Anodeless lithium secondary battery using sintered body of amorphous alloy powder or metallic glass powder, lithium metal secondary battery, and method for manufacturing same

Abstract

In order to improve the coulombic efficiency, electric capacity, and the like of an anode current collector, the present invention provides an anodeless lithium secondary battery using a sintered body of a mixture of an amorphous alloy powder or metallic glass powder and a non-metallic powder, or an anodeless lithium secondary battery comprising a current collector made of a sintered body of a mixture of an amorphous alloy powder or metallic glass powder containing two or more elements.

Description

Anode-less lithium secondary battery, lithium metal secondary battery and manufacturing method thereof using amorphous alloy powder or metallic glass powder sintered body

[0001] The present invention relates to a non-anode lithium secondary battery using a sintered body of an amorphous alloy powder or a metallic glass powder, a lithium metal secondary battery, and a method for manufacturing a non-anode lithium secondary battery using a sintered body of an amorphous alloy powder or a metallic glass powder, and more particularly, to a non-anode lithium secondary battery using a sintered body of an amorphous alloy powder or a mixture of metallic glass powder and a non-metal powder and a method for manufacturing the same, and to a non-anode lithium secondary battery using a sintered body of an amorphous alloy powder or a metallic glass powder and a method for manufacturing the same. The present invention relates to a lithium metal secondary battery including a lithium metal negative electrode in which lithium metal is filled in an empty space of a sintered body of an amorphous alloy powder or a mixture of metallic glass powder and a non-metal powder, and a lithium metal secondary battery including a lithium metal negative electrode in which lithium metal is filled in an empty space of a sintered body of an amorphous alloy powder or a metallic glass powder.

[0002] The current collector of a lithium secondary battery serves as a conductor that collects electrons generated through electrochemical reactions in the active material and channels them to an external conductor, or as an intermediate passage that supplies electrons provided from the external conductor to the electrode active material. Furthermore, it is a crucial material for implementing the shape of the electrode plate. Considering factors such as electronic conductivity, electrochemical stability, and the electrode plate manufacturing process, most current collectors use metallic materials. Since collectors that are too thin lack sufficient mechanical strength, a thickness of approximately 10 to 20 μm is typically used. Furthermore, the surface condition of the current collector significantly influences the application of the slurry. It must exhibit good wettability with the electrode slurry and ensure sufficient bonding strength between the binder and the current collector even after the solvent has evaporated.

[0003] Copper is primarily used as the negative current collector for lithium secondary batteries. This is because nickel and copper are electrochemically inactive metals within the operating range of carbon electrodes. However, nickel is expensive and therefore not widely used, while the relatively inexpensive copper is widely used.

[0004] Therefore, further research is needed on methods to improve the coulombic efficiency, electrical capacity, etc. of the negative electrode current collector using copper or nickel.

[0005] The present invention is intended to solve the above problems, and provides a non-anode lithium secondary battery including a current collector manufactured from a sintered body of a mixture of amorphous alloy powder or metallic glass powder and non-metallic powder, or a current collector manufactured from a sintered body of two or more types of amorphous alloy powder or metallic glass powder, in order to improve the coulombic efficiency, electric capacity, etc. of the negative electrode current collector.

[0006] In addition, it is an object of the present invention to provide a lithium metal secondary battery including a lithium metal negative electrode in which lithium metal is filled in a void space of a sintered body of a mixture of an amorphous alloy powder or a metallic glass powder and a non-metallic powder, or a sintered body of a mixture of two or more types of amorphous alloy powders or metallic glass powders.

[0007] In order to achieve the above-described object, a non-anode lithium secondary battery according to a first embodiment of the present invention comprises: a cathode; an anode current collector positioned facing the cathode and manufactured by sintering a mixture of amorphous alloy powder or metallic glass powder and non-metal powder; an electrolyte positioned between the cathode and the anode current collector; and a separator separating the cathode and the current collector.

[0008] In addition, a non-anode lithium secondary battery according to a second embodiment of the present invention includes: a cathode; an anode current collector positioned facing the cathode and manufactured by sintering an amorphous alloy powder or metallic glass powder mixture; an electrolyte positioned between the cathode and the current collector; and a separator separating the cathode and the anode current collector.

