JP7256560B2 - Anode material for secondary battery, anode for secondary battery, and secondary battery - Google Patents

Description

TECHNICAL FIELD The present invention relates to electrode materials, electrodes, and batteries, and more particularly to anode materials for secondary batteries, anodes for secondary batteries, and secondary batteries.

In recent years, the market demand for lithium-ion secondary batteries, which are capable of repeated charging and discharging, are lightweight, have high voltage values, and have high energy densities, is rapidly increasing. Therefore, the requirements for lightness, durability, high voltage, high energy density, high safety, etc. required for current lithium-ion secondary batteries are becoming more and more severe. Lithium-ion secondary batteries have great potential for applications and scalability in small electric vehicles, electric vehicles, and the large-scale power storage industry. The most common commercial electrode material is graphite, but graphite's low capacity (theoretical value is 372 mAh/g) limits the performance of batteries made from it. Therefore, finding an electrode material for a secondary battery with high stability and high capacity is one of the goals that those skilled in the art would like to achieve.

From this point of view, the present invention provides an anode material and an anode that can be used in secondary batteries to improve the capacity and stability of the secondary batteries.

The secondary battery anode material provided as one embodiment of the present invention contains a cobalt-copper-tin oxide represented by any of the following formulas (1) to (3):
_{Co5Cu1Sn3MOx1 Formula (} 1) _{,
Co2Cu1Sn1MO x2 formula (} 2),
_{Co1Cu1Sn1MO x3 formula (} 3),
where x1 is 8, 9 or 14, x2 is 4, 6 or 8, x3 is 3, 4 or 5, M is Ni, Cr, Mn, Zn, Al, Ti, In, At least one element selected from the group consisting of Mo and W, and the atomic ratio of M is represented by formula (1), formula (2) or formula (3) in cobalt-copper-tin oxide It is 10 atomic % or less with respect to the total number of atoms of the metal element.

Anode materials for secondary batteries according to other embodiments of the present invention include at least one of _Co3O4 , _{Co2O3 and} CoO, at least one of CuO and _Cu2O , and at least one of SnO and _{SnO2 .} and wherein the atomic ratio of cobalt, copper and tin in the oxide mixture is 5:1:3, 2:1:1 or 1:1: 1 containing oxide mixtures.

A secondary battery anode material provided by another embodiment of the present invention comprises a silicon-tin-iron oxide represented by any of the following formulas (4) to (6):
_{Si4Sn1Fe16MO x4} formula ₍ 4) _{,
Si1Sn1Fe1MO x5 formula (} 5),
_{Si4Sn1Fe1MO x6 formula} (6) _,
wherein x4 is 21-34, x5 is 3-5, x6 is 6-11.5, M is the group consisting of Cr, Mn, Zn, Al, Ti, In, Mo and W is at least one element selected from, and the atomic ratio of M is the number of elements other than the oxygen element in the silicon-tin-iron oxide represented by formula (4), formula (5) or formula (6) It is 10 atomic % or less with respect to the total number of atoms.

Anode materials for secondary batteries according to other embodiments of the present invention include at least one of _SiO2 and _SiO , at least one of SnO _{and SnO2} , and at least one of _Fe2O3 , _Fe3O4 and FeO. wherein the atomic ratio of silicon, tin and iron in the oxide mixture is 4:1:16, 1:1:1 or 4:1:1 Contains certain oxide mixtures.

A secondary battery anode material provided by another embodiment of the present invention comprises a copper-manganese-silicon oxide represented by the following formula (7):
Cu _x7 Mn _7-x7 SiMO ₁₂ formula (7),
Here, x7 is greater than 0 and less than or equal to 1, M is at least one element selected from the group consisting of Cr, Sn, Ni, Co, Zn, Al, Ti, In, Mo and W; is 10 atomic % or less with respect to the total number of atoms of elements other than oxygen in the copper-manganese-silicon oxide represented by formula (7).

Anode materials for _secondary batteries according to other embodiments of the present invention include at least one of CuO and _Cu2O , at least one of _SiO2 and SiO, and MnO, _MnO2 , _Mn2O3 and _{Mn3O4 .} wherein the atomic ratio of copper, manganese and silicon in the oxide mixture is 1:1:1, 1:4:1, 4: Including oxide mixtures that are 1:1 or 1:1:4.

A secondary battery anode material provided by another embodiment of the present invention comprises a tin-manganese-nickel oxide represented by any of the following formulas (8) to (11):
Sn ₁ Mn ₂ Ni ₁ MO _x8 formula (8),
Sn ₁ Mn ₁ Ni ₂ MO _x9 formula (9),
_{Sn2Mn1Ni1MO x10 formula} (10) _,
Sn ₁ Mn ₁ Ni ₁ MO _x11 Formula (11),
where x8 is 4-7, x9 is 4-7, x10 is 4-7, x11 is 3-6, M is selected from the group consisting of Cr, Mn, Zn, Al, Ti, In, Mo and W is at least one element, and the atomic ratio of M is represented by formula (8), formula (9), formula (10) or formula (11) of the metal element in the tin-manganese-nickel oxide It is 10 atomic % or less with respect to the total number of atoms.

Anode materials for secondary batteries provided by other embodiments of _the present invention _include at least one of SnO and _SnO2 , at least one of MnO, _MnO2 , _Mn2O3 and _Mn3O4 , and NiO and An oxide mixture obtained by performing a step of mixing at least one of Ni ₂ O ₃ , wherein the atomic ratio of tin, manganese and nickel in the oxide mixture is 1:2:1, 1:1: including oxide mixtures that are 1, 1:1:2 or 2:1:1.

A secondary battery anode material provided by another embodiment of the present invention comprises a manganese-copper-nickel oxide represented by any of the following formulas (12) to (14):
_{Mn3Cu2Ni1MO8 formula (} 12) _{,
Mn2Cu1Ni1MO4 formula (} 13) _{,
Mn1Cu1Ni1MO4 formula (} 14) _,
Here, M is at least one element selected from the group consisting of Fe, Cr, Zn, Al, Ti, In, Mo, W and Si, and the atomic ratio of M is expressed by formula (12), formula ( 13) or 10 atomic % or less of the total number of metal elements in the manganese-copper-nickel oxide represented by formula (14).

Anode materials for _secondary batteries provided by other _embodiments of the present invention include at least one of MnO, _MnO2 , _Mn2O3 and _Mn3O4 , at least one of CuO and _Cu2O , and NiO and Ni ₂ O ₃ , wherein the atomic ratio of manganese, copper and nickel in the oxide mixture is 3:2:1, 2: Including oxide mixtures that are 1:1 or 1:1:1.

A secondary battery anode material provided by another embodiment of the present invention comprises a nickel-copper-tin oxide represented by any of the following formulas (15) to (17):
_{NiCuSn2MO x15} formula (15),
_{Ni2CuSn3MO x16 formula} (16),
_{NiCu2Sn3MO x17 formula} (17),
where x15 is 3, 6 or 9, x16 is 4, 6 or 9, x17 is 4, 6 or 9, M is Cr, Mn, Zn, Al, Ti, In, Mo, At least one element selected from the group consisting of W and Co, and the atomic ratio of M is the nickel-copper-tin oxide represented by formula (15), formula (16) or formula (17) It is 10 atomic % or less with respect to the total number of atoms of the metal element.

An anode material for a secondary battery according to another embodiment of the present invention is a process of mixing at least one of _Ni2O3 and _NiO , at least one of CuO and _Cu2O , and at least one of SnO and _SnO2 wherein the atomic ratio of nickel, copper and tin in the oxide mixture is 1:1:2, 2:1:3 or 1:2:3 Contains mixtures.

A secondary battery anode according to one embodiment of the present invention includes a current collector and an anode material layer. The anode material layer is disposed on the current collector and contains any of the aforementioned secondary battery anode materials.

A secondary battery provided by one embodiment of the present invention includes a cathode, an anode, an electrolyte, and a package structure. The anode is arranged separately from the cathode and is the above-described secondary battery anode. An electrolyte is provided between the cathode and the anode. A package structure packs the cathode, anode and electrolyte.

Based on the above, the anode material for a secondary battery of the present invention contains a metal oxide represented by any one of formulas (1) to (17), or an oxide mixture containing cobalt, copper and tin, silicon , tin and iron, oxide mixtures containing copper, manganese and silicon, oxide mixtures containing tin, manganese and nickel, oxide mixtures containing manganese, copper and nickel, or nickel , copper, and tin, the oxide mixture having specific atomic proportions of the elements. Such an anode material for secondary batteries of the present invention can be used in secondary batteries, and as a result, can impart good capacity, stability, and charge/discharge cycle life to secondary batteries.

In order to make the above features and advantages of the present invention more comprehensible, embodiments are described in detail below in conjunction with the accompanying drawings.

FIG. 1 is a schematic cross-sectional view of a secondary battery according to one embodiment of the invention. 2 is a cycle life curve diagram of the secondary batteries of Example 1 and Comparative Example 1. FIG. 3 is a cycle life curve diagram of the secondary batteries of Example 2 and Comparative Example 1. FIG. 4 is a cycle life curve diagram of the secondary batteries of Example 3 and Comparative Example 1. FIG. FIG. 5 is a cycle life curve diagram of the secondary batteries of Example 4 and Comparative Examples 2-4. FIG. 6 is a cycle life curve diagram of the secondary batteries of Example 5 and Comparative Examples 4-6. FIG. 7 is a cycle life curve diagram of the secondary batteries of Example 6 and Comparative Examples 4-6. 8 is a cycle life curve diagram of the secondary battery of Example 7. FIG. FIG. 9 is a cycle life curve diagram of the secondary batteries of Example 8 and Comparative Examples 3, 5, and 7. As shown in FIG. FIG. 10 is a cycle life curve diagram of the secondary batteries of Example 9 and Comparative Examples 4 and 8-9. FIG. 11 is a cycle life curve diagram of the secondary batteries of Example 10 and Comparative Examples 4 and 8-9. 12 is a cycle life curve diagram of the secondary battery of Example 11. FIG. FIG. 13 is a cycle life curve diagram of the secondary batteries of Example 12 and Comparative Examples 3 and 8-9. 14 is a cycle life curve diagram of secondary batteries of Example 13 and Comparative Examples 3 to 4 and 9. FIG. 15 is a cycle life curve diagram of the secondary battery of Example 14. FIG.

