressing side reactions and suppressing the formation and growth of lithium dendrites at high currents.

[0058] In one embodiment of the present invention, the metal-containing layer may be grown directly on the surface of the current collector modified with the amorphous boron nitride layer, thereby reducing metal nucleation overpotential and forming a flat, dense metal-containing layer with suppressed dendrite formation on the surface of the current collector. That is, the metal-containing layer may be formed as a planar film with a compact, flat structure, thereby improving certain energy density and stability. The metal-containing layer may also be free of metal dendrite structures, containing very little or no metal dendrites, thereby suppressing the formation of metal dendrite structures. The metal-containing layer may be formed as a uniform, compact film, thereby suppressing side reactions at high currents and suppressing the formation of dendrites during battery operation.

[0059] In one example of the present invention, the metal-containing layer may include at least one metal 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); a compound containing the metal (or metal element), a compound between metals (or metal element), and an alloy. For example, the metal (or metal element)-containing compound is sulfide , halides, oxides, etc.

[0060] In one example of the present invention, the metal-containing layer is a lithium metal layer, and the lithium metal layer may include at least one selected from the group consisting of lithium metal, a lithium-containing compound, a lithium-containing intermetallic compound, and a lithium alloy.

[0061] For example, the lithium-containing compound is sulfide , halides, oxides, etc., and may be, for example, lithium sulfide (e.g., LiS), lithium halide (e.g., LiF), lithium oxide (e.g., LiO2), etc.

[0062] For example, the lithium alloy and intermetallic compound may include, for example, lithium; and at least one 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).

[0063] For example, the lithium metal layer may further include at least one metal (or element) 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).

[0064] In one embodiment of the present invention, the thickness of the metal-containing layer may be 1 nm to 100 μm (micrometers), 10 nm to 50 μm, 1 μm to 40 μm, or 10 μm to 35 μm, or may be an atomic thickness. Forming a thickness within the above thickness range or even thinner within the above range is advantageous for increasing the energy density per cell.

[0065] The present invention relates to a metal battery, and in accordance with one embodiment of the present invention, the lithium metal battery includes an anode portion, a cathode portion, and an electrolyte between the anode portion and the cathode portion. The lithium metal battery exhibits high energy density, high stability, and long life characteristics by using the anode current collector according to the present invention.

[0066] According to one embodiment of the present invention, the metal battery may be a lithium (Li), sodium (Na), aluminum (Al), calcium (Ca), silver (Ag), gold (Au), sodium (Na), zinc (Zn), magnesium (Mg), or potassium (K) based metal battery.

[0067] 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 non-negative electrode current collector by applying the metal-containing layer thereto.

[0068] According to one embodiment of the present invention, the electrolyte may include any electrolyte known in the art applicable to metal batteries, and may be formed between the metal-containing layer of the negative electrode current collector and the positive electrode, and may include a liquid electrolyte, a solid electrolyte, or both. A separator may be further included between the electrolyte and the positive electrode, and the separator may include a liquid electrolyte, a solid electrolyte, or both, and may be adapted to the function of the electrolyte.

[0069] In one embodiment of the present invention, the electrolyte may form an anodeless metal battery in contact with the metal-containing layer, for example, forming an anodeless lithium metal battery.

[0070] According to one embodiment of the present invention, the positive electrode may be applied to any metal battery known in the art without limitation, and may be made of any oxide, sulfide The positive electrode may further include a positive electrode current collector.

[0071] As an example of the present invention, the metal battery may incorporate any operating and driving configuration known in the art of the present invention without exceeding the scope and spirit of the present invention, and will not be specifically mentioned herein.

[0072] The present invention relates to a method for manufacturing a negative electrode current collector according to the present invention. According to one embodiment of the present invention, the method may modify the surface of a current collector substrate with amorphous boron nitride to have a metal affinity, and then directly grow a metal-containing layer on the current collector, thereby forming a uniform and dense metal-containing film in which the formation of a dendrite structure is suppressed.

[0073] According to one embodiment of the present invention, the manufacturing method includes the steps of: providing a current collector substrate; forming an amorphous boron nitride layer on at least a portion of at least one surface of the current collector substrate; and forming a metal-containing layer on at least a portion of the amorphous boron nitride layer.

[0074] According to an embodiment of the present invention, the step of forming the amorphous boron nitride layer may be performed by a physical method or a chemical method. For example, the physical method may include transferring the amorphous boron nitride layer onto the current collector, and a two-dimensional material grown on a separate substrate may be peeled off by an electrical peeling method and transferred onto the current collector substrate. The transferring step may be performed by a transfer method known in the art of the present invention, and is not specifically mentioned herein.