[0009] In addition, a lithium metal secondary battery according to a third embodiment of the present invention includes: a positive electrode; a lithium metal negative electrode positioned facing the positive electrode, the void space of a sintered body of an amorphous alloy powder or a mixture of metallic glass powder and non-metal powder being filled with lithium metal; an electrolyte positioned between the positive electrode and the lithium metal negative electrode; and a separator separating the positive electrode and the lithium metal negative electrode.

[0010] In addition, a lithium metal secondary battery according to a fourth embodiment of the present invention includes: a positive electrode; a lithium metal negative electrode positioned facing the positive electrode, the void space of a sintered body of a mixture of amorphous alloy powder or metallic glass powder being filled with lithium metal; an electrolyte positioned between the positive electrode and the lithium metal negative electrode; and a separator separating the positive electrode and the lithium metal negative electrode.

[0011] In the first to fourth embodiments, the electrolyte is characterized in that it is a liquid electrolyte or a solid electrolyte.

[0012] In addition, a method for manufacturing a non-anode lithium secondary battery of a fifth embodiment of the present invention includes: a first step of manufacturing a paste containing an amorphous alloy powder or a metallic glass powder and a non-metallic powder; a second step of printing the paste of the first step on a substrate using a screen mask pattern; a third step of heat-treating the paste of the second step to obtain a sintered body; and a fourth step of separating the sintered body obtained in the third step from the substrate. Here, in the second step, the paste mixed in the first step is printed using a squeegee. In the third step, the printed product in the second step is placed in an RTP (Rapid Thermal Process) equipment, purged in an Ar atmosphere, and then heat-treated while flowing Ar gas.

[0013] In addition, a method for manufacturing a non-anode lithium secondary battery of a sixth embodiment of the present invention includes: a first step of manufacturing a paste containing an amorphous alloy powder or a metallic glass powder; a second step of printing the paste of the first step on a substrate using a screen mask pattern; a third step of heat-treating the paste of the second step to obtain a sintered body; and a fourth step of separating the sintered body obtained in the third step from the substrate. Here, in the second step, the paste mixed in the first step is printed using a squeegee. In the third step, the printed product in the second step is placed in an RTP (Rapid Thermal Process) equipment, purged in an Ar atmosphere, and then heat-treated while flowing Ar gas.

[0014] In the present invention, in order to manufacture a current collector or a lithium metal negative electrode, a mixture of two or more types of amorphous alloy powders or two or more types of metallic glass powders and non-metallic powders is sintered and used, or a mixture of two or more types of amorphous alloy powders or two or more types of metallic glass powders is sintered and used.

[0015] The above metallic glass powder contains at least two different elements. Here, the metallic glass powder contains a component represented by the following formula 1.

[0016] (Am1) n1 + (Am2) n2 + (Am3) n3 + ····· + (Amx) ny (Formula 1)

[0017] Here, Am1, Am2, Am3, ····· , Amx represent different metallic glass elements, x is an integer greater than or equal to 2, more preferably x is an integer greater than or equal to 2 and less than or equal to 30, y is an integer greater than or equal to 2 and less than or equal to 30, and satisfies n1 > 0, n2 > 0, n3 ≥ 0, ····· , ny ≥ 0 and n1 + n2 + ····· + ny = 100.

[0018] For example, if the metallic glass is composed of two elements, it is represented by the following equation 1-1.

[0019] (Am1) n1 + (Am2) n2 (Formula 1-1)

[0020] Here, Am1 and Am2 represent different metallic glass elements, and satisfy n1 > 0, n2 > 0, n3 = 0, ····· , ny = 0, and n1 + n2 = 100.

[0021] Alternatively, if the metallic glass is composed of four elements, it is represented by the following equation 1-2.

[0022] (Am1) n1 + (Am2) n2 + (Am3) n3 + (Am4) n4 (Formula 1-2)

[0023] Here, Am1, Am2, Am3, and Am4 represent different metallic glass elements, and satisfy n1 > 0, n2 > 0, n3 > 0, n4 > 0, n5 = 0, ····· , ny = 0, and n1 + n2 + n3 + n4 = 100.

[0024] The metal glass powder containing the component represented by the above formula 1 satisfies the enthalpy relationship of the following formula 2, △H total ≥ 0 In the process of manufacturing an amorphous alloy powder or metallic glass powder, the amorphous alloy powder or metallic glass powder more easily undergoes a phase transformation into a crystalline phase, and thus the effect of the present invention is not obtained.

