JP7410593B2 - Anode materials for secondary batteries, anodes for secondary batteries, and secondary batteries - Google Patents

Description

The present invention relates to an electrode material, an electrode, and a battery, particularly an anode material for a secondary battery, an anode for a secondary battery, and a secondary battery.

In recent years, market demand for lithium-ion secondary batteries, which can be repeatedly charged and discharged, are lightweight, have high voltage values, and high energy density, has been rapidly increasing. Therefore, the requirements for current lithium ion secondary batteries, such as light weight, durability, high voltage, high energy density, and high safety, are becoming increasingly strict. Lithium-ion secondary batteries have great potential for applications and scalability, such as small electric vehicles, electric vehicles, and large-scale power storage industries. The most common commercially available electrode material is graphite, but graphite's low capacity (theoretical value is 372 mAh/g) limits the performance of batteries made with it. Therefore, finding a highly stable and high capacity electrode material for secondary batteries is one of the goals that those skilled in the art would like to achieve.

From this viewpoint, the present invention provides an anode material and an anode that can be used in a secondary battery and improve the capacity and stability of the secondary battery.

An anode material for a secondary battery provided as one embodiment of the present invention includes a cobalt-copper-tin oxide represented by any of the following formulas (1) to (3):
Co ₅ Cu ₁ Sn ₃ MO _x1 formula (1),
Co ₂ Cu ₁ Sn ₁ MO _x2 formula (2),
Co ₁ Cu ₁ Sn ₁ MO _x3 formula (3),
Here, x1 is 8, 9 or 14, x2 is 4, 6 or 8, x3 is 3, 4 or 5, and 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 in the cobalt-copper-tin oxide represented by formula (1), formula (2) or formula (3). It is 10 atomic % or less based on the total number of atoms of the metal element.

An anode material for a secondary battery according to another embodiment of the present invention includes at least one of _Co3O4 , _Co2O3 , and _CoO , at least one of CuO _{and Cu2O} , and at least one of SnO and _SnO2 . an oxide mixture obtained by performing a step of mixing cobalt, copper, and tin in the oxide mixture, the atomic ratio of cobalt, copper, and tin being 5:1:3, 2:1:1, or 1:1: 1.

An anode material for a secondary battery provided by another embodiment of the present invention includes a silicon-tin-iron oxide represented by any of the following formulas (4) to (6):
Si ₄ Sn ₁ Fe ₁₆ MO _x4 formula (4),
Si ₁ Sn ₁ Fe ₁ MO _x5 Formula (5),
Si ₄ Sn ₁ Fe ₁ MO _x6 formula (6),
Here, x4 is 21 to 34, x5 is 3 to 5, x6 is 6 to 11.5, and M is a group consisting of Cr, Mn, Zn, Al, Ti, In, Mo, and W. at least one element selected from the following, and the atomic ratio of M is at least one element selected from the following: It is 10 atomic % or less based on the total number of atoms.

An anode material for a secondary battery according to another embodiment of the present invention includes at least one of SiO ₂ and SiO, at least one of SnO and SnO ₂ , and at least one of Fe ₂ O ₃ , Fe ₃ O ₄ and FeO. An oxide mixture obtained by performing a step of mixing, 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.

An anode material for a secondary battery provided by another embodiment of the present invention includes 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; The atomic ratio of is 10 atomic % or less based on the total number of atoms of elements other than oxygen in the copper-manganese-silicon oxide represented by formula (7).

An anode material for a secondary battery according to another embodiment of the present invention includes at least one of CuO and Cu ₂ O, at least one of SiO ₂ and SiO, and MnO, MnO ₂ , Mn ₂ O ₃ and Mn ₃ O ₄ An oxide mixture obtained by mixing at least one of the following, wherein the atomic ratio of copper, manganese and silicon in the oxide mixture is 1:1:1, 1:4:1, 4: 1:1 or 1:1:4 oxide mixtures.

An anode material for a secondary battery provided by another embodiment of the present invention includes 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),
Sn ₂ Mn ₁ Ni ₁ MO _x10 formula (10),
Sn ₁ Mn ₁ Ni ₁ MO _x11 formula (11),
Here, x8 is 4 to 7, x9 is 4 to 7, x10 is 4 to 7, x11 is 3 to 6, and M is selected from the group consisting of Cr, Mn, Zn, Al, Ti, In, Mo, and W. The atomic ratio of M is at least one element in the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10) or formula (11). It is 10 atomic % or less based on the total number of atoms.

The anode material for a secondary battery provided by another embodiment of the present invention includes at least one of SnO and SnO ₂ , at least one of MnO, MnO ₂ , Mn ₂ O ₃ and Mn ₃ O ₄ , 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: 1, 1:1:2 or 2:1:1.

An anode material for a secondary battery provided by another embodiment of the present invention includes a manganese-copper-nickel oxide represented by any of the following formulas (12) to (14):
Mn ₃ Cu ₂ Ni ₁ MO ₈ formula (12),
Mn ₂ Cu ₁ Ni ₁ MO ₄ formula (13),
Mn ₁ Cu ₁ Ni ₁ MO ₄ 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 determined by the formula (12), the formula ( 13) or 10 atomic % or less based on the total number of atoms of the metal element in the manganese-copper-nickel oxide represented by formula (14).

The anode material for a secondary battery provided by another embodiment of the present invention includes at least one of MnO, MnO ₂ , Mn ₂ O ₃ and Mn ₃ O ₄ , at least one of CuO and Cu ₂ O, and NiO and _Ni2O3 , wherein the atomic ratio of manganese, copper, and nickel in _the oxide mixture is 3:2:1, 2: 1:1 or 1:1:1 oxide mixtures.

An anode material for a secondary battery provided by another embodiment of the present invention includes a nickel-copper-tin oxide represented by any of the following formulas (15) to (17):
_{NiCuSn2MO x15} formula (15),
Ni ₂ CuSn ₃ MO _x16 formula (16),
NiCu ₂ Sn ₃ MO _x17 formula (17),
Here, x15 is 3, 6 or 9, x16 is 4, 6 or 9, x17 is 4, 6 or 9, and M is Cr, Mn, Zn, Al, Ti, In, Mo, It is at least one element selected from the group consisting of W and Co, and the atomic ratio of M is as follows: It is 10 atomic % or less based on the total number of atoms of the metal element.

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

An anode for a secondary battery according to an 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 includes any of the above-described anode materials for secondary batteries.

A secondary battery provided by an 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 anode for a secondary battery described above. An electrolyte is provided between the cathode and the anode. The package structure packs the cathode, anode, and electrolyte.