As used herein, ranges expressed as "from one value to another" are shorthand to avoid listing all the values in the range recited herein. Accordingly, the recitation of a particular numerical range includes any number within the numerical range and any number less than defined by any numerical value within the numerical range, as well as any numerical value and lesser numerical ranges herein. Numerical ranges are also covered.

As used herein, "about", "approximately", "essentially" or "substantially" includes the stated value and relates to the measurement in question and the measurement of the specified quantity. within an acceptable range of deviation for a particular value as determined by one of ordinary skill in the art, taking into account the errors in measurement (ie, limitations of the measurement system). For example, "about" can mean within one or more standard deviations, or within ±30%, ±20%, ±15%, ±10%, ±5%, eg, of the stated value. Further, as used herein, “about,” “approximately,” “essentially,” or “substantially” are based on measured properties or other properties, rather than applying one standard deviation across all properties. A relatively acceptable range of deviations or standard deviations may be selected for the term "typically".

In order to prepare an anode material that can be applied to the anode of a secondary battery and can impart good stability and capacity to the secondary battery, the present invention provides an anode material that can achieve the above advantages. . Specific embodiments are described below as examples by which the present invention can be reliably implemented.

One embodiment of the invention provides an anode material that can comprise a metal oxide containing four or more elements, or an oxide mixture containing four or more elements. In this embodiment, the anode material can be a powder, film, or bulk material.

In this embodiment, methods for preparing metal oxides containing four or more elements include, for example, hydrothermal methods, coprecipitation methods, sol-gel methods, solid state methods, evaporation methods, sputtering methods, or vapor deposition methods. but the invention is not limited thereto. In one embodiment of using a hydrothermal method to prepare metal oxides containing four or more elements, the temperature is about 200° C. or more, the holding time is about 5 hours or more, and the ambient pressure is about 10 ⁻² Torr or more. obtain. In one embodiment of using a coprecipitation method to prepare a metal oxide containing four or more elements, the coprecipitation is performed first, the reaction temperature is 200° C. or higher, the pH of the solution is about 2 to about 12, and the temperature is maintained. The time may be about 1 hour or longer; after completion of the reaction, calcination may be performed at a calcination temperature of about 300° C. or higher, and the heat retention time may be about 1 hour or longer. In one embodiment of using a sol-gel method to prepare metal oxides containing four or more elements, the temperature is about 100° C. or higher, the pH of the solution is about 2 to about 12, and the temperature holding time is about 5 hours or longer. can be Further, in one embodiment where a solid state method is used to prepare metal oxides containing four or more elements, the temperature can be about 100° C. or higher and the incubation time can be about 8 hours or longer. In one embodiment where an evaporation method is used to prepare a metal oxide containing four or more elements, the temperature can be about 25° C. or greater, the evaporation time can be about 1 hour or greater, and the ambient pressure can be about 10 ⁻³ Torr or greater. . In one embodiment using a sputtering method to prepare a metal oxide containing four or more elements, the temperature is about 25° C. or greater, the sputtering time is about 0.5 hours or greater, and the ambient pressure is about 10 ⁻³ Torr or greater. could be. In one embodiment using a vapor deposition method to prepare a metal oxide containing four or more elements, the temperature can be about 25° C. or greater, the deposition time can be about 1 hour or greater, and the ambient pressure can be about 10 ⁻³ Torr or greater. .

In this embodiment, metal oxides containing four or more elements are cobalt-copper-tin oxide, silicon-tin-iron oxide, copper-manganese-silicon oxide, tin-manganese-nickel oxide, manganese - may contain copper-nickel oxide or nickel-copper-tin oxide. The various oxides mentioned above are described in detail below.

Cobalt-Copper-Tin Oxide In this embodiment, cobalt-copper-tin oxide can be represented by any of the following formulas (1) to (3):
_{Co5Cu1Sn3MOx1 Formula (} 1) _{,
Co2Cu1Sn1MO x2 formula (} 2),
_{Co1Cu1Sn1MO x3 formula} (3) _.

In formula (1), x1 is 8, 9, or 14. In equation (2), x2 is 4, 6, or 8. In equation (3), x3 is 3, 4, or 5. When x1, x2, and x3 each satisfy the above specific values, the secondary battery to which the anode material containing cobalt-copper-tin oxide is applied has excellent capacity, improved capacity retention, and excellent Provide cycle life.

In each of formulas (1), (2), and (3), M is at least one element selected from the group consisting of Ni, Cr, Mn, Zn, Al, Ti, In, Mo, and W; could be. The atomic ratio of M is 10 atomic % or less with respect to the total number of metal elements in the cobalt-copper-tin oxide represented by formula (1), formula (2), or formula (3). In other words, the cobalt-copper-tin oxide represented by formula (1), formula (2), or formula (3) may be free of the element M, and the four elements namely cobalt, copper , tin, and oxygen. In addition, compared to cobalt-copper-tin oxide that does not contain element M, cobalt-copper-tin oxide containing M with an atomic ratio of more than 0 atomic % and 10 atomic % or less has an electrical conductivity of about 10. % or more. Further, in this embodiment, for cobalt-copper-tin oxides containing the element M, M can replace part of the cobalt, copper, and/or tin. For example, in one embodiment, a portion of the cobalt can be replaced with M; in another embodiment, a portion of the cobalt and a portion of the copper can be replaced with M; , part of copper, and part of tin can be replaced with M, but the invention is not so limited. In this embodiment, the number of atoms of the cobalt-copper-tin oxide represented by formula (1), formula (2), or formula (3) is due to the formation of oxygen vacancies or uneven diffusion. , an error of ±10% may occur.

In embodiments, the cobalt-copper-tin oxide represented by formula (1), formula (2), or formula (3) has a spinel structure, a perovskite structure, a sodium chloride structure, or a chalcopyrite structure. can have Note that the cobalt-copper-tin oxide represented by formula (1), formula (2), or formula (3) has the above structure, thereby enabling more oxygen vacancies, thereby In the secondary battery to which the anode material containing the cobalt-copper-tin oxide is applied, lithium ions can be easily and quickly taken in and out, so that the diffusion rate and ionic conductivity of lithium ions are effectively improved. Furthermore, since the cobalt-copper-tin oxide represented by formula (1), formula (2), or formula (3) has the above structure, it is difficult to disintegrate during the charging and discharging process, and as a result, A secondary battery to which the anode material including the cobalt-copper-tin oxide is applied can maintain a good charge-discharge cycle life.

In this embodiment, the average particle size of cobalt-copper-tin oxide is, for example, between about 10 nm and about 1 mm. When the average particle size of the cobalt-copper-tin oxide is within the above range, it is advantageous to form an anode with good properties. In one embodiment for producing cobalt-copper-tin oxide by a solid phase method, a mortar, a ball mill, a sand mill, Grinding can be performed using a vibrating ball mill or a planetary ball mill, but the invention is not so limited.

Silicon-Tin-Iron Oxide In this embodiment, the silicon-tin-iron oxide can be represented by any of the following formulas (4) to (6):
_{Si4Sn1Fe16MO x4} formula ₍ 4) _{,
Si1Sn1Fe1MO x5 formula (} 5),
_{Si4Sn1Fe1MO x6 formula} ( ₆ ).

In equation (4), x4 is 21-34. In equation (5), x5 is 3-5. In equation (6), x6 is between 6 and 11.5. When x4, x5 and x6 are within the above ranges, the secondary battery to which the anode material containing silicon-tin-iron oxide is applied has excellent capacity and improved capacity retention.

In each of formulas (4), (5), and (6), M can be at least one element selected from the group consisting of Cr, Mn, Zn, Al, Ti, In, Mo, and W . The atomic ratio of M is 10 atomic % or less with respect to the total number of atoms of elements other than oxygen in the silicon-tin-iron oxide represented by formula (4), formula (5), or formula (6). is. In other words, the silicon-tin-iron oxide represented by formula (4), formula (5), or formula (6) may be free of the element M and contain four elements: silicon, tin , iron, and oxygen. In addition, compared to silicon-tin-iron oxides that do not contain element M, silicon-tin-iron oxides containing M with an atomic ratio of greater than 0 atomic % and 10 atomic % or less have an electrical conductivity of about 10. % or more. Also, in this embodiment, in the case of silicon-tin-iron oxides containing element M, M can be substituted for a portion of silicon, tin, and/or iron. For example, in one embodiment, a portion of silicon can be replaced with M; in another embodiment, a portion of silicon and a portion of tin can be replaced with M; , tin, and iron can be replaced with M, but the invention is not so limited. In this embodiment, the number of atoms of the silicon-tin-iron oxide represented by formula (4), formula (5), or formula (6) is due to the formation of oxygen vacancies or uneven diffusion. , an error of ±10% may occur.

In this embodiment, the silicon-tin-iron oxide represented by formula (4), formula (5), or formula (6) has a rhombohedral crystal structure, a cubic bixbyite structure, a spinel structure, or may have an orthorhombic structure. Note that the silicon-tin-iron oxide represented by formula (4), formula (5), or formula (6) has the above structure, thereby enabling more oxygen vacancies, thereby In a secondary battery to which the anode material containing the silicon-tin-iron oxide is applied, lithium ions can be easily and quickly taken in and out, so that the diffusion rate and ionic conductivity of lithium ions are effectively improved. Furthermore, since the silicon-tin-iron oxide represented by formula (4), formula (5), or formula (6) has the above structure, it is difficult to disintegrate during the charging and discharging process, and as a result, A secondary battery to which the anode material containing the silicon-tin-iron oxide is applied can maintain good charge-discharge cycle life.

In this embodiment, the silicon-tin-iron oxide has an average particle size, for example, between about 10 nm and about 1 mm. When the average particle size of the silicon-tin-iron oxide is within the above range, it is advantageous to form an anode with good properties. In an embodiment for producing silicon-tin-iron oxides by a solid phase method, a mortar, a ball mill, a sand mill, a vibrating Grinding can be performed using a ball mill, or a planetary ball mill, although the invention is not so limited.