[0025] △H total = △H 12 + △H 13 + △H 14 + ····· + △H 1x

[0026] + △H 23 + △H 24 + ····· + △H 2x

[0027] + △H 34 + ····· + △H 3x

[0028] + ····· + △H (x-1)x < 0 (Equation 2)

[0029] Here, △H (x-1)x represents the mixture series of elements Am(x-1) and Am(x). For example, the mixture series of elements in the above equation 2 is defined as follows.

[0030] △H 12 : Mixing heat of Am1 and Am2 elements

[0031] △H 13 : Mixing heat of Am1 and Am3 elements

[0032] △H 14 : Mixing heat of Am1 and Am4 elements

[0033] △H 1x : Mixing heat of Am1 and Amx elements

[0034] △H 23 : Mixing heat of Am2 and Am3 elements

[0035] △H 24 : Mixing heat of Am2 and Am4 elements

[0036] △H 2x : Mixing heat of Am2 and Amx elements

[0037] △H 34 : Mixing heat of Am3 and Am4 elements

[0038] △H 3x : Mixing heat of Am3 and Amx elements

[0039] For example, if the above metal glass powder is composed of three elements, it is represented by the following formula 2-1.

[0040] △H total = △H 12 + △H 13

[0041] + △H 23 < 0 (Formula 2-1)

[0042] The above metallic glass powder is selected from the group consisting of lanthanum (La), cerium (Ce), praseodymium (Pr), promethium (Pm), samarium (Sm), lutetium (Lu), yttrium (Y), neodymium (Nd), gadolinium (Gd), terbium (Tb), dysprosium (Dy), hormium (Ho), erbium (Er), thulium (Tm), thorium (Th), calcium (Ca), scandium (Sc), barium (Ba), beryllium (Be), bismuth (Bi), rubidium (Rb), germanium (Ge), lead (Pb), ytterbium (Yb), chromium (Cr), strontium (Sr), europium (Eu), zirconium (Zr), thallium (Tl), lithium (Li), hafnium (Hf), magnesium (Mg), phosphorus (P), arsenic (As), iron (Fe), It is characterized by being a mixture of two or more elements selected from palladium (Pd), gold (Au), plutonium (Pu), cobalt (Co), gallium (Ga), tungsten (W), germanium (Ge), silver (Ag), sodium (Na), molybdenum (Mo), nickel (Ni), aluminum (Al), copper (Cu), zinc (Zn), antimony (Sb), silicon (Si), tin (Sn), titanium (Ti), cadmium (Cd), indium (In), platinum (Pt), and mercury (Hg).

[0043] The glass transition temperature of the above metallic glass powder is characterized by being 100°C or higher.

[0044] The above amorphous alloy powder is characterized in that one or more of Li powder, Mg powder, Cu powder, Ni powder, Al powder, Ti powder, and Sn powder is selected and used.

[0045] The above non-metallic powder is characterized in that one or more of graphite powder, ZrO2 powder, LLZO (lithium lanthanum zirconate oxide) powder, and solid electrolyte powder are selected and used. Here, ZrO2 can be used in the form of Zr(OH)4.

[0046] The size of the above amorphous alloy powder or metallic glass powder may be 50 nm to 30 μm, and more preferably 500 nm to 20 μm.

[0047] The paste containing the above amorphous alloy powder or metallic glass powder may contain the amorphous alloy powder or metallic glass powder and a solvent, and the weight ratio of the amorphous alloy powder or metallic glass powder and the solvent may be mixed in a range of 5 to 9.5:1.5 to 5.

[0048] The paste containing the amorphous alloy powder or metallic glass powder and graphite may contain the amorphous alloy powder or metallic glass powder, graphite, and a solvent, and the weight ratio of the amorphous alloy powder or metallic glass powder and the graphite may be mixed in a range of 60 to 95:5 to 40. In addition, the weight ratio of the mixture of the amorphous alloy powder or metallic glass powder and graphite and the solvent may be mixed in a range of 5 to 9.5:1.5 to 5.

[0049] A paste containing Cu powder and Zr(OH)4 of an amorphous alloy powder or metallic glass powder may contain Cu powder, Zr(OH)4 and a solvent, and the at% ratio of Cu and Zr may be 90 to 99:1 to 10. The weight ratio of the mixture of Cu powder and Zr(OH)4 and the solvent may be mixed in a ratio of 5 to 9.5:1.5 to 5.