Based on the above, the anode material for secondary batteries of the present invention contains a metal oxide represented by any 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, said oxide mixture having a particular atomic ratio of the elements. Such an anode material for a secondary battery of the present invention can be used in a secondary battery, and as a result, it can provide the secondary battery with good capacity, stability, and charge/discharge cycle life.

In order to better understand the above features and advantages of the present invention, embodiments are described in detail below along with the accompanying drawings.

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

As used herein, ranges expressed as "from one number to another" are shorthand expressions to avoid listing every number in the range set forth in the specification. Accordingly, the recitation of a particular numerical range herein refers to any numerical value within the numerical range and to any numerical range less than that defined by any numerical value within the numerical range. It also covers numerical ranges.

As used herein, "about," "approximately," "essentially," or "substantially" includes the stated value and relates to the measurement in question and the measurement of the particular quantity. within an acceptable deviation range for a particular value, as determined by a person skilled in the art, taking into account the errors (i.e., limitations of the measurement system). For example, "about" can mean within one or more standard deviations, or, for example, within ±30%, ±20%, ±15%, ±10%, ±5% of the stated value. Additionally, rather than applying one standard deviation across all characteristics, "about," "approximately," "essentially," or "substantially" as used herein may be based on measured or other characteristics. A relatively acceptable range of deviation or standard deviation may be selected for the term ``in terms of''.

In order to provide an anode material that can be applied to the anode of a secondary battery and can provide good stability and capacity to the secondary battery, the present invention provides an anode material that can achieve the above advantages. . Hereinafter, specific embodiments will be described as examples that can reliably implement the present invention.

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

In this embodiment, the method for preparing the metal oxide containing four or more elements is, for example, a hydrothermal method, a co-precipitation method, a sol-gel method, a solid state method, an evaporation method, a sputtering method, or a vapor deposition method. However, the present invention is not limited thereto. In one embodiment in which a metal oxide containing four or more elements is prepared using a hydrothermal method, the temperature is about 200° C. or more, the incubation time is about 5 hours or more, and the ambient pressure is about 10 ⁻² Torr or more. obtain. In one embodiment of preparing a metal oxide containing four or more elements using a coprecipitation method, coprecipitation is first performed, the reaction temperature is 200° C. or higher, the pH of the solution is between about 2 and about 12, and the temperature is kept warm. The time can be about 1 hour or more; after the reaction is finished, a calcination treatment is performed, the calcination temperature can be about 300° C. or more, and the incubation time can be about 1 hour or more. In one embodiment in which a metal oxide containing four or more elements is prepared using a sol-gel method, the temperature is about 100° C. or more, the pH of the solution is about 2 to about 12, and the temperature holding time is about 5 hours or more. It 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 more and the incubation time can be about 8 hours or more. In one embodiment in which a metal oxide containing four or more elements is prepared using an evaporation method, the temperature can be about 25° C. or more, the evaporation time can be about 1 hour or more, and the ambient pressure can be about 10 ⁻³ Torr or more. . In one embodiment in which a metal oxide containing four or more elements is prepared using a sputtering method, the temperature is about 25° C. or more, the sputtering time is about 0.5 hours or more, and the ambient pressure is about 10 ⁻³ Torr or more. could be. In one embodiment in which a metal oxide containing four or more elements is prepared using a vapor deposition method, the temperature can be about 25° C. or more, the deposition time can be about 1 hour or more, and the ambient pressure can be about 10 ⁻³ Torr or more. .

In this embodiment, the metal oxide containing four or more elements includes cobalt-copper-tin oxide, silicon-tin-iron oxide, copper-manganese-silicon oxide, tin-manganese-nickel oxide, and manganese. - May contain copper-nickel oxide or nickel-copper-tin oxide. The various oxides mentioned above will be explained in detail below.

Cobalt-Copper-Tin Oxide In this embodiment, the cobalt-copper-tin oxide can be represented by any of the following formulas (1) to (3):
Co ₅ Cu ₁ Sn ₃ MO _x1 formula (1),
Co ₂ Cu ₁ Sn ₁ MO _x2 formula (2),
Co ₁ Cu ₁ Sn ₁ MO _x3 Formula (3).

In formula (1), x1 is 8, 9, or 14. In formula (2), x2 is 4, 6, or 8. In formula (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 Has a 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 based on the total number of atoms of the metal element 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 not contain element M, but may contain 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 that contains M in an atomic ratio greater than 0 atomic % and less than 10 atomic % has an electrical conductivity of about 10. It has increased by more than %. Furthermore, in the present embodiment, in the case of a cobalt-copper-tin oxide containing element M, a portion of cobalt, copper, and/or tin can be replaced with M. For example, in one embodiment, some of the cobalt can be replaced with M; in another embodiment, some of the cobalt and some of the copper can be replaced with M; in yet another embodiment, some of the cobalt and some of the copper can be replaced with M; , some of the copper, and some of the tin can be replaced by M, but the invention is not limited thereto. In addition, in this embodiment, the number of atoms of the cobalt-copper-tin oxide represented by formula (1), formula (2), or formula (3) is determined by the formation of oxygen vacancies or non-uniform diffusion. Therefore, 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. may have. In addition, the cobalt-copper-tin oxide represented by formula (1), formula (2), or formula (3) has the above structure, thereby enabling more oxygen vacancies. In a secondary battery to which the anode material containing the cobalt-copper-tin oxide is applied, lithium ions can be easily and quickly taken out and taken out, thereby effectively improving the diffusion rate and ionic conductivity of lithium ions. 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 the 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 for forming 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, Milling can be carried out using a vibratory ball mill or a planetary ball mill, but the invention is not limited thereto.

Silicon-tin-iron oxide In this embodiment, silicon-tin-iron oxide can be represented by any of the following formulas (4) to (6):
Si ₄ Sn ₁ Fe ₁₆ MO _x4 formula (4),
Si ₁ Sn ₁ Fe ₁ MO _x5 Formula (5),
Si ₄ Sn ₁ Fe ₁ MO _x6 Formula (6).