Copper-Manganese-Silicon Oxide In this embodiment, the copper-manganese-silicon oxide can be represented by the following formula (7):
Cu _x7 Mn _7-x7 SiMO ₁₂ formula (7).

In Equation (7), x7 is greater than 0 and less than or equal to 1. When x7 is within the above range, the secondary battery to which the anode material containing copper-manganese-silicon oxide is applied has excellent capacity and improved capacity retention.

In formula (7), M may be at least one element selected from the group consisting of Cr, Sn, Ni, Co, Zn, Al, Ti, In, Mo, and W. The atomic ratio of M is 10 atomic % or less with respect to the total number of atoms of elements other than oxygen in the copper-manganese-silicon oxide represented by formula (7). In other words, the copper-manganese-silicon oxide represented by formula (7) may contain no element M, and may contain only four elements: copper, manganese, silicon, and oxygen. In addition, compared to the copper-manganese-silicon oxide that does not contain the element M, the copper-manganese-silicon oxide containing M with an atomic ratio of greater than 0 atomic % and 10 atomic % or less has an electrical conductivity of about 10. % or more. Also, in this embodiment, in the case of a copper-manganese-silicon oxide containing the element M, M can be substituted for a portion of the copper, manganese, and/or silicon. For example, in one embodiment, a portion of the copper can be replaced with M; in another embodiment, a portion of the copper and a portion of the manganese can be replaced with M; , a portion of manganese, and a portion of silicon can be replaced with M, but the invention is not so limited. In this embodiment, the number of atoms of the copper-manganese-silicon oxide represented by formula (7) may have an error of ±10% due to uneven diffusion or formation of oxygen vacancies. , thereby forming a non-stoichiometric compound.

In this embodiment, the copper-manganese-silicon oxide represented by formula (7) may have an Abswurmbachite structure, a Pyroxmangite structure, or a Braunite structure. . Since the copper-manganese-silicon oxide represented by the formula (7) has the above structure, in a secondary battery to which the anode material containing the copper-manganese-silicon oxide is applied, energy due to overpotential Loss can be reduced, lithium ion diffusivity and ion conductivity can be improved, and charge-discharge cycle life can be improved.

In this embodiment, the copper-manganese-silicon oxide has an average particle size, for example, between about 10 nm and about 1 mm. When the average particle size of the copper-manganese-silicon oxide is within the above range, it is advantageous to form an anode with good properties. In an embodiment for producing copper-manganese-silicon oxide by a solid phase method, a mortar, a ball mill, a sand mill, a vibration Grinding can be performed using a ball mill, or a planetary ball mill, although the invention is not so limited.

Tin-Manganese-Nickel Oxide In this embodiment, the tin-manganese-nickel oxide can be represented by any of the following formulas (8)-(11):
Sn ₁ Mn ₂ Ni ₁ MO _x8 formula (8),
Sn ₁ Mn ₁ Ni ₂ MO _x9 formula (9),
_{Sn2Mn1Ni1MO x10 formula} (10) _{,
Sn1Mn1Ni1MO x11 formula} (11) _.

In equation (8), x8 is 4-7. In equation (9), x9 is 4-7. In equation (10), x10 is 4-7. In equation (11), x11 is 3-6. When x8, x9, x10, and x11 are within the above ranges, the secondary battery to which the anode material containing tin-manganese-nickel oxide is applied has excellent capacity and improved capacity retention. .

In each of formula (8), formula (9), formula (10), and formula (11), M is selected from the group consisting of Cr, Mn, Zn, Al, Ti, In, Mo, and W It can be at least one element. The atomic ratio of M is 10 atoms with respect to the total number of metal elements in the tin-manganese-nickel oxide represented by formulas (8), (9), (10), and (11). % or less. In other words, the tin-manganese-nickel oxides represented by formulas (8), (9), (10), and (11) may be free of the element M, the four elements That is, it may contain only tin, manganese, nickel, and oxygen. Note that, compared to tin-manganese-nickel oxides that do not contain element M, tin-manganese-nickel oxides containing M with an atomic ratio of greater than 0 atomic % and 10 atomic % or less have an electrical conductivity of about 10. % or more. Also, in this embodiment, for tin-manganese-nickel oxides containing the element M, M can replace part of the tin, manganese, and/or nickel. For example, in one embodiment, a portion of the tin can be replaced with M; in another embodiment, a portion of the tin and a portion of the manganese can be replaced with M; , manganese, and nickel can be replaced with M, but the invention is not so limited. In the present embodiment, the number of atoms of the tin-manganese-nickel oxide represented by formulas (8), (9), (10), and (11) is An error of ±10% can occur due to uniform diffusion.

In the present embodiment, the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10), or formula (11) has a spinel structure, rutile structure, or rock salt structure. obtain. Note that the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10), or formula (11) has more oxygen vacancies by having the above structure. As a result, in the secondary battery to which the anode material containing the tin-manganese-nickel oxide is applied, lithium ions can be easily and quickly taken in and out, so that the diffusion rate and ionic conductivity of lithium ions are effectively improved. improves. Furthermore, since the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10), or formula (11) has the above structure, it collapses during the charging and discharging process. As a result, the secondary battery to which the anode material containing the tin-manganese-nickel oxide is applied can maintain good charge-discharge cycle life.

In this embodiment, the tin-manganese-nickel oxide has an average particle size, for example, between about 10 nm and about 1 mm. When the tin-manganese-nickel oxide has an average particle size within the above range, it is advantageous to form an anode with good properties. In an embodiment for producing tin-manganese-nickel oxide by a solid phase method, a mortar, a ball mill, a sand mill, a vibrating Grinding can be performed using a ball mill, or a planetary ball mill, although the invention is not so limited.

Manganese-Copper-Nickel Oxide In this embodiment, the manganese-copper-nickel oxide can be represented by any of the following formulas (12)-(14):
_{Mn3Cu2Ni1MO8 formula (} 12) _{,
Mn2Cu1Ni1MO4 formula (} 13) _{,
Mn1Cu1Ni1MO4 formula (} 14) _.

That is, in this embodiment, the atomic ratio of manganese to copper to nickel to oxygen in the manganese-copper-nickel oxide is 3:2:1:8, 2:1:1:4, or 1:1:1: can be four. The manganese-copper-nickel oxide is represented by any of the formulas (12) to (14), and the secondary battery to which the anode material containing the manganese-copper-nickel oxide is applied has excellent capacity. and improved capacity retention.

In each of formula (12), formula (13), and formula (14), M is at least one selected from the group consisting of Fe, Cr, Zn, Al, Ti, In, Mo, W, and Si. can be an element. The atomic ratio of M is 10 atomic % or less with respect to the total number of metal elements in the manganese-copper-nickel oxide represented by formula (12), formula (13), or formula (14). In other words, the manganese-copper-nickel oxide represented by formula (12), formula (13), or formula (14) may not contain the element M, but the four elements, namely manganese, copper , nickel, and oxygen. Note that, compared to manganese-copper-nickel oxides that do not contain element M, manganese-copper-nickel oxides containing M with an atomic ratio of greater than 0 atomic % and 10 atomic % or less have an electrical conductivity of about 10. % or more. Also, in this embodiment, in the case of a manganese-copper-nickel oxide containing the element M, M can be substituted for a portion of the manganese, copper, and/or nickel. For example, in one embodiment, a portion of the manganese can be replaced with M; in another embodiment, a portion of the manganese and a portion of the copper can be replaced with M; , a portion of copper, and a portion of nickel can be replaced with M, but the present invention is not limited thereto. In this embodiment, the number of atoms of the manganese-copper-nickel oxide represented by formula (12), formula (13), or formula (14) is due to the formation of oxygen vacancies or uneven diffusion. , an error of ±10% may occur.

In the present embodiment, the manganese-copper-nickel oxide represented by formula (12), formula (13), or formula (14) has a tetragonal structure, a spinel structure, a perovskite structure, or a chalcopyrite structure. can have Note that the manganese-copper-nickel oxide represented by formula (12), formula (13), or formula (14) has the above structure, thereby enabling more oxygen vacancies, thereby In the secondary battery to which the anode material containing the manganese-copper-nickel oxide is applied, lithium ions can be easily and quickly taken in and out, so that the diffusion rate and ionic conductivity of lithium ions are effectively improved. Furthermore, since the manganese-copper-nickel oxide represented by formula (12), formula (13), or formula (14) has the above structure, it is difficult to disintegrate during the charging and discharging process, and as a result, A secondary battery to which the anode material including the manganese-copper-nickel oxide is applied can maintain good charge-discharge cycle life.

In this embodiment, the manganese-copper-nickel oxide has an average particle size, for example, between about 10 nm and about 1 mm. When the manganese-copper-nickel oxide has an average particle size within the above range, it is advantageous to form an anode with good properties. In an embodiment for producing manganese-copper-nickel oxide by a solid phase method, a mortar, a ball mill, a sand mill, a vibrating Grinding can be performed using a ball mill, or a planetary ball mill, although the invention is not so limited.

Nickel-Copper-Tin Oxide In this embodiment, the nickel-copper-tin oxide can be represented by any of the following formulas (15)-(17):
_{NiCuSn2MO x15} formula (15),
_{Ni2CuSn3MO x16 formula} (16),
NiCu ₂ Sn ₃ MO _x17 formula Formula (17).

In equation (15), x15 is 3, 6 or 9. In equation (16), x16 is 4, 6 or 9. In equation (17), x17 is 4, 6 or 9. When x15, x16, and x17 are within the above ranges, the secondary battery to which the anode material containing nickel-copper-tin oxide is applied has excellent capacity and improved capacity retention.