[0050] A paste containing Cu powder, graphite and Zr(OH)4 of an amorphous alloy powder or metallic glass powder may contain Cu powder, graphite, Zr(OH)4 and a solvent, and the at% ratio of Cu and Zr may be 90 to 99:1 to 10. A weight ratio of a mixture of Cu powder and Zr(OH)4 and graphite may be 80 to 99:1 to 20. A weight ratio of a mixture of Cu powder, graphite and Zr(OH)4 and a solvent may be mixed in a ratio of 5 to 9.5:1.5 to 5.

[0051] The paste containing LLZO powder may contain LLZO powder and a solvent, and a weight ratio of LLZO powder and solvent may be 3 to 30:7 to 70.

[0052] The solvent may be any one of methanol, ethanol, propanol, isopropanol, n-butanol, 2-butanol, isobutanol, tert-butanol, 2-ethoxyethanol, 2-butoxyethanol, 3-methoxypropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propane, diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, butyl acetate, polyethylene glycol, or a mixture thereof.

[0053] The method of obtaining a sintered body by heat treatment of the present invention includes a step of vaporizing a solvent by heat treatment at a temperature of 200°C to 300°C for 1 to 10 minutes, and a step of sintering by heat treatment at a temperature of 500°C to 1,000°C for 1 to 10 minutes.

[0054] As described above, the present invention has the effect of improving the coulombic efficiency and electric capacity of a negative electrode collector by using a negative electrode collector having a sintered body of a mixture of an amorphous alloy powder or a metallic glass powder and a non-metallic powder, or a negative electrode collector having a sintered body of an amorphous alloy powder or a metallic glass powder.

[0055] Figure 1 shows the capacity-to-cycle relationship when charge-discharge is performed under 0.2 C (3.0-3.8 V cutoff) conditions using composites of Zr-Cu-Ni-Al, Mo-Zr-Co-Si, Mo-Zr-Ti-Si, Ti-Cu-Ni-Zr, and Al-Ni-Y-Co metallic glass powders, 10 wt% graphite, and 1 at% Zr(OH)4 as the cathode and LFP as the anode.

[0056] Figure 2 is an SEM image before cycling for analysis of the surface shape of a cathode to which a composite of Mo-Zr-Co-Si metallic glass powder, 10 wt% graphite, and 1 at% Zr(OH)4 is applied. Figure 2(a) shows an SEM image of the surface of the cathode, and Figure 2(b) is an SEM image of a cross-section of the cathode.

[0057] Figure 3 shows the 0.1 mA cm of a half-cell having a cathode applied with a composite of Zr-Cu-Ni-Al, Mo-Zr-Co-Si, Mo-Zr-Ti-Si, Ti-Cu-Ni-Zr, and Al-Ni-Y-Co metallic glass powders, 10 wt% graphite, and 1 at% Zr(OH)4. -2 0.5 mAh cm at a current density -2 The overpotential measured by the yulrang is compared with the overpotential measured under the same conditions for a half-cell manufactured with copper foil.

[0058] The present invention is susceptible to various modifications and embodiments. Specific embodiments are illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, but rather to encompass all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention. Throughout the description of each drawing, similar reference numerals have been used to designate similar components.

[0059] Terms such as first, second, A, and B may be used to describe various components, but these components should not be limited by these terms. These terms are used solely to distinguish one component from another.

[0060] For example, without departing from the scope of the present invention, the first component could be referred to as the second component, and similarly, the second component could also be referred to as the first component. The term "and / or" includes any combination of a plurality of related listed items or any one of a plurality of related listed items.

[0061] When a component is referred to as being "connected" or "connected" to another component, it should be understood that it may be directly connected or connected to that other component, but that there may be other components intervening. Conversely, when a component is referred to as being "directly connected" or "connected" to another component, it should be understood that there are no other components intervening.

[0062] The terminology used in this application is only used to describe specific embodiments and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, it should be understood that the terms "comprise" or "have" indicate the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0063] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and will not be interpreted in an idealized or overly formal sense unless explicitly defined herein.