In formula (4), x4 is 21 to 34. In formula (5), x5 is 3 to 5. In equation (6), x6 is 6 to 11.5. When x4, x5, and x6 are each within the above ranges, a secondary battery to which an 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 may 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 based on 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). It is. In other words, the silicon-tin-iron oxide represented by formula (4), formula (5), or formula (6) may not contain element M, but may contain four elements, namely silicon and tin. , iron, and oxygen. In addition, compared to a silicon-tin-iron oxide that does not contain the element M, a silicon-tin-iron oxide that contains M in an atomic ratio greater than 0 atomic % and less than 10 atomic % has an electrical conductivity of about 10. It has increased by more than %. Furthermore, in the present embodiment, in the case of a silicon-tin-iron oxide containing the element M, a portion of silicon, tin, and/or iron can be replaced with M. For example, in one embodiment, some of the silicon can be replaced with M; in another embodiment, some of the silicon and some of the tin can be replaced with M; in yet another embodiment, some of the silicon and some of the tin can be replaced with M; , some of the tin, and some of the iron can be replaced by M, but the invention is not limited thereto. In addition, in this embodiment, the number of atoms of the silicon-tin-iron oxide represented by formula (4), formula (5), or formula (6) is determined by the formation of oxygen vacancies or non-uniform diffusion. Therefore, an error of ±10% may occur.

In the present 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 it may have an orthorhombic structure. In addition, the silicon-tin-iron oxide represented by formula (4), formula (5), or formula (6) has the above structure, thereby enabling more oxygen vacancies. 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 out and taken out, thereby effectively improving the diffusion rate and ionic conductivity of lithium ions. 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 including the silicon-tin-iron oxide is applied can maintain a good charge/discharge cycle life.

In this embodiment, the average particle size of the silicon-tin-iron oxide is, 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 for forming an anode with good properties. In an embodiment for producing silicon-tin-iron oxide by a solid phase method, a mortar, a ball mill, a sand mill, a vibration Milling can be carried out using a ball mill or a planetary ball mill, although the invention is not limited thereto.

Copper-manganese-silicon oxide In the present 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 based on 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 not contain element M and may contain only four elements, namely copper, manganese, silicon, and oxygen. In addition, compared to a copper-manganese-silicon oxide that does not contain the element M, a copper-manganese-silicon oxide that contains M in an atomic ratio greater than 0 atomic % and less than 10 atomic % has an electrical conductivity of about 10. It has increased by more than %. Furthermore, in the present embodiment, in the case of a copper-manganese-silicon oxide containing the element M, a portion of copper, manganese, and/or silicon can be replaced with M. 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; in yet another embodiment, the copper , some of the manganese, and some of the silicon can be replaced by M, but the invention is not limited thereto. Note that in this embodiment, the number of atoms in the copper-manganese-silicon oxide represented by formula (7) may have an error of ±10% due to non-uniform diffusion or the formation of oxygen vacancies. , thereby forming a non-stoichiometric compound.

In the present embodiment, the copper-manganese-silicon oxide represented by formula (7) may have an absurmbachite structure, a pyroxmangite structure, or a braunite structure. . The copper-manganese-silicon oxide represented by the formula (7) has the above structure, so that in a secondary battery to which an anode material containing the copper-manganese-silicon oxide is applied, energy due to overpotential is reduced. 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 average particle size of the copper-manganese-silicon oxide is, 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 for forming 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 Milling can be carried out using a ball mill or a planetary ball mill, although the invention is not limited thereto.

Tin-manganese-nickel oxide In this embodiment, the tin-manganese-nickel oxide can be 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),
Sn ₂ Mn ₁ Ni ₁ MO _x10 formula (10),
Sn ₁ Mn ₁ Ni ₁ MO _x11 Formula (11).

In equation (8), x8 is 4 to 7. In equation (9), x9 is 4 to 7. In equation (10), x10 is 4 to 7. In formula (11), x11 is 3 to 6. When x8, x9, x10, and x11 are each 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 to the total number of atoms of the metal elements in the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10), and formula (11). % or less. In other words, the tin-manganese-nickel oxides represented by formula (8), formula (9), formula (10), and formula (11) do not need to contain the element M, but can contain the four elements, That is, it may contain only tin, manganese, nickel, and oxygen. In addition, compared to the tin-manganese-nickel oxide which does not contain the element M, the tin-manganese-nickel oxide containing M in an atomic ratio greater than 0 atomic % and 10 atomic % or less has an electrical conductivity of about 10 It has increased by more than %. Furthermore, in the present embodiment, in the case of a tin-manganese-nickel oxide containing the element M, a portion of tin, manganese, and/or nickel can be replaced with M. For example, in one embodiment, some of the tin can be replaced with M; in another embodiment, some of the tin and some of the manganese can be replaced with M; in yet another embodiment, some of the tin and some of the manganese can be replaced with M; A part of M, a part of manganese, and a part of nickel can be replaced by M, but the present invention is not limited thereto. Note that in this embodiment, the number of atoms of the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10), and formula (11) is determined depending on the formation of oxygen vacancies or non-formation. Due to uniform diffusion, an error of ±10% may occur.

In this 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 the above structure, so that it has more oxygen vacancies. As a result, in a 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, thereby effectively increasing the diffusion rate and ionic conductivity of lithium ions. improves. Furthermore, since the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10), or formula (11) has the above structure, it disintegrates during the charging and discharging process. As a result, a secondary battery to which the anode material containing the tin-manganese-nickel oxide is applied can maintain a good charge-discharge cycle life.

In this embodiment, the average particle size of the tin-manganese-nickel oxide is, for example, between about 10 nm and about 1 mm. When the average particle size of the tin-manganese-nickel oxide is within the above range, it is advantageous for forming 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 vibration Milling can be carried out using a ball mill or a planetary ball mill, although the invention is not limited thereto.

Manganese-Copper-Nickel Oxide In this embodiment, the manganese-copper-nickel oxide can be represented by any of the following formulas (12) to (14):
Mn ₃ Cu ₂ Ni ₁ MO ₈ formula (12),
Mn ₂ Cu ₁ Ni ₁ MO ₄ formula (13),
Mn ₁ Cu ₁ Ni ₁ MO ₄ Formula (14).

That is, in this embodiment, the atomic ratio of manganese, copper, nickel, and oxygen in the manganese-copper-nickel oxide is 3:2:1:8, 2:1:1:4, or 1:1:1: It can be 4. Note that the manganese-copper-nickel oxide is represented by any of formulas (12) to (14), and a secondary battery to which an anode material containing the manganese-copper-nickel oxide is applied has an 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 based on the total number of atoms of the metal element 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 element M, but may contain four elements, namely manganese and copper. , nickel, and oxygen. In addition, compared to a manganese-copper-nickel oxide that does not contain the element M, a manganese-copper-nickel oxide that contains M in an atomic ratio greater than 0 atomic % and less than 10 atomic % has an electrical conductivity of about 10. It has increased by more than %. Furthermore, in the present embodiment, in the case of a manganese-copper-nickel oxide containing the element M, a part of manganese, copper, and/or nickel can be replaced with M. For example, in one embodiment, some of the manganese can be replaced with M; in another embodiment, some of the manganese and some of the copper can be replaced with M; in yet another embodiment, some of the manganese and some of the copper can be replaced with M; , some of the copper, and some of the nickel can be replaced by M, but the invention is not limited thereto. In addition, in this embodiment, the number of atoms of the manganese-copper-nickel oxide represented by formula (12), formula (13), or formula (14) is determined by the formation of oxygen vacancies or non-uniform diffusion. Therefore, an error of ±10% may occur.