In each of Formula (15), Formula (16), and Formula (17), M is at least one selected from the group consisting of Cr, Mn, Zn, Al, Ti, In, Mo, W, and Co. can be an element. The atomic ratio of M is 10 atomic % or less with respect to the total number of metal elements in the nickel-copper-tin oxide represented by formula (15), formula (16) or formula (17). In other words, the nickel-copper-tin oxide represented by formula (15), formula (16) or formula (17) may be free of the element M, and the four elements namely nickel, copper, It may contain only tin and oxygen. It should be noted that, compared to nickel-copper-tin oxides that do not contain element M, nickel-copper-tin oxides containing M with an atomic ratio of greater than 0 atomic % and 10 atomic % or less have an electrical conductivity of about 15. % or more. Also, in this embodiment, in the case of a nickel-copper-tin oxide containing the element M, M can be substituted for a portion of the nickel, copper, and/or tin. For example, in one embodiment, a portion of the nickel can be replaced with M; in another embodiment, a portion of the nickel and a portion of the copper can be replaced with M; , part of copper, and part of tin can be replaced with M, but the invention is not so limited. In this embodiment, the number of atoms of the nickel-copper-tin oxide represented by formula (15), formula (16), or formula (17) is , an error of ±10% may occur.

In this embodiment, the nickel-copper-tin oxide represented by formula (15), formula (16) or formula (17) may have a perovskite structure, a sodium chloride structure, or a chalcopyrite structure. . Note that the nickel-copper-tin oxide represented by formula (15), formula (16), or formula (17) has the above structure, so that more oxygen vacancies are possible, thereby In a secondary battery to which the anode material containing the nickel-copper-tin oxide is applied, lithium ions can be easily and quickly taken in and out, so that the diffusion rate and ionic conductivity of lithium ions are effectively improved. Furthermore, since the nickel-copper-tin oxide represented by formula (15), formula (16) or formula (17) has the above structure, it is difficult to disintegrate during the charging and discharging process, and as a result, the above A secondary battery to which an anode material containing nickel-copper-tin oxide is applied can maintain good charge-discharge cycle life.

In this embodiment, the average particle size of nickel-copper-tin oxide is, for example, between about 10 nm and about 1 mm. When the nickel-copper-tin oxide has an average particle size within the above range, it is advantageous to form an anode with good properties. In an embodiment for producing nickel-copper-tin oxide by a solid phase method, a mortar, a ball mill, a sand mill, a vibrating Grinding can be performed using a ball mill, or a planetary ball mill, although the invention is not so limited.

Moreover, in this embodiment, as a method of preparing an oxide mixture containing four or more elements, for example, a mixing step is performed. The mixing step is performed by, for example, a physical dry mixing method or a physical wet mixing method, but the present invention is not limited thereto. In one embodiment in which a physical dry mixing method is used to prepare an oxide mixture containing four or more elements, the mixing temperature may be room temperature, eg, about 25° C. or higher. In one embodiment of preparing an oxide mixture comprising four or more elements using a physical wet mixing method, the mixing temperature can be room temperature, such as about 25° C. or higher, and the solvent can be water, alcohol, acetone, or can be methanol.

In this embodiment, oxide mixtures containing four or more elements include oxide mixtures containing cobalt, copper, and tin; oxide mixtures containing silicon, tin, and iron; and copper, manganese, and silicon. an oxide mixture comprising tin, manganese and nickel; an oxide mixture comprising manganese, copper and nickel; or an oxide mixture comprising nickel, copper and tin. The various oxide mixtures described above are described in detail below.

Oxide Mixture Comprising Cobalt, Copper, and Tin In this embodiment, the oxide mixture _comprising cobalt, copper, and tin comprises at least one of _Co3O4 , _Co2O3 , and CoO, _CuO and Cu2 _. It can be obtained by performing a step of mixing at least one of O and at least one of SnO and SnO ₂ . That is, an oxide mixture containing cobalt, copper and tin can be obtained by a mixing process of cobalt oxide, copper oxide and tin oxide. Further, in this embodiment, the atomic ratio of cobalt to copper to tin in the oxide mixture containing cobalt, copper and tin can be 5:1:3, 2:1:1 , or 1:1:1. . When the atomic ratio of cobalt, copper and tin satisfies the above specific ratio, the secondary battery to which the anode material comprising the oxide mixture containing cobalt, copper and tin is applied has excellent capacity and improved capacity. It has excellent capacity retention.

In this embodiment, during the mixing step, the M-containing oxides are optionally at least one of _Co3O4 , _{Co2O3 and} CoO, _at least one of CuO and _Cu2O , and SnO and can be mixed together with at least one of _SnO2 . Here, M is at least one element selected from the group consisting of Ni, Cr, Mn, Zn, Al, Ti, In, Mo, and W. That is, an oxide mixture containing cobalt, copper, and tin may optionally contain the element M. The atomic ratio of M is 10 atomic % or less with respect to the total number of metal elements in the oxide mixture containing cobalt, copper, and tin. It should be noted that compared to an oxide mixture containing cobalt, copper, and tin that is not mixed with an oxide containing M, it is mixed with an oxide containing M, and the atomic ratio of M is 10 atomic% or less. Oxide mixtures containing cobalt, copper, and tin have an increase in electrical conductivity of about 8% or more. It should be noted that, in this embodiment, the numerical values of the atomic ratios of the elements in the oxide mixture containing cobalt, copper, and tin may have an error of ±10% due to the formation of oxygen vacancies or uneven diffusion. be.

In this embodiment, an anode material comprising a mixture of oxides including cobalt, copper, and tin is used to form the anode, allowing lithium ions to enter and exit through different pathways, reducing polarization effects. , the charge-discharge cycle life can be improved. This can significantly increase the capacity of a secondary battery to which an anode material containing an oxide mixture containing cobalt, copper, and tin is applied. Also, tin oxide used as anode material can achieve high capacity performance, copper oxide used as anode material can achieve good cycle life, and cobalt oxide used as anode material can achieve good lithium ion conductivity. can be achieved, the secondary battery applying the anode material containing the oxide mixture obtained by the mixing process of cobalt oxide, copper oxide and tin oxide has excellent performance and safety.

Oxide Mixture Comprising Silicon, Tin, and Iron In this embodiment, the oxide mixture comprising silicon, tin, and iron comprises SiO ₂ and at least one of SiO, at least one of SnO and SnO ₂ , and Fe It can be obtained by performing a step _{of mixing at least one of 2O3 , Fe3O4} and _FeO . That is, an oxide mixture containing silicon, tin and iron oxide can be obtained by a mixing process of silicon oxide, tin oxide and iron oxide. Further, in this embodiment, the atomic ratio of silicon to tin to iron in the oxide mixture comprising silicon, tin and iron is 4:1:16, 1:1:1, or 4:1:1. obtain. When the atomic ratios of silicon, tin and iron satisfy the above specific ratios, secondary batteries using anode materials containing oxide mixtures containing silicon, tin and iron show excellent capacity and improved performance. It has excellent capacity retention.

In this embodiment, during the mixing step, the oxide containing M is optionally _SiO2 and at least one of SiO _, at least one of SnO and _SnO2 , and _Fe2O3 , _{Fe3O4 .} and FeO. Here, M is at least one element selected from the group consisting of Cr, Mn, Zn, Al, Ti, In, Mo, and W. That is, an oxide mixture containing silicon, tin, and iron may optionally contain the element M. The atomic ratio of M is 10 atomic % or less with respect to the total number of atoms of elements other than oxygen in the oxide mixture containing silicon, tin and iron. It should be noted that compared to an oxide mixture containing silicon, tin, and iron that is not mixed with an oxide containing M, it is mixed with an oxide containing M, and the atomic ratio of M is 10 atomic% or less. Oxide mixtures containing silicon, tin, and iron have an increase in electrical conductivity of about 10% or more. It should be noted that, in this embodiment, the numerical values of the atomic ratios of the elements in the oxide mixture containing silicon, tin, and iron may have an error of ±10% due to the formation of oxygen vacancies or uneven diffusion. be.

In this embodiment, an anode material comprising an oxide mixture comprising silicon, tin, and iron is used to form the anode, allowing lithium ions to enter and exit through different pathways, reducing polarization effects. , the charge-discharge cycle life can be improved. This can significantly increase the capacity of a secondary battery to which an anode material containing an oxide mixture containing silicon, tin and iron is applied. In addition, tin oxide used as anode material can achieve high capacity performance, iron oxide used as anode material can achieve good cycle life, and silicon oxide used as anode material can achieve good lithium ion conductivity. can be achieved, the secondary battery applying the anode material containing the oxide mixture obtained by the mixing process of silicon oxide, tin oxide and iron oxide has excellent performance and safety.

Oxide Mixture Comprising Copper, Manganese, and Silicon In this embodiment, the oxide mixture comprising copper, manganese, and silicon comprises at least one of CuO and _Cu2O , at least one of _SiO2 and SiO, and MnO , MnO ₂ , Mn ₂ O ₃ and Mn ₃ O ₄ . That is, an oxide mixture containing copper, manganese and silicon can be obtained by a mixing process of copper oxide, manganese oxide and silicon oxide. Further, in this embodiment, the atomic ratio of copper to manganese to silicon in the oxide mixture comprising copper, manganese and silicon is 1:1:1, 1:4:1, 4:1:1, or 1 : 1:4. When the atomic ratios of copper, manganese and silicon meet the above specific ratios, secondary batteries using anode materials containing oxide mixtures containing copper, manganese and silicon exhibit excellent capacity and improved performance. It has excellent capacity retention.

In this embodiment, during the mixing step, the M-containing oxide is optionally at least one of CuO and _Cu2O , at least one of _SiO2 and SiO, and MnO, _MnO2 , _{Mn2O3 .} and Mn ₃ O ₄ together. Here, M is at least one element selected from the group consisting of Cr, W, Sn, Ni, Zn, Al, Ti, In, and Mo. That is, an oxide mixture containing copper, manganese, and silicon may optionally contain the element M. The atomic ratio of M is 10 atomic % or less with respect to the total number of atoms of elements other than oxygen in the oxide mixture containing copper, manganese and silicon. Note that compared to an oxide mixture containing copper, manganese, and silicon that is not mixed with an oxide containing M, it is mixed with an oxide containing M, and the atomic ratio of M is 10 atomic% or less. Oxide mixtures containing copper, manganese, and silicon have increased electrical conductivity by about 10% or more. It should be noted that in the present embodiment, the numerical values of the atomic ratios of the elements in the oxide mixture containing copper, manganese, and silicon may have an error of ±10% due to the formation of oxygen vacancies or uneven diffusion. be.