[0064]

[0065] (Reference Example 1) Cu powder sintered body

[0066] 1. Coin cell manufacturing

[0067] Half cells were manufactured by sintering 500 nm Cu powder to produce an 18 mm diameter electrode as a working electrode, and a 16 mm diameter lithium metal (200 μm thick) was used as a counter electrode. Coin cells were manufactured using a CR2032 model in a glove box under an Ar atmosphere (O2 < 1 ppm, H2O < 1 ppm). The half cells were manufactured in the following order: a case, an 18 mm electrode, a separator (Celgard 2400), 70 μL of electrolyte (2 wt% lithium nitrate (LiNO3) mixed with 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in 1:1 1,3-dioxolane / 1,2-dimethoxyethane (DOL / DME)), a 16 mm lithium metal, a spacer, a wave spring, and a cap.

[0068] 2. Evaluation of half-cell charge-discharge voltage profile of Cu powder sintered cathode

[0069] Using Cu powder sintered body as working electrode and lithium metal as counter electrode, current density was 0.1 mA / cm 2 0.5 mAh / cm as a condition 2 The performance of the electrode was evaluated by charging it as much as possible.

[0070] 3. Evaluation of full-cell charge-discharge performance of Cu powder sintered cathode

[0071] The cell performance was evaluated by charging and discharging the Cu powder sintered body as the cathode and LFP as the anode under 0.2 C (3.0–3.8 V cutoff) conditions.

[0072]

[0073] (Examples 1 to 5) Secondary batteries manufactured by mixing metallic glass powders of Zr-Cu-Ni-Al, Mo-Zr-Co-Si, Mo-Zr-Ti-Si, Ti-Cu-Ni-Zr, and Al-Ni-Y-Co, Zr(OH)4, and graphite, respectively.

[0074] 1. Preparation of paste

[0075] Zr-Cu-Ni-Al metallic glass powder, Zr(OH)4, graphite paste (Example 1), Mo-Zr-Co-Si metallic glass powder, Zr(OH)4, graphite paste (Example 2), Mo-Zr-Ti-Si metallic glass powder, Zr(OH)4, graphite paste (Example 3), Ti-Cu-Ni-Zr metallic glass powder, Zr(OH)4, graphite paste (Example 4), Al-Ni-Y-Co metallic glass powder, Zr(OH)4, graphite paste (Example 5) were prepared, and when each metallic glass powder and Zr(OH)4 were mixed, the ratio of the mixture of Cu, Mo, and Al and Zr was 99:1 at%, respectively. And the metallic glass powders of Zr-Cu-Ni-Al, Mo-Zr-Co-Si, Mo-Zr-Ti-Si, Ti-Cu-Ni-Zr, and Al-Ni-Y-Co, and the mixture of Zr(OH)4 and graphite were mixed in a ratio of 90:10 wt%. The metallic glass powders of Zr-Cu-Ni-Al, Mo-Zr-Co-Si, Mo-Zr-Ti-Si, Ti-Cu-Ni-Zr, and Al-Ni-Y-Co, the mixture of Zr(OH)4 and graphite, and PEG (Polyethylene glycol) were placed in a paste mixer container in a ratio of 8.5:1.5 wt%. Using a paste mixer, the first condition was set to 1000 revolutions, the resolution was set to 1000, and the second condition was set to 100 revolutions, the resolution was set to 100, and the second condition was set to 100 revolutions, the resolution was set to 100, and the second condition was set to 1 minute, and then mixing was performed.

[0076] 2. Electrode manufacturing

[0077] Half cells were printed using a circular pattern screen mask with a diameter of 18 mm, and full cells were printed using a circular pattern screen mask with a diameter of 16 mm. A certain amount of a mixed paste of Zr-Cu-Ni-Al, Mo-Zr-Co-Si, Mo-Zr-Ti-Si, Ti-Cu-Ni-Zr, and Al-Ni-Y-Co metallic glass powders, Zr(OH)4, and graphite, manufactured on the upper part of the screen mask pattern, was printed on the substrate using a squeegee. The substrate printed with the mixed paste of Zr-Cu-Ni-Al, Mo-Zr-Co-Si, Mo-Zr-Ti-Si, Ti-Cu-Ni-Zr, and Al-Ni-Y-Co metallic glass powders, Zr(OH)4, and graphite was placed in an RTP (Rapid Thermal Process) equipment and processed in a vacuum. After purging the inside of the RTP equipment twice with Ar atmosphere, heat treatment was performed while flowing Ar gas at a rate of 70 sccm. Heat treatment was performed at the internal temperature of the RTP at 250℃ for 5 minutes to vaporize the solvent PEG, and then heat treatment was performed at 700℃ for 5 minutes to allow sintering between the metallic glass powders of Zr-Cu-Ni-Al, Mo-Zr-Co-Si, Mo-Zr-Ti-Si, Ti-Cu-Ni-Zr, and Al-Ni-Y-Co, Zr(OH)4, and graphite powders, respectively. After the heat treatment was completed, the printed substrate was removed from the RTP equipment, and the circular electrode formed by sintering was separated from the substrate.