In this 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. may have. In addition, the manganese-copper-nickel oxide represented by formula (12), formula (13), or formula (14) has the above structure, which enables more oxygen vacancies, thereby In a secondary battery to which the anode material containing the manganese-copper-nickel oxide is applied, lithium ions can be easily and quickly taken out and taken out, thereby effectively improving the diffusion rate and ionic conductivity of lithium ions. 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 a good charge/discharge cycle life.

In this embodiment, the average particle size of the manganese-copper-nickel oxide is, for example, between about 10 nm and about 1 mm. When the average particle size of the manganese-copper-nickel oxide is within the above range, it is advantageous for forming 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 vibration Milling can be carried out using a ball mill or a planetary ball mill, although the invention is not limited thereto.

Nickel-Copper-Tin Oxide In this embodiment, the nickel-copper-tin oxide can be represented by any of the following formulas (15) to (17):
_{NiCuSn2MO x15} formula (15),
Ni ₂ CuSn ₃ MO _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 each within the above ranges, a secondary battery to which an 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 based on the total number of atoms of the metal element 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 not contain element M, but may contain four elements, namely nickel, copper, It may contain only tin and oxygen. In addition, compared to a nickel-copper-tin oxide that does not contain the element M, a nickel-copper-tin oxide that contains M in an atomic ratio greater than 0 atomic % and less than 10 atomic % has an electrical conductivity of about 15 It has increased by more than %. Furthermore, in the present embodiment, in the case of a nickel-copper-tin oxide containing the element M, a portion of nickel, copper, and/or tin can be replaced with M. 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; in yet another embodiment, the nickel , some of the copper, and some of the tin can be replaced by M, but the invention is not limited thereto. Note that in this embodiment, the number of atoms in the nickel-copper-tin oxide represented by formula (15), formula (16), or formula (17) is determined by the formation of oxygen vacancies or nonuniform diffusion. , 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, thereby enabling more oxygen vacancies, and 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, thereby effectively improving the diffusion rate and ionic conductivity of lithium ions. 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 the nickel-copper-tin oxide is, for example, between about 10 nm and about 1 mm. When the average particle size of the nickel-copper-tin oxide is within the above range, it is advantageous for forming 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 vibration Milling can be carried out using a ball mill or a planetary ball mill, although the invention is not limited thereto.

Further, in this embodiment, as a method for preparing an oxide mixture containing four or more elements, for example, a mixing step may be performed. The mixing step is performed, for example, by 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, such as about 25° C. or higher. In one embodiment in which a physical wet mixing method is used to prepare an oxide mixture containing four or more elements, the mixing temperature can be room temperature, e.g., about 25° C. or higher, and the solvent is water, alcohol, acetone, or Can be methanol.

In this embodiment, the oxide mixture containing four or more elements includes an oxide mixture containing cobalt, copper, and tin, an oxide mixture containing silicon, tin, and iron, and an oxide mixture containing copper, manganese, and silicon. oxide mixtures containing tin, manganese, and nickel; oxide mixtures containing manganese, copper, and nickel; or oxide mixtures containing nickel, copper, and tin. The various oxide mixtures mentioned above will be explained in detail below.

Oxide mixture containing cobalt, copper, and tin In the present embodiment, the oxide mixture containing cobalt, copper, and tin includes 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 _SnO2 . 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 may be 5:1:3, 2:1:1, or 1:1:1. . If the atomic ratios of cobalt, copper, and tin meet the above specific ratios, the secondary battery to which the anode material containing the oxide mixture containing cobalt, copper, and tin is applied will have excellent capacity and improved performance. It has good capacity retention.

In this embodiment, during the mixing step, the M-containing oxide is optionally mixed with at least one of Co ₃ O ₄ , Co ₂ O ₃ and CoO, at least one of CuO and Cu ₂ O, 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, the oxide mixture containing cobalt, copper, and tin may optionally contain element M. The atomic ratio of M is 10 atomic % or less based on the total number of atoms of metal elements in the oxide mixture containing cobalt, copper, and tin. In addition, compared to an oxide mixture containing cobalt, copper, and tin that is not mixed with an oxide containing M, the oxide mixture containing M 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 increased electrical conductivity by about 8% or more. Note that in this embodiment, the numerical value of the atomic ratio of elements in the oxide mixture containing cobalt, copper, and tin may have an error of ±10% due to the formation of oxygen vacancies or nonuniform diffusion. be.

In this embodiment, by forming the anode using an anode material containing an oxide mixture containing cobalt, copper, and tin, lithium ions can enter and exit through different routes, and the polarization effect can be reduced. , the charge/discharge cycle life can be improved. As a result, the capacity of a secondary battery using an anode material containing an oxide mixture containing cobalt, copper, and tin can be significantly increased. In addition, 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 has good lithium ion conductivity. Therefore, a secondary battery using an anode material containing an oxide mixture obtained by a mixing process of cobalt oxide, copper oxide, and tin oxide has excellent performance and safety.

Oxide mixture containing silicon, tin, and iron In the present embodiment, the oxide mixture containing silicon, tin, and iron includes SiO ₂ and at least one of SiO, SnO and at least one of SnO ₂ , and Fe. It can be obtained by performing a step of mixing at least one of ₂ O ₃ , Fe ₃ O ₄ 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. Furthermore, in this embodiment, the atomic ratio of silicon, tin, and iron in the oxide mixture containing silicon, tin, and iron is 4:1:16, 1:1:1, or 4:1:1. obtain. If the atomic ratios of silicon, tin, and iron meet the specific ratios mentioned above, a secondary battery using an anode material containing an oxide mixture containing silicon, tin, and iron will have excellent capacity and improved performance. It has good capacity retention.