In this embodiment, the oxide mixture containing copper, manganese, and silicon obtained by performing the mixing step of copper oxide, manganese oxide, and silicon oxide provides a synergistic effect due to the interaction of multiple oxides, The capacity of a secondary battery applying an anode material containing an oxide mixture containing manganese and silicon is greatly increased. Further, in this embodiment, by forming the anode using an anode material comprising an oxide mixture comprising copper, manganese, and silicon, lithium ions can enter and exit through different pathways, reducing polarization effects. It is possible to improve the charge-discharge cycle life. Also, copper oxide used as anode material can achieve good cycle life, manganese oxide used as anode material can achieve low overvoltage, and silicon oxide used as anode material can achieve good lithium ion conductivity. As can be achieved, the secondary battery applying the anode material containing the oxide mixture obtained by the mixing process of copper oxide, manganese oxide and silicon oxide has excellent performance and safety.

Oxide Mixture Comprising Tin, Manganese, and Nickel In _this embodiment, the oxide mixture comprising tin _, manganese, and nickel comprises at least one of SnO and SnO2, MnO, _MnO2 , _Mn2O3 and _Mn3 It can be obtained by performing a step of mixing at least one of O ₄ and at least one of NiO and Ni ₂ O ₃ . That is, an oxide mixture containing tin, manganese and nickel can be obtained by a mixing process of tin oxide, manganese oxide and nickel oxide. Further, in this embodiment, the atomic ratio of tin to manganese to nickel in the oxide mixture comprising tin, manganese and nickel is 1:2:1, 1:1:1, 1:1:2, or 2 : 1:1. When the atomic ratio of tin, manganese and nickel satisfies the above specific ratio, the secondary battery to which the anode material comprising the oxide mixture containing tin, manganese and nickel is applied shows excellent capacity and improvement. with high capacity retention.

In this embodiment, during the mixing step, the M-containing oxide is optionally at least one of SnO and _{SnO2 , at least one of MnO, MnO2 , Mn2O3 and Mn3O4} , and It can be mixed together _with at least one of NiO and _Ni2O3 . Here, M is at least one element selected from the group consisting of Cr, W, Si, Cu, Zn, Al, Ti, In, and Mo. That is, an oxide mixture containing tin, manganese, and nickel may optionally contain the element M. The atomic ratio of M is 10 atomic % or less with respect to the total number of atoms of metal elements in the oxide mixture containing tin, manganese and nickel. Note that compared to an oxide mixture containing tin, manganese, and nickel that is not mixed with an oxide containing M, it is mixed with an oxide containing M, and the atomic ratio of M is 10 atomic% or less. Oxide mixtures containing tin, manganese, and nickel have increased electrical conductivity by about 10% or more. It should be noted that, in this embodiment, the numerical values of the atomic ratios of the elements in the oxide mixture containing tin, manganese, and nickel may have an error of ±10% due to the formation of oxygen vacancies or non-uniform diffusion. be.

In this embodiment, the oxide mixture containing tin, manganese, and nickel obtained by performing the step of mixing tin oxide, manganese oxide, and nickel oxide provides a synergistic effect due to the interaction of multiple oxides, and tin, The capacity of a secondary battery containing an anode material containing an oxide mixture containing manganese and nickel is greatly increased. Further, in this embodiment, by forming the anode using an anode material comprising a mixture of oxides including tin, manganese, and nickel, lithium ions can enter and exit through different pathways, reducing polarization effects. It is possible to improve the charge-discharge cycle life. In addition, tin oxide used as anode material can achieve high capacity performance, manganese oxide used as anode material can achieve low overvoltage, and nickel oxide used as anode material can achieve good lithium ion conductivity. Therefore, a secondary battery using an anode material containing an oxide mixture obtained by a mixing process of tin oxide, manganese oxide and nickel oxide has excellent performance and safety.

Oxide Mixture Comprising Manganese, _{Copper and Nickel In this embodiment, the oxide mixture comprising manganese, copper and nickel comprises at least one of MnO, MnO2 , Mn2O3 and Mn3O4} , CuO and It can be obtained by performing a step of mixing at least one of Cu ₂ O and at least one of NiO and Ni ₂ O ₃ . That is, an oxide mixture containing manganese, copper and nickel can be obtained by a mixing process of manganese oxide, copper oxide and nickel oxide. Further, in this embodiment, the atomic ratio of manganese to copper to nickel in the oxide mixture comprising manganese, copper and nickel is 3:2:1, 2:1:1, or 1:1:1. obtain. When the atomic ratio of manganese, copper and nickel satisfies the above specific ratio, the secondary battery to which the anode material comprising the oxide mixture containing manganese, copper and nickel is applied has excellent capacity and improvement. with high capacity retention.

In this embodiment, during the mixing step, the M- _{containing oxide is optionally at least one of MnO, MnO2, Mn2O3 and Mn3O4 , at least} one of CuO and _Cu2O , and at least one _of NiO and _Ni2O3 . Here, M is at least one element selected from the group consisting of Fe, Cr, Zn, Al, Ti, In, Mo, W, and Si. That is, an oxide mixture containing manganese, copper and nickel may optionally contain the element M. The atomic ratio of M is 10 atomic % or less with respect to the total number of metal elements in the oxide mixture containing manganese, copper and tin. It should be noted that compared to an oxide mixture containing manganese, copper, and nickel that is not mixed with an oxide containing M, it is mixed with an oxide containing M, and the atomic ratio of M is 10 atomic% or less. Oxide mixtures containing manganese, copper, and nickel have increased electrical conductivity by about 5% or more. It should be noted that, in this embodiment, the numerical values of the atomic ratios of the elements in the oxide mixture containing manganese, copper, and nickel may have an error of ±10% due to the formation of oxygen vacancies or non-uniform diffusion. be.

In this embodiment, by forming the anode using an anode material comprising an oxide mixture comprising manganese, copper, and nickel, lithium ions can enter and exit through different pathways, reducing polarization effects. , the charge-discharge cycle life can be improved. Also, manganese oxide used as anode material can achieve low overvoltage, copper oxide used as anode material can achieve good cycle life, and nickel oxide used as anode material can achieve high capacity performance. , manganese oxide, copper oxide, and nickel oxide.

Oxide Mixture Comprising Nickel, Copper, and Tin In this embodiment, the oxide mixture comprising nickel, _copper , and tin comprises at least one of _Ni2O3 and NiO, at least one of CuO and _Cu2O , and by performing a step of mixing at least one of SnO and _SnO2 . That is, an oxide mixture containing nickel, copper and tin can be obtained by a mixing process of nickel oxide, copper oxide and tin oxide. Further, in this embodiment, the atomic ratio of nickel to copper to tin in the oxide mixture comprising nickel, copper and tin is 1:1:2, 2:1:3, or 1:2:3. obtain. When the atomic ratios of nickel, copper and tin meet the above specific ratios, secondary batteries using anode materials comprising oxide mixtures containing nickel, copper and tin exhibit superior capacity and improved performance. It has excellent capacity retention.

In this embodiment, during the mixing step, the M-containing oxide is optionally at least one of _Ni2O3 and NiO, _at least one of CuO and _Cu2O , and at least one of SnO and _SnO2 . can be mixed together. Here, M is at least one element selected from the group consisting of Cr, Mn, Zn, Al, Ti, In, Mo, W, and Co. That is, an oxide mixture containing nickel, copper, and tin may optionally contain the element M. The atomic ratio of M is 10 atomic % or less with respect to the total number of metal elements in the oxide mixture containing nickel, copper, and tin. Note that compared to an oxide mixture containing nickel, copper, and tin that is not mixed with an oxide containing M, it is mixed with an oxide containing M, and the atomic ratio of M is 10 atomic% or less. Oxide mixtures containing nickel, copper, and tin have increased electrical conductivity by about 8% or more. It should be noted that, in this embodiment, the numerical values of the atomic ratios of the elements in the oxide mixture containing nickel, copper, and tin may have an error of ±10% due to the formation of oxygen vacancies or uneven diffusion. be.

In this embodiment, an anode material comprising a mixture of oxides including nickel, copper, and tin is used to form the anode, allowing lithium ions to enter and exit through different pathways, reducing polarization effects. , the charge-discharge cycle life can be improved. This can significantly increase the capacity of a secondary battery to which an anode material containing an oxide mixture containing nickel, copper and tin is applied. Also, the tin oxide used as anode material can achieve high capacity performance, the copper oxide used as anode material can achieve good cycle life, and the nickel oxide used as anode material has good lithium ion conductivity. can be achieved, the secondary battery to which the anode material containing the oxide mixture obtained by the mixing process of nickel oxide, copper oxide and tin oxide is applied has excellent performance and safety.

Another embodiment of the present invention provides a secondary battery using any of the anode materials proposed in the above embodiments.

FIG. 1 is a schematic cross-sectional view of a secondary battery according to one embodiment of the present invention. Referring to FIG. 1, secondary battery 100 can include anode 102 , cathode 104 , electrolyte 108 , and package structure 112 . In this embodiment, the secondary battery 100 may further include a separator 106 . Furthermore, in this embodiment, the secondary battery 100 may be a lithium ion battery.

In this embodiment, the anode 102 can include a current collector 102a and an anode material layer 102b disposed on the current collector 102a. In this embodiment, the current collector 102a may be a metal foil such as copper foil, nickel foil, or highly conductive foil. In this embodiment, the thickness of current collector 102a may be from about 5 μm to about 300 μm.

In this embodiment, the anode material layer 102b comprises any of the anode materials suggested in the above embodiments. In this embodiment, the anode material can be deposited on the current collector 102a by, for example, coating, sputtering, hot pressing, sintering, physical vapor deposition, or chemical vapor deposition. Also, in this embodiment, the anode material layer 102b may further contain a conductive agent and a binder. In the present embodiment, the conductive agent is natural graphite, artificial graphite, carbon black, conductive black (VGCF, Super P, KS 4, KS 6, or ECP, etc.), acetylene black, ketjen black, carbon whisker, carbon fiber , metal powder, metal fiber, or ceramic material. Specifically, conductive agents are used to improve the electrical contact between the molecules of the anode material. In embodiments, the binder may be polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), polyamide, melamine resin, or combinations thereof. Specifically, the anode material may be adhered to the current collector 102a by a binder.