[0075] For example, the electrochemical method may include directly growing an amorphous boron nitride layer on a current collector by vapor deposition, and may include directly growing amorphous boron nitride on a current collector substrate using chemical vapor deposition (CVD). The electrochemical method may further include atomic layer deposition (ALD), plasma-enhanced chemical vapor deposition (PECVD), and the like.

[0076] For example, the step of forming the amorphous boron nitride layer may be performed at a temperature between room temperature and 700° C., between room temperature and 500° C., between 50° C. and 500° C., between 100° C. and 500° C., or between 100° C. and 450° C. The layer may also be grown at atmospheric pressure or in a vacuum.

[0077] According to one embodiment of the present invention, the step of forming the metal-containing layer may be performed by directly growing the metal-containing layer on the amorphous boron nitride layer by a deposition method, or by directly growing the metal-containing layer on the current collector substrate whose surface has been modified with the amorphous boron nitride layer by electrochemical deposition, physical adsorption (e.g., pressing), alloying (e.g., a melting and alloying reaction such as "melting and alloying"), etc.

[0078] For example, the step of forming the metal-containing layer may be performed at a temperature between room temperature and 100° C., between room temperature and 90° C., between room temperature and 50° C., or between room temperature and 40° C. The layer may also be grown at atmospheric pressure or in a vacuum.

[0079] The present invention may provide a method for manufacturing a metal battery that incorporates or utilizes the negative electrode current collector or the method for manufacturing the negative electrode current collector according to the present invention. For example, the method may include the steps of preparing the negative electrode current collector, preparing an electrolyte and / or a separator, preparing a positive electrode, and sequentially arranging, connecting, bonding, adhering, and / or squeezing the negative electrode current collector, the electrolyte and / or the separator, and the positive electrode.

[0080] Although the present invention will be described with reference to preferred embodiments thereof, the present invention is not limited thereto, and various modifications and changes can be made to the present invention without departing from the spirit and scope of the present invention as described in the following claims, detailed description of the invention, and the accompanying drawings.

[0081] Embodiment

[0082] Manufacturing Example 1

[0083] A monolayer of amorphous boron nitride atoms thick was fabricated and transferred onto the current collector.

[0084] Manufacturing Example 2

[0085] Amorphous boron nitride films with atomic thickness were formed on the surface of the Cu current collector by directly growing amorphous boron nitride on the Cu foil by PECVD deposition (temperature: 500°C and pressure: 120 mTorr).

[0086] Manufacturing Example 3

[0087] Fabrication of an electrochemical cell consisting of a lithium metal-negative electrode current collector

[0088] A lithium metal layer of a desired thickness was deposited by electrochemical deposition on the surface of the negative electrode current collector on which the amorphous boron nitride film was formed, prepared using the negative electrode current collector prepared in Preparation Examples 1 to 3. Then, a separator and an electrolyte were added.

[0089] Current collector: Pristine Cu, a-BN Monolayer / Cu

[0090] Electrolyte: 1M LiTFSI in 1, 3-dioxolane(DOL) / 1, 2-dimethyoxyethane(DME)=1 / 1(v / v)+2wt% LiNO3

[0091] The surface characteristics and crystallographic characteristics of the prepared current collector were analyzed and are shown in FIGS.

[0092] 1A to 1C show SEM images of the lithium metal deposition surface according to one embodiment of the present invention. FIG. 1A shows pristine Cu, and FIG. 1B shows Li metal (0.1 mAh / cm) deposited on a-BN (1 nm) / Cu and a-BN (3 nm) / Cu. 2 The surface morphology was compared with the SEM image after electrochemical deposition. It can be seen that the most uniform Li metal deposition was achieved on a-BN (1 nm) / Cu.

[0093] In other words, the image of the lithium layer formed on the Cu current collector differs from one with a dendritic structure, and the image of the lithium layer formed on the a-BN (1 nm) / Cu shows that the dendritic structure is barely formed. This indicates that the amorphous boron nitride coated Cu current collector reduces the lithium nucleation resistance and allows the formation of a dense, flat lithium layer on the surface of the current collector without dendritic lithium.

[0094] Figures 2A and 2B show optical microscope and scanning electron microscope images of an amorphous boron nitride film grown on a Cu current collector after it was transferred to the surface of SiO2, confirming that the film has amorphous properties without crystallinity.

[0095] FIG. 3 shows Raman spectroscopy results at various locations on an amorphous boron nitride film, which confirms the absence of crystallinity in the amorphous boron nitride film, according to one embodiment of the present invention.