In this embodiment, during the mixing step, the M-containing oxide is optionally mixed with SiO ₂ and at least one of SiO, SnO and at least one of SnO ₂ , and Fe ₂ O ₃ , Fe ₃ O ₄ 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, the oxide mixture containing silicon, tin, and iron may optionally contain element M. The atomic ratio of M is 10 atomic % or less based on the total number of atoms of elements other than oxygen in the oxide mixture containing silicon, tin, and iron. In addition, compared to an oxide mixture containing silicon, tin, and iron that is not mixed with an oxide containing M, the oxide mixture containing M 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 increased electrical conductivity by about 10% or more. Note that in this embodiment, the numerical value of the atomic ratio 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 nonuniform diffusion. be.

In this embodiment, by forming the anode using an anode material containing an oxide mixture containing silicon, tin, and iron, lithium ions can enter and exit through different routes, and the polarization effect can be reduced. , the charge/discharge cycle life can be improved. As a result, the capacity of a secondary battery using an anode material containing an oxide mixture containing silicon, tin, and iron can be significantly increased. 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 has good lithium ion conductivity. Therefore, a secondary battery using an anode material containing an oxide mixture obtained by a mixing process of silicon oxide, tin oxide, and iron oxide has excellent performance and safety.

Oxide mixture containing copper, manganese, and silicon In this embodiment, the oxide mixture containing copper, manganese, and silicon includes at least one of CuO and Cu ₂ O, at least one of SiO ₂ 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. Furthermore, in this embodiment, the atomic ratio of copper, manganese, and silicon in the oxide mixture containing copper, manganese, and silicon is 1:1:1, 1:4:1, 4:1:1, or 1. :1:4. If the atomic ratios of copper, manganese, and silicon meet the specific ratios mentioned above, a secondary battery using an anode material containing an oxide mixture containing copper, manganese, and silicon will have excellent capacity and improved performance. It has good capacity retention.

In this embodiment, during the mixing step, the M-containing oxide is optionally mixed with at least one of CuO and Cu ₂ O, at least one of SiO ₂ and SiO, and MnO, MnO ₂ , Mn ₂ O ₃ and Mn ₃ O ₄ . 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, the oxide mixture containing copper, manganese, and silicon may optionally contain element M. The atomic ratio of M is 10 atomic % or less based on the total number of atoms of elements other than oxygen in the oxide mixture containing copper, manganese, and silicon. In addition, compared to an oxide mixture containing copper, manganese, and silicon that is not mixed with an oxide containing M, the oxide mixture containing M 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. In addition, in this embodiment, the numerical value of the atomic ratio 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, an oxide mixture containing copper, manganese, and silicon obtained by performing a mixing step of copper oxide, manganese oxide, and silicon oxide has a synergistic effect due to the interaction of multiple oxides, and copper, The capacity of a secondary battery to which an anode material containing an oxide mixture containing manganese and silicon is applied is significantly increased. Furthermore, in this embodiment, by forming the anode using an anode material containing an oxide mixture containing copper, manganese, and silicon, lithium ions can enter and exit through different routes, reducing the polarization effect. It is possible to improve the charge/discharge cycle life. Additionally, 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. Therefore, a secondary battery using an anode material including an oxide mixture obtained by a mixing process of copper oxide, manganese oxide, and silicon oxide has excellent performance and safety.

Oxide mixture containing tin, manganese, and nickel In this embodiment, the oxide mixture containing tin, manganese, and nickel includes 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. Furthermore, in this embodiment, the atomic ratio of tin, manganese, and nickel in the oxide mixture containing tin, manganese, and nickel is 1:2:1, 1:1:1, 1:1:2, or 2. :1:1. If the atomic ratio of tin, manganese, and nickel meets the above specific ratio, the secondary battery to which the anode material containing the oxide mixture containing tin, manganese, and nickel is applied has excellent capacity and improvement. It has excellent capacity retention.

In this embodiment, during the mixing step, the M-containing oxide is optionally mixed with at least one of SnO and SnO ₂ , at least one of MnO, MnO ₂ , Mn ₂ O ₃ and Mn ₃ O ₄ , 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, the oxide mixture containing tin, manganese, and nickel may optionally contain element M. The atomic ratio of M is 10 atomic % or less based on the total number of atoms of metal elements in the oxide mixture containing tin, manganese, and nickel. In addition, compared to an oxide mixture containing tin, manganese, and nickel that is not mixed with an oxide containing M, the oxide mixture containing M 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. In addition, in this embodiment, the numerical value of the atomic ratio 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 uneven diffusion. be.

In this embodiment, the oxide mixture containing tin, manganese, and nickel obtained by performing the mixing step of tin oxide, manganese oxide, and nickel oxide has 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 significantly increased. Furthermore, in this embodiment, by forming the anode using an anode material containing an oxide mixture containing tin, manganese, and nickel, lithium ions can enter and exit through different routes, reducing the polarization effect. It is possible to improve the charge/discharge cycle life. In addition, tin oxide used as an anode material can achieve high capacity performance, manganese oxide used as an anode material can achieve low overvoltage, and nickel oxide used as an 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 containing manganese, copper, and nickel In this embodiment, the oxide mixture containing manganese, copper, and nickel contains at least one of MnO, MnO ₂ , Mn ₂ O ₃ and Mn ₃ O ₄ , 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. Furthermore, in this embodiment, the atomic ratio of manganese, copper, and nickel in the oxide mixture containing manganese, copper, and nickel is 3:2:1, 2:1:1, or 1:1:1. obtain. If the atomic ratio of manganese, copper, and nickel meets the above specific ratio, the secondary battery to which the anode material containing the oxide mixture containing manganese, copper, and nickel is applied has excellent capacity and improvement. It has excellent capacity retention.

In this embodiment, during the mixing step, the M-containing oxide _{is optionally mixed with 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, the oxide mixture containing manganese, copper, and nickel may optionally contain element M. The atomic ratio of M is 10 atomic % or less based on the total number of atoms of metal elements in the oxide mixture containing manganese, copper, and tin. In addition, 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. Note that in this embodiment, the numerical value of the atomic ratio of elements in the oxide mixture containing manganese, copper, and nickel may have an error of ±10% due to the formation of oxygen vacancies or uneven diffusion. be.

In this embodiment, by forming the anode using an anode material containing an oxide mixture containing manganese, copper, and nickel, lithium ions can enter and exit through different routes, and the polarization effect can be reduced. , the charge/discharge cycle life can be improved. In addition, 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. A secondary battery using an anode material containing an oxide mixture obtained by a mixing process of , manganese oxide, copper oxide, and nickel oxide has excellent performance and safety.