In this embodiment, the cathode 104 and the anode 102 are arranged separately. In this embodiment, the cathode 104 includes a current collector 104a and a cathode material layer 104b disposed on the current collector 104a. In this embodiment, the current collector 104a may be a metal foil such as copper foil, nickel foil, aluminum foil, or highly conductive foil. In this embodiment, the thickness of current collector 104a may be from about 5 μm to about 300 μm.

In this embodiment, cathode material layer 104b comprises a cathode material. In this embodiment, the cathode material comprises lithium cobaltate ( _LiCoO2 ), lithium manganate ( _LiMn2O4 ), lithium nickelate ( _LiNiO2 ), lithium iron phosphate ( _LiFePO4 ), or _combinations thereof. obtain. In this embodiment, the cathode material can be deposited on current collector 104a by, for example, coating, sputtering, hot pressing, sintering, physical vapor deposition, or chemical vapor deposition. Moreover, in this embodiment, the cathode material layer 104b may further contain a binder. In this embodiment, the binder may be PVDF, SBR, polyamide, melamine resin, or combinations thereof. Specifically, the cathode material can be adhered to the current collector 104a by a binder.

In this embodiment, electrolyte 108 is provided between anode 102 and cathode 104, and electrolyte 108 may include a liquid electrolyte, a gel electrolyte, a molten salt electrolyte, or a solid electrolyte.

In this embodiment, separator 106 is positioned between anode 102 and cathode 104, separator 106, anode 102, and cathode 104 define a containment area 110 in the storage system, and electrolyte 108 is contained in containment area 110. are placed. In this embodiment, the material of the separator 106 may be an insulating material such as polyethylene (PE), polypropylene (PP), or a composite structure (eg, PE/PP/PE) made of these materials.

In this embodiment, the secondary battery 100 separates the anode 102 from the cathode 104 and includes a separator 106 for permeation of ions, but the invention is not so limited. In other embodiments, electrolyte 108 is a solid electrolyte and secondary battery 100 does not include a separator.

In this embodiment, package structure 112 covers anode 102 , cathode 104 and electrolyte 108 . In this embodiment, the material of the package structure 112 is, for example, aluminum foil or stainless steel.

In this embodiment, the structure of the secondary battery 100 is not limited to the structure shown in FIG. In other embodiments, the secondary battery 100 may have a rolled structure in which the anode, cathode, and optional separator are wound, or a laminated structure formed by stacking flat layers. . Furthermore, in this embodiment, the secondary battery 100 is, for example, a paper battery, a button battery, a coin battery, a laminated battery, a cylindrical battery, or a rectangular battery.

In particular, since the anode 102 of the secondary battery 100 uses any of the anode materials proposed in the previous embodiments, the secondary battery 100 has good capacity, stability, and charge/discharge characteristics as described above. It can have a cycle life.

Features of the present invention are described in more detail below with reference to Examples 1-14 and Comparative Examples 1-9. Examples 1-14 are set forth below, but the materials used, their respective amounts and ratios, detailed process flows, etc., can be modified appropriately without departing from the scope of the present disclosure. can. Accordingly, the scope of this disclosure should not be limited by the following embodiments.

Example 1
Preparation of Anode Materials At room temperature, CoO powder (precursor containing cobalt), CuO powder (precursor containing copper), SnO powder (precursor containing tin), and W oxide powder (elemental A precursor containing M) was ground and the resulting powders were mixed and pressed into green pellets approximately 1 cm in diameter. The green pellets were placed in a high temperature furnace to obtain the cobalt-copper-tin oxide bulk material represented by formula (1) above (ie, the anode material of Example 1). Here, x1 is 8, the element M is W, the atomic ratio of the element M is 10 atomic % or less, and the cobalt-copper-tin oxide has an average particle size of about 0.1 μm to about 10 μm. Range.

Secondary Battery Preparation The ground anode material of Example 1 and Super P conductive carbon and binder (i.e. sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed at a weight ratio of 7:2:1. mixed in ratio. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into Example 1 anodes with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 1 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 1 was prepared.

Example 2
Preparation of Anode Materials At room temperature, CoO powder (precursor containing cobalt), CuO powder (precursor containing copper), SnO powder (precursor containing tin), and W oxide powder (elemental A precursor containing M) was ground and the resulting powders were mixed and pressed into green pellets approximately 1 cm in diameter. The green pellets were placed in a high temperature furnace to obtain the cobalt-copper-tin oxide bulk material represented by formula (2) above (ie, the anode material of Example 2). Here, x2 is 4, the element M is W, the atomic ratio of the element M is 10 atomic % or less, and the cobalt-copper-tin oxide has an average particle size of about 0.1 μm to about 10 μm. Range.

Secondary Battery Preparation The ground anode material of Example 2 and Super P conductive carbon and binder (i.e. sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed at a weight ratio of 7:2:1. mixed in ratio. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into Example 2 anodes with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 2 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 2 was prepared.

Example 3
Preparation of Anode Materials At room temperature, CoO powder (precursor containing cobalt), CuO powder (precursor containing copper), SnO powder (precursor containing tin), and W oxide powder (elemental A precursor containing M) was ground and the resulting powders were mixed and pressed into green pellets approximately 1 cm in diameter. The green pellets were placed in a high temperature furnace to obtain the cobalt-copper-tin oxide bulk material represented by formula (3) above (ie, the anode material of Example 3). Here, x3 is 4, the element M is W, the atomic ratio of the element M is 10 atomic % or less, and the cobalt-copper-tin oxide has an average particle size of about 0.1 μm to about 10 μm. Range.

Secondary Battery Preparation The ground and comminuted anode material of Example 3, Super P conductive carbon and binder (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed at a weight ratio of 7:2:1. mixed in ratio. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into Example 3 anodes with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 3 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 3 was prepared.

Example 4
Preparation of Anode Materials CoO powder (cobalt oxide), CuO powder (copper oxide), _SnO2 powder (tin oxide), and W oxide powder (oxide containing element M) were prepared at room temperature using a ball mill. ) were ground and mixed to obtain an oxide mixture containing cobalt, copper, and tin (ie, the anode material of Example 4). Here, the atomic ratio of cobalt, copper and tin is 1:1:1, the element M is W, and the atomic ratio of the element M is 10 atomic % or less.

Secondary Battery Preparation The anode material of Example 4, Super P conductive carbon and a binder (ie sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into Example 4 anodes with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 4 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 4 was prepared.

Example 5
Preparation of anode materials At room temperature, using a ball mill, _SiO2 powder (precursor containing silicon ₎ , _SnO2 powder (precursor containing tin), _Fe2O3 powder (precursor containing iron), _TiO2 The powder (precursor containing element M) was ground and the resulting powders were mixed and pressed into green pellets approximately 1 cm in diameter. The green pellets were placed in a high temperature furnace to obtain the silicon-tin-iron oxide bulk material represented by formula (4) above (ie, the anode material of Example 4). Here, x4 is 21, the element M is Ti, the atomic ratio of the element M is 10 atomic % or less, and the average particle size of the silicon-tin-iron oxide is about 0.1 μm to about 10 μm. Range.

Secondary Battery Preparation The ground and comminuted anode material of Example 5, Super P conductive carbon and binder (i.e. sodium carboxymethylcellulose (CMC) dissolved in water) were mixed at a weight ratio of 7:2:1. mixed in ratio. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into Example 5 anodes with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 5 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 5 was prepared.

Example 6
Preparation of anode materials At room temperature, using a ball mill, _SiO2 powder (silicon oxide), _SnO2 powder (tin oxide), _Fe2O3 powder (iron oxide), _TiO2 powder (oxide _containing element M) were ground and mixed to obtain an oxide mixture containing silicon, tin and iron (ie, the anode material of Example 6). The atomic ratio of silicon, tin and iron is 4:1:16, the element M is Ti, and the atomic ratio of the element M is 10 atomic % or less.

Secondary Battery Preparation The anode material of Example 6 was mixed with Super P conductive carbon and a binder (ie sodium carboxymethylcellulose (CMC) dissolved in water) in a weight ratio of 7:2:1. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into Example 6 anodes with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 6 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 6 was prepared.

Example 7
Preparation of Anode Materials CuO powder (precursor containing copper), MnO powder (precursor containing manganese), _SiO2 powder (precursor containing silicon), and _TiO2 powder (elemental) were prepared using a ball mill at room temperature. A precursor containing M) was ground and the resulting powders were mixed and pressed into green pellets approximately 1 cm in diameter. The green pellets were placed in a high temperature furnace to obtain the copper-manganese-silicon oxide bulk material represented by formula (7) above (ie, the anode material of Example 7). Here, x7 is 1, the element M is Ti, the atomic ratio of the element M is 10 atomic % or less, and the average particle size of the copper-manganese-silicon oxide is about 0.1 μm to about 10 μm. Range.

Secondary Battery Preparation The ground anode material of Example 7 and Super P conductive carbon and binder (i.e. sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed at a weight ratio of 7:2:1. mixed in ratio. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into Example 7 anodes with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 7 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 7 was prepared.

Example 8
Preparation of anode materials At room temperature, using a ball mill, grind and mix CuO powder (copper oxide), MnO powder (manganese oxide), _SiO2 powder (silicon oxide), _TiO2 powder (oxide containing element M) to obtain an oxide mixture containing copper, manganese and silicon (ie, the anode material of Example 8). The atomic ratio of copper, manganese and silicon is 1:4:1, the element M is Ti, and the atomic ratio of the element M is 10 atomic % or less.

Secondary Battery Preparation The anode material of Example 8, Super P conductive carbon and binder (ie, sodium carboxymethylcellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into Example 8 anodes with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 8 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 8 was prepared.