[0096] Figure 4 shows atomic force microscopy data showing the change in thickness of the amorphous boron nitride deposited on a Cu current collector over deposition time. (a) The surface of an amorphous boron nitride film deposited by PECVD for 30 minutes and showing a film thickness of 1.40 nm. (b) The surface of an amorphous boron nitride film deposited by PECVD for 40 minutes and showing a film thickness of 1.79 nm. (c) The surface of an amorphous boron nitride film deposited by PECVD for 60 minutes and showing a film thickness of 2.73 nm.

[0097] 5A to 5C show the B1s spectrum, N1s spectrum, and Cu2p spectrum of the amorphous boron nitride thin film deposited on the Cu current collector measured by X-ray photoelectron spectroscopy, which confirm the formation of amorphous boron nitride.

[0098] FIG. 6 shows the results of absorption spectroscopy measurements of amorphous boron nitride thin films, according to one embodiment of the present invention, where optical absorption at 190 nm wavelength confirms the formation of amorphous boron nitride.

[0099] The present invention provides an anode current collector that is surface-treated with a lithium-affinity material with an atomic thickness (10 nm or less). The improved lithium affinity of the anode current collector surface reduces resistance to lithium nucleation during lithium deposition, suppresses lithium deposition with a lithium dendritic structure, and allows for uniform lithium deposition even at high current densities. Furthermore, the anode current collector has a certain energy density and stability, and can be used as a non-anode current collector for high-energy-density lithium metal batteries.

[0100] Although the embodiments have been described above using limited examples and figures, those skilled in the art will appreciate that various modifications and variations may be made to the above description. For example, the described techniques may be performed in an order different from that described, and / or the described components may be combined or combined in a manner different from that described, or other components or equivalents may be substituted or substituted, and still achieve suitable results. Therefore, the scope of the present invention is not limited to the disclosed embodiments, but is defined by the claims and their equivalents.

Claims

1. a current collector substrate; an amorphous boron nitride layer formed on at least a portion of at least one surface of the current collector substrate; a metal-containing layer formed at least partially on the amorphous boron nitride layer; Including, The metal-containing layer includes at least one of lithium metal, lithium halide, and a lithium alloy.

2. 2. The negative electrode current collector according to claim 1, wherein the current collector substrate comprises at least one 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; sintered carbon; and stainless steel.

3. The current collector substrate is a first component containing Cu, Ni, Ti, stainless steel, or Al; a second component (excluding the same elements as in the first component) containing at least one 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; The negative electrode current collector of claim 1 , comprising:

4. 2. The negative electrode current collector according to claim 1, wherein the amorphous boron nitride layer has a thickness of 10 nm or less.

5. 2. The negative electrode current collector according to claim 1, wherein the amorphous boron nitride layer has a thickness of 0.1 nm to 1 nm.

6. 10. The negative electrode current collector of claim 1, wherein the metal-containing layer is free of a metal-containing dendrite structure, and the metal-containing layer is a planar film.

7. The negative electrode current collector according to claim 1, wherein the metal-containing layer has a thickness of 1 nm to 100 μm.

8. 2. The negative electrode current collector according to claim 1, wherein the lithium alloy contains lithium and at least one 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).

9. A negative electrode portion; A positive electrode portion; an electrolyte between the negative electrode portion and the positive electrode portion; Including, the negative electrode part includes a negative electrode current collector, The negative electrode current collector is a current collector substrate; an amorphous boron nitride layer formed on at least a portion of at least one surface of the current collector substrate; a metal-containing layer formed at least partially on the amorphous boron nitride layer; Including, The metal battery, wherein the metal-containing layer includes at least one of lithium metal, lithium halide, and lithium alloy.

10. 10. The metal battery of claim 9, wherein the electrolyte comprises a liquid electrolyte, a solid electrolyte, or two thereof.

11. The metal battery according to claim 9 , wherein the negative electrode current collector is a non-negative electrode current collector in which an electrolyte is in contact with the metal-containing layer.

12. The metal battery of claim 9, wherein the metal battery is a lithium metal battery.

13. providing a current collector substrate; forming an amorphous boron nitride layer on at least a portion of at least one surface of the current collector substrate; forming a metal-containing layer on at least a portion of the amorphous boron nitride layer; Including, The step of forming the amorphous boron nitride layer comprises: growing amorphous boron nitride directly on the current collector by vapor deposition; The step of forming the metal-containing layer comprises: growing a metal-containing layer directly on the amorphous boron nitride layer by vapor deposition; The step of forming the amorphous boron nitride layer comprises directly growing the layer at a temperature between room temperature and 700° C. The step of forming the metal-containing layer comprises directly growing the metal-containing layer at a temperature between room temperature and 100° C. The metal-containing layer contains at least one of lithium metal, lithium halide, and a lithium alloy.

14. A method for manufacturing a negative electrode current collector as described in claim 13, wherein the thickness of the amorphous boron nitride layer is 10 nm or less.

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