[0078] 3. Coin cell manufacturing

[0079] The half-cells were made of a mixed paste of metallic glass powders of Zr-Cu-Ni-Al, Mo-Zr-Co-Si, Mo-Zr-Ti-Si, Ti-Cu-Ni-Zr, and Al-Ni-Y-Co, Zr(OH)4, and graphite, each with a diameter of 18 mm, as a working electrode, and lithium metal (200 μm thick) with a diameter of 16 mm was used as a counter electrode. Coin cells were manufactured in a glove box under an Ar atmosphere (O2<1 ppm, H2O<1 ppm) using a CR2032 model. The half-cells were manufactured in the following order: case, 18 mm electrode, separator (Celgard 2400), 70 μL of electrolyte (2 wt% lithium nitrate (LiNO3) mixed with 1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in 1:1 1,3-dioxolane / 1,2-dimethoxyethane (DOL / DME)), 16 mm lithium metal, spacer, wave spring, and cap.

[0080] 4. Half-cell charge-discharge performance evaluation of cathodes with metallic glass powders of Zr-Cu-Ni-Al, Mo-Zr-Co-Si, Mo-Zr-Ti-Si, Ti-Cu-Ni-Zr, and Al-Ni-Y-Co, Zr(OH)4, and graphite composites, respectively.

[0081] The cathode having a metal glass powder of Zr-Cu-Ni-Al, Mo-Zr-Co-Si, Mo-Zr-Ti-Si, Ti-Cu-Ni-Zr, and Al-Ni-Y-Co, Zr(OH)4, and graphite composite as the working electrode and lithium metal as the counter electrode was used at a current density of 0.1 mA / cm 2 0.5 mAh / cm as a condition 2 The overvoltage of the electrode was evaluated by charging it as much as possible.

[0082] The cathodes equipped with metallic glass powders of Zr-Cu-Ni-Al, Mo-Zr-Co-Si, Mo-Zr-Ti-Si, Ti-Cu-Ni-Zr, and Al-Ni-Y-Co, Zr(OH)4, and graphite composites were compared for cell performance by mixing one type of metallic glass alloy powder with Zr(OH)4 and graphite. As shown in Fig. 1, the x-axis represents the charge capacity, and the y-axis represents the number of charge / discharge cycles. The capacity of the Cu powder sintered body decreased rapidly as the number of cycles increased. It was confirmed that the metallic glass powder, Zr(OH)4, and graphite composite electrodes initially decreased in capacity but maintained a stable capacity up to 1000 cycles.

[0083] Meanwhile, Fig. 3 is a voltage profile of the charging stage of a composite electrode of copper powder sintered body and metallic glass powder, Zr(OH)41 at%, and graphite 10 wt%. As shown in Fig. 3, the x-axis is the capacity, the y-axis is the voltage, and it represents the nucleation overvoltage, and in the charging stage, due to the graphite in the electrode, about 0.5 mAh / cm 2 A step occurred due to Li intercalation until , and thereafter, a voltage peak tended to occur as Li was deposited on the electrode surface. Compared to the Cu 500 nm and graphite 10 wt% composite cathode, it was confirmed that the nucleation overvoltage was reduced when using metallic glass.

[0084]

[0085] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and will not be interpreted in an idealized or overly formal sense unless explicitly defined herein.

Claims

1. Bipolar; A current collector positioned facing the anode and manufactured by sintering a mixture of amorphous alloy powder or metallic glass powder and non-metallic powder; An electrolyte positioned between the positive electrode and the current collector; and A non-anode lithium secondary battery using an amorphous alloy powder or metallic glass powder sintered body including a separator separating the positive electrode and the current collector.