Example 9
Preparation of anode materials At room temperature, using a ball mill, _SnO2 powder (precursor containing tin), _MnO2 powder (precursor containing manganese), NiO powder (precursor containing nickel), Mo oxide powder ( A precursor containing the element M) was ground and the resulting powders were mixed and pressed into green pellets with a diameter of about 1 cm. The green pellets were placed in a high temperature furnace to yield the tin-manganese-nickel oxide bulk material represented by formula (8) above (ie, the anode material of Example 9). Here, x8 is 7, the element M is Mo, the atomic ratio of the element M is 10 atomic % or less, and the tin-manganese-nickel oxide has an average particle size of about 0.1 μm to about 10 μm. Range.

Secondary Battery Preparation The ground anode material of Example 9 and Super P conductive carbon and binder (i.e. sodium carboxymethylcellulose (CMC) dissolved in water) were mixed at a weight ratio of 7:2:1. mixed in ratio. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into Example 9 anodes with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 9 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 9 was prepared.

Example 10
Preparation of anode materials At room temperature, using a ball mill, grind _SnO2 powder (tin oxide), _MnO2 powder (manganese oxide), NiO powder (nickel oxide), Mo oxide powder (oxide containing element M) • Mixed to obtain an oxide mixture containing tin, manganese and nickel (ie the anode material of Example 10). The atomic ratio of tin, manganese and nickel is 1:2:1, the element M is Mo, and the atomic ratio of the element M is 10 atomic % or less.

Secondary Battery Preparation The anode material of Example 10 was mixed with Super P conductive carbon and a binder (ie sodium carboxymethylcellulose (CMC) dissolved in water) in a weight ratio of 7:2:1. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into Example 10 anodes with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 10 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 10 was prepared.

Example 11
Preparation of anode materials _MnO powder (precursor containing manganese), CuO powder (precursor containing copper), NiO powder (precursor containing nickel), Mo oxide powder (elemental A precursor containing M) was ground and the resulting powders were mixed and pressed into green pellets approximately 1 cm in diameter. The green pellets were placed in a high temperature furnace to obtain the manganese-copper-nickel oxide bulk material represented by formula (13) above (ie, the anode material of Example 11). Here, the element M is Mo, the atomic ratio of the element M is 10 atomic % or less, and the average particle size of the manganese-copper-nickel oxide is in the range of about 0.1 μm to about 10 μm.

Secondary Battery Preparation The ground and comminuted anode material of Example 11, Super P conductive carbon and binder (i.e. sodium carboxymethylcellulose (CMC) dissolved in water) were mixed at a weight ratio of 7:2:1. mixed in ratio. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into Example 11 anodes with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 11 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 11 was prepared.

Example 12
Preparation of anode materials At room temperature, _MnO2 powder (manganese oxide), CuO powder (copper oxide), NiO powder (nickel oxide), Mo oxide powder (oxide containing element M) were ground using a ball mill. Mixing yielded an oxide mixture containing manganese, copper, and nickel (ie, the anode material of Example 12). Here, the atomic ratio of manganese, copper and nickel is 2:1:1, the element M is Mo, and the atomic ratio of the element M is 10 atomic % or less.

Secondary Battery Preparation The anode material of Example 12 was mixed with Super P conductive carbon and a binder (ie sodium carboxymethylcellulose (CMC) dissolved in water) in a weight ratio of 7:2:1. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into Example 12 anodes with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 12 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 12 was prepared.

Example 13
Preparation of Anode Materials Grind NiO powder (nickel oxide), CuO powder (copper oxide), _SnO2 powder (tin oxide), and W oxide powder (oxide containing element M) using a ball mill at room temperature. • Mixed to obtain an oxide mixture containing nickel, copper and tin (ie, the anode material of Example 13). The atomic ratio of nickel, copper and tin is 1:1:2, element M is W, and the atomic ratio of element M is 10 atomic % or less.

Secondary Battery Preparation The anode material of Example 13 was mixed with Super P conductive carbon and a binder (ie sodium carboxymethylcellulose (CMC) dissolved in water) in a weight ratio of 7:2:1. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into Example 13 anodes with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 13 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 13 was prepared.

Example 14
Preparation of anode materials NiO powder (precursor containing nickel), CuO powder (precursor containing copper), _SnO2 powder (precursor containing tin), W oxide powder (elemental A precursor containing M) was ground and the resulting powders were mixed and pressed into green pellets approximately 1 cm in diameter. The green pellets were placed in a high temperature furnace to yield the nickel-copper-tin oxide bulk material represented by formula (15) above (ie, the anode material of Example 14). Here, x15 is 6, the element M is W, the atomic ratio of the element M is 10 atomic % or less, and the nickel-copper-tin oxide has an average particle size of about 0.1 μm to about 10 μm. Range.

Secondary Battery Preparation The ground and comminuted anode material of Example 14, Super P conductive carbon and binder (i.e. sodium carboxymethylcellulose (CMC) dissolved in water) were mixed at a weight ratio of 7:2:1. mixed in ratio. Next, zirconia balls were added and mixed for about 30 minutes to form an anode slurry. Next, a spatula (100 μm) is used to evenly apply the slurry to a copper foil (the current collector described above), and then the slurry-applied copper foil is placed in a vacuum oven and heated at about 110°C. Allow to dry for about 12 hours. The dried copper foil was then cut into anodes of Example 14 with a diameter of about 12.8 mm by a cutting machine.

The anode of Example 14 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to an organic solvent as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) as the separator, and stainless steel 304 as the package structure. Or a button cell (model: CR2032) was assembled using a 316 cover. Up to this point, the secondary battery of Example 14 was prepared.

Comparative example 1
Preparation of Secondary Battery A secondary battery of Comparative Example 1 was prepared by the same manufacturing procedure as in Example 1. The difference between the secondary battery of Comparative Example 1 and the secondary battery of Example 1 is mainly that in the secondary battery of Example 1, the working electrode is the anode of Example 1; , the material of _the working electrode is _Co2SnO4 .

Comparative example 2
Preparation of Secondary Battery A secondary battery of Comparative Example 2 was prepared by the same manufacturing procedure as in Example 1. The difference between the secondary battery of Comparative Example 2 and the secondary battery of Example 1 is mainly that in the secondary battery of Example 1, the working electrode is the anode of Example 1; , the material of the working electrode is CoO.

Comparative example 3
Preparation of Secondary Battery A secondary battery of Comparative Example 3 was prepared by the same manufacturing procedure as in Example 1. The difference between the secondary battery of Comparative Example 3 and the secondary battery of Example 1 is mainly that in the secondary battery of Example 1, the working electrode is the anode of Example 1; , the material of the working electrode is CuO.

Comparative example 4
Preparation of Secondary Battery A secondary battery of Comparative Example 4 was prepared by the same manufacturing procedure as in Example 1. The difference between the secondary battery of Comparative Example 4 and the secondary battery of Example 1 is mainly that in the secondary battery of Example 1, the working electrode is the anode of Example 1; , the material of the working electrode is _SnO2 .

Comparative example 5
Preparation of Secondary Battery A secondary battery of Comparative Example 5 was prepared by the same manufacturing procedure as in Example 1. The difference between the secondary battery of Comparative Example 5 and the secondary battery of Example 1 is mainly that in the secondary battery of Example 1, the working electrode is the anode of Example 1; , the material of the working electrode is _SiO2 .

Comparative example 6
Preparation of Secondary Battery A secondary battery of Comparative Example 6 was prepared by the same manufacturing procedure as in Example 1. The difference between the secondary battery of Comparative Example 6 and the secondary battery of Example 1 is mainly that in the secondary battery of Example 1, the working electrode is the anode of Example 1; , the material of the working electrode is Fe ₂ O ₃ .

Comparative example 7
Preparation of Secondary Battery A secondary battery of Comparative Example 7 was prepared by the same manufacturing procedure as in Example 1. The difference between the secondary battery of Comparative Example 7 and the secondary battery of Example 1 is mainly that in the secondary battery of Example 1, the working electrode is the anode of Example 1; , the material of the working electrode is MnO.

Comparative example 8
Preparation of Secondary Battery A secondary battery of Comparative Example 8 was prepared by the same manufacturing procedure as in Example 1. The difference between the secondary battery of Comparative Example 8 and the secondary battery of Example 1 is mainly that in the secondary battery of Example 1, the working electrode is the anode of Example 1; , the material of the working electrode is _MnO2 .

Comparative example 9
Preparation of Secondary Battery A secondary battery of Comparative Example 9 was prepared by the same manufacturing procedure as in Example 1. The difference between the secondary battery of Comparative Example 9 and the secondary battery of Example 1 is mainly that in the secondary battery of Example 1, the working electrode is the anode of Example 1; , the material of the working electrode is NiO.

After preparing the secondary batteries of Examples 1 to 14 and the secondary batteries of Comparative Examples 1 to 9, each of the secondary batteries of Examples 1 to 14 and the secondary batteries of Comparative Examples 1 to 9 was subjected to charge-discharge cycles. did the test.

Charge-discharge cycle test For each of the secondary batteries of Examples 1 to 14 and the secondary batteries of Comparative Examples 1 to 9, the battery cycle life capacity was measured under an environment of voltage 0.01 V to 3 V and about 15 ° C. to about 30 ° C. did the test. Measurement results are shown in FIGS.

As can be seen from FIGS. 2-4, compared to the secondary battery of Comparative Example 1, the secondary batteries of Examples 1-3 have better capacity and capacity retention after a high number of cycles (>250 times). have sex.

In the secondary battery containing cobalt-copper-tin oxide represented by formula (1), where x1 is 9 or 14, the above test was not performed, but the above-mentioned test of cobalt-copper-tin oxide According to the description and the test results of Example 1, those skilled in the art can see that the secondary battery containing cobalt-copper-tin oxide represented by formula (1), where x1 is 9 or 14, has good capacity and capacity retention. It should be understood that the

The secondary battery containing cobalt-copper-tin oxide represented by formula (2) and x2 being 6 or 8 was not subjected to the above test, but the above-mentioned According to the description and the test results of Example 2, those skilled in the art can see that the secondary battery containing cobalt-copper-tin oxide represented by formula (2), where x2 is 6 or 8, has good capacity and capacity. It should be understood that it can have retentive properties.

In the secondary battery containing cobalt-copper-tin oxide represented by formula (3), where x3 is 3 or 5, the above test was not performed, but the above-mentioned According to the description and the test results of Example 1, those skilled in the art can see that the secondary battery containing cobalt-copper-tin oxide represented by formula (3), where x3 is 3 or 5, has good capacity and capacity. It should be understood that it can have retentive properties.