Oxide mixture containing nickel, copper, and tin In this embodiment, the oxide mixture containing nickel, copper, and tin includes at least one of Ni ₂ O ₃ and NiO, at least one of CuO and Cu ₂ O, It can be obtained 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. Furthermore, in this embodiment, the atomic ratio of nickel, copper, and tin in the oxide mixture containing nickel, copper, and tin is 1:1:2, 2:1:3, or 1:2:3. obtain. If the atomic ratios of nickel, copper, and tin meet the specific ratios mentioned above, a secondary battery using an anode material containing an oxide mixture containing nickel, copper, and tin will have excellent capacity and improved performance. It has good capacity retention.

In this embodiment, during the mixing step, the M- _containing oxide is optionally mixed with 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, the oxide mixture containing nickel, copper, and tin may optionally contain element M. The atomic ratio of M is 10 atomic % or less based on the total number of atoms of metal elements in the oxide mixture containing nickel, copper, and tin. In addition, compared to an oxide mixture containing nickel, copper, and tin that is not mixed with an oxide containing M, the oxide mixture containing M 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. In addition, in this embodiment, the numerical value of the atomic ratio 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, by forming the anode using an anode material containing an oxide mixture containing nickel, copper, and tin, lithium ions can enter and exit through different routes, and the polarization effect can be reduced. , the charge/discharge cycle life can be improved. As a result, the capacity of a secondary battery using an anode material containing an oxide mixture containing nickel, copper, and tin can be significantly increased. In addition, tin oxide used as anode material can achieve high capacity performance, copper oxide used as anode material can achieve good cycle life, and nickel oxide used as anode material has good lithium ion conductivity. Therefore, a secondary battery using an anode material containing an oxide mixture obtained by a mixing process of nickel oxide, copper oxide, and tin oxide 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 an embodiment of the present invention. Referring to FIG. 1, a secondary battery 100 may include an anode 102, a cathode 104, an electrolyte 108, and a packaging 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 about 5 μm to about 300 μm.

In this embodiment, the anode material layer 102b includes any of the anode materials proposed in the embodiments above. In this embodiment, the anode material can be disposed on the current collector 102a by, for example, coating, sputtering, hot pressing, sintering, physical vapor deposition, or chemical vapor deposition. Further, in this embodiment, the anode material layer 102b may further include a conductive agent and a binder. In this 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. In particular, conductive agents are used to improve electrical contact between molecules of the anode material. In this embodiment, the binder may be polyvinylidene fluoride (PVDF), styrene butadiene rubber (SBR), polyamide, melamine resin, or a combination 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, cathode 104 includes a current collector 104a and a cathode material layer 104b disposed on 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 about 5 μm to about 300 μm.

In this embodiment, cathode material layer 104b includes cathode material. In this embodiment, the cathode material includes lithium cobalt oxide (LiCoO ₂ ), lithium manganate (LiMn ₂ O ₄ ), lithium nickel oxide (LiNiO ₂ ), lithium iron phosphate (LiFePO ₄ ), or a combination thereof. obtain. In this embodiment, the cathode material can be disposed on the 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 a combination thereof. Specifically, the cathode material may be adhered to 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 disposed between anode 102 and cathode 104, separator 106, anode 102, and cathode 104 define a containment region 110 in the storage system, and electrolyte 108 is disposed in containment region 110. It is located. In this embodiment, the material of the separator 106 may be an insulating material such as polyethylene (PE) or polypropylene (PP), or a composite structure made of these materials (for example, PE/PP/PE).

In this embodiment, the secondary battery 100 includes a separator 106 that separates the anode 102 from the cathode 104 and allows ions to pass therethrough, but the present invention is not limited thereto. 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. 1. In other embodiments, the secondary battery 100 may have a roll-type structure in which an anode, a cathode, and an optional separator are wound, or a laminated structure formed by laminating flat layers. . Further, in this embodiment, the secondary battery 100 is, for example, a paper type battery, a button type battery, a coin type 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. can have a cycle life.

The features of the invention are described in more detail below with reference to Examples 1-14 and Comparative Examples 1-9. Examples 1-14 are described below; however, the materials used, their respective amounts and ratios, detailed process flows, etc. may be modified as appropriate without departing from the scope of this disclosure. can. Therefore, the scope of the present disclosure should not be limited by the following embodiments.

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

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

The anode of Example 1 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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 has been prepared.

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

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

The anode of Example 2 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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 has been prepared.

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

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

The anode of Example 3 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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 At room temperature, use a ball mill to prepare CoO powder (cobalt oxide), CuO powder (copper oxide), _SnO2 powder (tin oxide), and W oxide powder (oxide containing element M). ) was ground and mixed to obtain an oxide mixture containing cobalt, copper, and tin (i.e., 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 binder (i.e. sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. The zirconia balls were then added and mixed for approximately 30 minutes to form an anode slurry. Next, using a spatula (100 μm), the slurry was evenly applied to the copper foil (the above current collector), and then the copper foil coated with the slurry was placed in a vacuum oven at about 110°C. It was dried for about 12 hours. Thereafter, the dried copper foil was cut into the anode of Example 4 with a diameter of about 12.8 mm using a cutting machine.

The anode of Example 4 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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, SiO ₂ powder (silicon-containing precursor), SnO ₂ powder (tin-containing precursor), Fe ₂ O ₃ powder (iron-containing precursor), TiO ₂ The powder (precursor containing element M) was ground, and the resulting powder was mixed and pressed into green pellets with a diameter of about 1 cm. The green pellets were placed in a high temperature furnace to obtain a bulk material of silicon-tin-iron oxide represented by the above formula (4) (ie, the anode material of Example 4). Here, x4 is 21, element M is Ti, the atomic ratio of element M is 10 at% 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 finely ground anode material of Example 5, Super P conductive carbon and binder (i.e. sodium carboxymethylcellulose (CMC) dissolved in water) were mixed in a 7:2:1 weight ratio. mixed in ratio. The zirconia balls were then added and mixed for approximately 30 minutes to form an anode slurry. Next, using a spatula (100 μm), the slurry was evenly applied to the copper foil (the above current collector), and then the copper foil coated with the slurry was placed in a vacuum oven at about 110°C. It was dried for about 12 hours. The dried copper foil was then cut into the anode of Example 5 with a diameter of about 12.8 mm using a cutting machine.

The anode of Example 5 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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, SiO ₂ powder (silicon oxide), SnO ₂ powder (tin oxide), Fe ₂ O ₃ powder (iron oxide), TiO ₂ 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.

Preparation of Secondary Battery The anode material of Example 6, Super P conductive carbon and binder (i.e. sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. The zirconia balls were then added and mixed for approximately 30 minutes to form an anode slurry. Next, using a spatula (100 μm), the slurry was evenly applied to the copper foil (the above current collector), and then the copper foil coated with the slurry was placed in a vacuum oven at about 110°C. It was dried for about 12 hours. Thereafter, the dried copper foil was cut into the anode of Example 6 with a diameter of about 12.8 mm using a cutting machine.