2. Bipolar; A current collector positioned facing the anode and manufactured by sintering a mixture of amorphous alloy powder or metallic glass powder; An electrolyte positioned between the positive electrode and the current collector; and A non-anode lithium secondary battery using an amorphous alloy powder or metallic glass powder sintered body including a separator separating the positive electrode and the current collector.

3. In claim 1 or 2, The above metallic glass powder contains at least two different elements, The above metal glass powder is a non-anode lithium secondary battery containing a component represented by the following formula 1. (Am1) n1 + (Am2) n2 + (Am3) n3 + ····· + (Amx) ny (Formula 1) (In the above formula 1, Am1, Am2, Am3, ····· , Amx represent different metallic glass elements, x is an integer greater than or equal to 2, and satisfies n1 > 0, n2 > 0, n3 ≥ 0, ····· , ny ≥ 0 and n1 + n2 + ····· + ny = 100) 4. In claim 3, The above metal glass powder is a non-anode lithium secondary battery that satisfies the enthalpy relationship of Equation 2 below. △H total = △H 12 + △H 13 + △H 14 + ····· + △H 1x + △H 23 + △H 24 + ····· + △H 2x + △H 34 + ····· + △H 3x + ····· + △H (x-1)x < 0 (Equation 2) (In the above equation 2, △H (x-1)x represents a mixed series of elements Am(x-1) and Am(x)) 5. In claim 4, The above metallic glass powder is selected from the group consisting of lanthanum (La), cerium (Ce), praseodymium (Pr), promethium (Pm), samarium (Sm), lutetium (Lu), yttrium (Y), neodymium (Nd), gadolinium (Gd), terbium (Tb), dysprosium (Dy), hormium (Ho), erbium (Er), thulium (Tm), thorium (Th), calcium (Ca), scandium (Sc), barium (Ba), beryllium (Be), bismuth (Bi), rubidium (Rb), germanium (Ge), lead (Pb), ytterbium (Yb), chromium (Cr), strontium (Sr), europium (Eu), zirconium (Zr), thallium (Tl), lithium (Li), hafnium (Hf), magnesium (Mg), phosphorus (P), arsenic (As), iron (Fe), A non-anode lithium secondary battery comprising a mixture of two or more elements selected from palladium (Pd), gold (Au), plutonium (Pu), cobalt (Co), gallium (Ga), tungsten (W), germanium (Ge), silver (Ag), sodium (Na), molybdenum (Mo), nickel (Ni), aluminum (Al), copper (Cu), zinc (Zn), antimony (Sb), silicon (Si), tin (Sn), titanium (Ti), cadmium (Cd), indium (In), platinum (Pt), and mercury (Hg).

6. In claim 1, A non-anode lithium secondary battery using a metal powder amorphous alloy powder or a metallic glass powder sintered body, characterized in that the non-metallic powder is selected from one or more of graphite powder, ZrO2 powder, LLZO (lithium lanthanum zirconate oxide) powder, and solid electrolyte powder.

7. In claim 1 or 2, A non-anode lithium secondary battery using a sintered body of metal powder, amorphous alloy powder or metallic glass powder, characterized in that part or all of the amorphous alloy powder or metallic glass powder is crystallized during charging and discharging.

8. In claim 1 or 2, A non-anode lithium secondary battery using an amorphous alloy powder or metallic glass powder sintered body, characterized in that the electrolyte is a liquid electrolyte or a solid electrolyte.

9. A method for manufacturing a non-anode lithium secondary battery using a sintered body of amorphous alloy powder or metallic glass powder, A first step of preparing a paste containing an amorphous alloy powder or a metallic glass powder and a non-metallic powder; A second step of printing the paste of the first step using a screen mask pattern on a substrate; A third step of heat-treating the paste of the second step to obtain a sintered body; and A method for manufacturing a non-anode lithium secondary battery using an amorphous alloy powder or metallic glass powder sintered body, comprising: a fourth step of separating the sintered body obtained in the third step from the substrate.

10. A method for manufacturing a non-anode lithium secondary battery using a sintered body of amorphous alloy powder or metallic glass powder, A first step of preparing a paste containing an amorphous alloy powder or a metallic glass powder; A second step of printing the paste of the first step using a screen mask pattern on a substrate; A third step of heat-treating the paste of the second step to obtain a sintered body; and A method for manufacturing a non-anode lithium secondary battery using an amorphous alloy powder or metallic glass powder sintered body, comprising: a fourth step of separating the sintered body obtained in the third step from the substrate.

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