As can be seen from FIG. 5, compared to the secondary batteries of Comparative Examples 2-4, the secondary battery of Example 4 exhibits better capacity and capacity retention after a high number of cycles (>250 times). have.

Secondary batteries containing oxide mixtures containing cobalt, copper and tin with an atomic ratio of cobalt to copper to tin of 5:1:3 or 2:1:1 were not tested as described above. , cobalt, copper and tin, and the test results of Example 4, a person skilled in the art will know that the oxide mixture contains cobalt, copper and tin and the atomic ratio of cobalt to copper to tin is 5:1. :3 or 2:1:1 secondary batteries can have good capacity and capacity retention.

As can be seen from FIGS. 6 and 7, compared to the secondary batteries of Comparative Examples 4-6, the secondary batteries of Examples 5 and 6 have better capacity after a high number of cycles (>250 times). and capacity retention.

In the secondary battery containing silicon-tin-iron oxide represented by formula (4) and x4 being greater than 21 and not more than 34, the above test was not performed, but the silicon-tin-iron oxide According to the above description and the test results of Example 5, a person skilled in the art can say that a secondary battery containing silicon-tin-iron oxide, represented by formula (4), wherein x4 is greater than 21 and less than or equal to 34, is good. It should be understood that it can have a different capacity and capacity retention.

The foregoing tests were not performed on secondary batteries containing silicon-tin-iron oxides represented by formula (5) or (6), but the above description and implementation of silicon-tin-iron oxides According to the test results of Example 5, those skilled in the art know that secondary batteries containing silicon-tin-iron oxide represented by formula (5) or (6) can have good capacity and capacity retention. should be understood.

Secondary batteries containing oxide mixtures containing silicon, tin and iron and having an atomic ratio of silicon to tin to iron of 1:1:1 or 4:1:1 were not tested as described above. , silicon, tin and iron, and the test results of Example 6, a person skilled in the art will know that the oxide mixture contains silicon, tin and iron and the atomic ratio of silicon to tin to iron is 1:1. It should be understood that secondary batteries containing oxide mixtures that are :1 or 4:1:1 can have good capacity and capacity retention.

As can be seen from FIG. 8, the secondary battery of Example 7 has good capacity and capacity retention after a high number of cycles (>250 times).

The above-described test was not performed on the secondary battery containing the copper-manganese-silicon oxide represented by the formula (7), where x7 is greater than 0 and less than 1. and the test results of Example 7, those skilled in the art know that a secondary battery containing copper-manganese-silicon oxide, represented by formula (7), wherein x7 is greater than 0 and less than 1, has a good capacity and capacity retention.

As can be seen from FIG. 9, compared to the secondary batteries of Comparative Examples 3, 5 and 7, the secondary battery of Example 8 has better capacity and capacity retention after a high number of cycles (>250 times). have sex.

For secondary batteries containing oxide mixtures containing copper, manganese and silicon and having an atomic ratio of copper, manganese and silicon of 1:1:1, 4:1:1 or 1:1:4, the above test However, according to the foregoing description of the oxide mixture containing copper, manganese and silicon and the test results of Example 8, one skilled in the art would know that the mixture containing copper, manganese and silicon contains copper, manganese and silicon. It should be understood that secondary batteries containing oxide mixtures with atomic ratios of 1:1:1, 4:1:1 or 1:1:4 can have good capacity and capacity retention. .

As can be seen from FIGS. 10 and 11, compared to the secondary batteries of Comparative Examples 4, 8 and 9, the secondary batteries of Examples 9 and 10 are better after a high number of cycles (>250 times). It has a good capacity and capacity retention.

The secondary battery containing tin-manganese-nickel oxide represented by formula (8) and x8 being 4 or more and less than 7 was not subjected to the above test, but the above-mentioned tin-manganese-nickel oxide According to the description and the test results of Example 9, those skilled in the art can see that the secondary battery containing tin-manganese-nickel oxide represented by formula (8) and x8 is 4 or more and less than 7 has good capacity and capacity. It should be understood that it can have retentive properties.

Secondary batteries containing tin-manganese-nickel oxides represented by formulas (9), (10) or (11) were not subjected to the above tests, but the above-mentioned and the test results of Example 9, those skilled in the art know that the secondary battery containing tin-manganese-nickel oxide represented by formula (9), (10) or (11) has a good capacity. and capacity retention.

For secondary batteries containing oxide mixtures containing tin, manganese and nickel and having an atomic ratio of tin:manganese:nickel of 1:1:1, 1:1:2 or 2:1:1, the above test However, according to the foregoing description of the oxide mixture containing tin, manganese and nickel and the test results of Example 10, one skilled in the art would know that It should be understood that secondary batteries containing oxide mixtures with atomic ratios of 1:1:1, 1:1:2 or 2:1:1 can have good capacity and capacity retention. .

As can be seen from FIG. 12, the secondary battery of Example 11 has good capacity and capacity retention after a high number of cycles (>250 times).

The foregoing tests were not performed on secondary batteries containing manganese-copper-nickel oxides represented by formula (12) or (14), but the foregoing description and implementation of manganese-copper-nickel oxides According to the test results of Example 11, those skilled in the art know that secondary batteries containing manganese-copper-nickel oxide represented by formula (12) or (14) can have good capacity and capacity retention. should be understood.

As can be seen from FIG. 13, compared to the secondary batteries of Comparative Examples 3, 8 and 9, the secondary battery of Example 12 has better capacity and capacity retention after a high number of cycles (>250 times). have sex.

Secondary batteries containing oxide mixtures containing manganese, copper and nickel and having an atomic ratio of manganese to copper to nickel of 3:2:1 or 1:1:1 were not tested as described above. , manganese, copper and nickel, and the test results of Example 12, a person skilled in the art will know that the oxide mixture contains manganese, copper and nickel and the atomic ratio of manganese to copper to nickel is 3:2. It should be understood that secondary batteries containing oxide mixtures that are :1 or 1:1:1 can have good capacity and capacity retention.

As can be seen from FIG. 14, compared to the secondary batteries of Comparative Examples 3, 4 and 9, the secondary battery of Example 13 has better capacity and capacity retention after a high number of cycles (>250 times). have sex.

Secondary batteries containing oxide mixtures containing nickel, copper and tin and having an atomic ratio of nickel:copper:tin of 2:1:3 or 1:2:3 were not subjected to the above tests. , nickel, copper and tin, and the test results of Example 13, a person skilled in the art will know that the oxide mixture contains nickel, copper and tin, and the atomic ratio of nickel:copper:tin is 2:1. It should be understood that secondary batteries containing oxide mixtures that are :3 or 1:2:3 can have good capacity and capacity retention.

As can be seen from FIG. 15, the secondary battery of Example 14 has good capacity and capacity retention after a high number of cycles (>250 times).

The above test was not performed on the secondary battery containing the nickel-copper-tin oxide represented by the formula (15) and x15 is 3 or 9, but the above-mentioned nickel-copper-tin oxide According to the description and the test results of Example 14, those skilled in the art can see that the secondary battery containing the nickel-copper-tin oxide represented by formula (15), where x15 is 3 or 9, has good capacity and capacity retention. It should be understood that the

The above tests were not performed on the secondary battery containing the nickel-copper-tin oxide represented by formula (16) or formula (17), but the above description and implementation of the nickel-copper-tin oxide According to the test results of Example 14, those skilled in the art know that secondary batteries containing nickel-copper-tin oxide represented by formula (16) or formula (17) can have good capacity and capacity retention. should be understood.

From the above-mentioned test results, by producing an anode using the anode material for a secondary battery of the present invention, the secondary battery to which the anode is applied has good capacity, stability, and charge-discharge cycle life. confirmed to be obtained.

In addition, a secondary battery using an anode made of the anode material for a secondary battery of the present invention has a larger capacity than commercially available graphite (theoretical value of capacity is 372 mAh / g). Anode materials can effectively improve battery performance.

Although the invention has been described with reference to the above embodiments, it will be apparent to those skilled in the art that modifications can be made to the described embodiments without departing from the spirit of the invention. Accordingly, the scope of the invention is defined by the appended claims rather than by the above detailed description.

With the disclosure herein, the anode materials and anodes of the present invention can be applied in secondary batteries, resulting in improved secondary battery capacity and stability.

100: Secondary Battery 102: Anode 102a, 104a: Current Collector 102b: Anode Material Layer 104: Cathode 104b: Cathode Material Layer 106: Separator 108: Electrolyte 110: Housing Area 112: Package Structure

Claims (5)

Anode material for secondary battery containing cobalt-copper-tin oxide represented by any one of the following formulas (1) to (3):
_{Co5Cu1Sn3MOx1 Formula (} 1) _{,
Co2Cu1Sn1MO x2 formula (} 2),
_{Co1Cu1Sn1MO x3 formula (} 3),
where x1 is 8, 9 or 14, x2 is 4, 6 or 8, x3 is 3, 4 or 5, M is Ni, Cr, Mn, Zn, Al, Ti, In, At least one element selected from the group consisting of Mo and W, and the atomic ratio of M is represented by formula (1), formula (2) or formula (3) in cobalt-copper-tin oxide It is 10 atomic % or less with respect to the total number of atoms of the metal element. Claim 1, wherein the cobalt-copper-tin oxide represented by formula (1), formula (2), or formula (3) has a spinel structure, perovskite structure, sodium chloride structure, or chalcopyrite structure. The anode material for secondary batteries as described in 1. A secondary battery anode comprising: a current collector; and an anode material layer disposed on said current collector and comprising the secondary battery anode material of claim 1 . cathode;
an anode arranged separately from the cathode, the anode being the secondary battery anode according to claim 3 ;
A secondary battery comprising: an electrolyte provided between the cathode and the anode; and a package structure packing the cathode, the anode, and the electrolyte. further comprising a separator positioned between the cathode and the anode;
said separator, said cathode and said anode define a containment area of a storage system;
5. The secondary battery according to claim 4 , wherein said electrolyte is disposed in said containing area.

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