The anode of Example 6 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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 At room temperature, using a ball mill, CuO powder (precursor containing copper), MnO powder (precursor containing manganese), SiO ₂ powder (precursor containing silicon), and TiO ₂ powder (element The resulting powder was mixed and pressed into green pellets with a diameter of about 1 cm. The green pellets were placed in a high temperature furnace to obtain a bulk material of copper-manganese-silicon oxide represented by the above formula (7) (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 at% 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 and finely ground anode material of Example 7, Super P conductive carbon and binder (i.e. sodium carboxymethylcellulose (CMC) dissolved in water) were mixed in a 7:2:1 weight ratio. mixed in ratio. The zirconia balls were then added and mixed for approximately 30 minutes to form an anode slurry. Next, using a spatula (100 μm), the slurry was evenly applied to the copper foil (the above current collector), and then the copper foil coated with the slurry was placed in a vacuum oven at about 110°C. It was dried for about 12 hours. The dried copper foil was then cut into the anode of Example 7 with a diameter of about 12.8 mm using a cutting machine.

The anode of Example 7 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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 Grind and mix CuO powder (copper oxide), MnO powder (manganese oxide), _SiO2 powder (silicon oxide), _TiO2 powder (oxide containing element M) using a ball mill at room temperature. An oxide mixture containing copper, manganese and silicon was obtained (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 (i.e. sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. The zirconia balls were then added and mixed for approximately 30 minutes to form an anode slurry. Next, using a spatula (100 μm), the slurry was evenly applied to the copper foil (the above current collector), and then the copper foil coated with the slurry was placed in a vacuum oven at about 110°C. It was dried for about 12 hours. The dried copper foil was then cut into the anode of Example 8 with a diameter of about 12.8 mm using a cutting machine.

The anode of Example 8 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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, SnO ₂ powder (tin-containing precursor), MnO ₂ powder (manganese-containing precursor), NiO powder (nickel-containing precursor), Mo oxide powder ( A precursor containing element M) was ground, and the resulting powder was mixed and pressed into green pellets with a diameter of about 1 cm. The green pellets were placed in a high temperature furnace to obtain a bulk material of tin-manganese-nickel oxide represented by the above formula (8) (ie, the anode material of Example 9). Here, x8 is 7, element M is Mo, the atomic ratio of element M is 10 at% or less, and the average particle size of the tin-manganese-nickel oxide is about 0.1 μm to about 10 μm. range.

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

The anode of Example 9 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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 Grind _SnO2 powder (tin oxide), _MnO2 powder (manganese oxide), NiO powder (nickel oxide), Mo oxide powder (oxide containing element M) using a ball mill at room temperature. - Mixed to obtain an oxide mixture containing tin, manganese and nickel (i.e. 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.

Preparation of Secondary Battery The anode material of Example 10, Super P conductive carbon and binder (i.e. sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. The zirconia balls were then added and mixed for approximately 30 minutes to form an anode slurry. Next, using a spatula (100 μm), the slurry was evenly applied to the copper foil (the above current collector), and then the copper foil coated with the slurry was placed in a vacuum oven at about 110°C. It was dried for about 12 hours. Thereafter, the dried copper foil was cut into the anode of Example 10 with a diameter of about 12.8 mm using a cutting machine.

The anode of Example 10 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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 At room temperature, using a ball mill, _MnO2 powder (precursor containing manganese), CuO powder (precursor containing copper), NiO powder (precursor containing nickel), Mo oxide powder (precursor containing elemental The resulting powder was mixed and pressed into green pellets with a diameter of about 1 cm. The green pellets were placed in a high temperature furnace to obtain a bulk material of manganese-copper-nickel oxide represented by the above formula (13) (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.

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

The anode of Example 11 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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, use a ball mill to crush and crush _MnO2 powder (manganese oxide), CuO powder (copper oxide), NiO powder (nickel oxide), Mo oxide powder (oxide containing element M). Mixing resulted in an oxide mixture containing manganese, copper, and nickel (i.e., 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.

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

The anode of Example 12 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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 At room temperature, use a ball mill to grind NiO powder (nickel oxide), CuO powder (copper oxide), _SnO2 powder (tin oxide), and W oxide powder (oxide containing element M). - Mixed to obtain an oxide mixture containing nickel, copper and tin (i.e. the anode material of Example 13). The atomic ratio of nickel, copper, and tin is 1:1:2, 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 13, Super P conductive carbon and binder (i.e. sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. The zirconia balls were then added and mixed for approximately 30 minutes to form an anode slurry. Next, using a spatula (100 μm), the slurry was evenly applied to the copper foil (the above current collector), and then the copper foil coated with the slurry was placed in a vacuum oven at about 110°C. It was dried for about 12 hours. Thereafter, the dried copper foil was cut into the anode of Example 13 with a diameter of about 12.8 mm using a cutting machine.

The anode of Example 13 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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 At room temperature, using a ball mill, NiO powder (nickel-containing precursor), CuO powder (copper-containing precursor), _SnO2 powder (tin-containing precursor), W oxide powder (element The resulting powder was mixed and pressed into green pellets with a diameter of about 1 cm. The green pellets were placed in a high temperature furnace to obtain a bulk material of nickel-copper-tin oxide represented by the above formula (15) (ie, the anode material of Example 14). Here, x15 is 6, element M is W, the atomic ratio of element M is 10 at% or less, and the average particle size of the nickel-copper-tin oxide is about 0.1 μm to about 10 μm. range.

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

The anode of Example 14 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ added to an organic solvent was used as the electrolyte, polypropylene film (trade name: Celgard #2400, manufactured by Celgard) was used as the separator, and stainless steel 304 was used 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 using the same manufacturing procedure as in Example 1. The main difference between the secondary battery of Comparative Example 1 and the secondary battery of Example 1 is that in the secondary battery of Example 1, the working electrode is the anode of Example 1; In this case, the material of the working electrode is Co ₂ SnO ₄ .

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

Comparative example 3
Preparation of secondary battery A secondary battery of Comparative Example 3 was prepared using the same manufacturing procedure as in Example 1. The main difference between the secondary battery of Comparative Example 3 and the secondary battery of Example 1 is that in the secondary battery of Example 1, the working electrode is the anode of Example 1; In this case, the material of the working electrode is CuO.

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

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

Comparative example 6
Preparation of Secondary Battery A secondary battery of Comparative Example 6 was prepared using the same manufacturing procedure as in Example 1. The main difference between the secondary battery of Comparative Example 6 and the secondary battery of Example 1 is that in the secondary battery of Example 1, the working electrode is the anode of Example 1; In this case, 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 using the same manufacturing procedure as in Example 1. The main difference between the secondary battery of Comparative Example 7 and the secondary battery of Example 1 is that in the secondary battery of Example 1, the working electrode is the anode of Example 1; In this case, the material of the working electrode is MnO.

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

Comparative example 9
Preparation of secondary battery A secondary battery of Comparative Example 9 was prepared using the same manufacturing procedure as in Example 1. The main difference between the secondary battery of Comparative Example 9 and the secondary battery of Example 1 is that in the secondary battery of Example 1, the working electrode is the anode of Example 1; In this case, 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, charging and discharging cycles were performed for each of the secondary batteries of Examples 1 to 14 and the secondary batteries of Comparative Examples 1 to 9. The test was conducted.

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 at a voltage of 0.01 V to 3 V and in an environment of about 15° C. to about 30° C. The test was conducted. The measurement results are shown in Figures 2-15.

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

Although the above-mentioned test was not conducted on a secondary battery containing a cobalt-copper-tin oxide represented by formula (1) and where x1 is 9 or 14, the above-mentioned secondary battery containing a cobalt-copper-tin oxide According to the description and the test results of Example 1, those skilled in the art can understand that the secondary battery containing the cobalt-copper-tin oxide represented by formula (1) and in which x1 is 9 or 14 has good capacity and capacity retention. It should be understood that it can have a sexual nature.

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

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

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

The above tests were not conducted on secondary batteries containing oxide mixtures containing cobalt, copper and tin, with an atomic ratio of cobalt, copper and tin of 5:1:3 or 2:1:1. According to the above description of the oxide mixture containing cobalt, copper and tin and the test results of Example 4, one skilled in the art can understand that the oxide mixture containing cobalt, copper and tin has an atomic ratio of cobalt, copper and tin of 5:1. It should be understood that secondary batteries comprising oxide mixtures that are: 3:3 or 2:1:1 may have good capacity and capacity retention.

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

Although the above-mentioned test was not conducted on a secondary battery containing a silicon-tin-iron oxide represented by formula (4), where x4 is greater than 21 and less than or equal to 34, According to the above explanation and the test results of Example 5, those skilled in the art will find that a secondary battery containing a silicon-tin-iron oxide represented by formula (4) and in which x4 is greater than 21 and less than or equal to 34 is good. It should be understood that the capacitance and capacity retention properties can be increased.

Although the above-mentioned test was not performed on a secondary battery containing silicon-tin-iron oxide represented by formula (5) or (6), the above-mentioned description and implementation of silicon-tin-iron oxide According to the test results of Example 5, those skilled in the art can understand that the secondary battery containing silicon-tin-iron oxide represented by formula (5) or (6) can have good capacity and capacity retention. You should understand that.

Although secondary batteries containing oxide mixtures containing silicon, tin, and iron with an atomic ratio of silicon, tin, and iron of 1:1:1 or 4:1:1, the aforementioned tests were not conducted. According to the above description of the oxide mixture containing , silicon, tin and iron and the test results of Example 6, one skilled in the art can understand that the oxide mixture containing silicon, tin and iron has an atomic ratio of silicon, tin and iron of 1:1. It should be understood that secondary batteries comprising oxide mixtures that are: 1:1 or 4:1:1 may 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-mentioned test was not conducted on a secondary battery containing a copper-manganese-silicon oxide represented by formula (7), where x7 is greater than 0 and less than 1; According to the explanation and the test results of Example 7, those skilled in the art can understand that a secondary battery containing a copper-manganese-silicon oxide represented by formula (7), where x7 is greater than 0 and smaller 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, with an atomic ratio of copper, manganese and silicon of 1:1:1, 4:1:1 or 1:1:4, the above-mentioned test However, according to the above 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 oxide mixture containing copper, manganese and silicon It should be understood that secondary batteries comprising oxide mixtures with an atomic ratio of 1:1:1, 4:1:1 or 1:1:4 may have good capacity and capacity retention. .

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

Although the above-mentioned test was not conducted on a secondary battery containing a tin-manganese-nickel oxide represented by formula (8), where x8 is 4 or more and smaller than 7, According to the description and the test results of Example 9, those skilled in the art can understand that a secondary battery containing tin-manganese-nickel oxide represented by formula (8) and in which x8 is 4 or more and smaller than 7 has good capacity and capacity. It should be understood that it may have retentive properties.

Although the above-mentioned test was not conducted on the secondary battery containing tin-manganese-nickel oxide represented by formula (9), (10) or (11), According to the explanation and the test results of Example 9, those skilled in the art can understand that the secondary battery containing tin-manganese-nickel oxide represented by formula (9), (10) or (11) has good capacity. and capacity retention.

For secondary batteries containing oxide mixtures containing tin, manganese and nickel, with an atomic ratio of tin, manganese and nickel of 1:1:1, 1:1:2 or 2:1:1, the above test However, according to the above 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 the oxide mixture containing tin, manganese and nickel It should be understood that secondary batteries comprising oxide mixtures with an atomic ratio of 1:1:1, 1:1:2 or 2:1:1 may 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).

Although the above-mentioned test was not performed on the secondary battery containing the manganese-copper-nickel oxide represented by formula (12) or (14), the above-mentioned explanation and implementation of the manganese-copper-nickel oxide According to the test results of Example 11, those skilled in the art can understand that the secondary battery containing manganese-copper-nickel oxide represented by formula (12) or (14) can have good capacity and capacity retention. You should understand that.

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.

The above tests were not conducted for secondary batteries containing oxide mixtures containing manganese, copper and nickel, with an atomic ratio of manganese, copper and nickel of 3:2:1 or 1:1:1. According to the above description of the oxide mixture containing , manganese, copper and nickel and the test results of Example 12, one skilled in the art can understand that the oxide mixture containing manganese, copper and nickel has an atomic ratio of 3:2 of manganese, copper and nickel. It should be understood that secondary batteries comprising oxide mixtures that are: 1:1 or 1:1:1 may 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.

The aforementioned tests were not conducted for secondary batteries containing oxide mixtures containing nickel, copper, and tin, with an atomic ratio of nickel, copper, and tin of 2:1:3 or 1:2:3. According to the above description of the oxide mixture containing nickel, copper and tin and the test results of Example 13, one skilled in the art can understand that the oxide mixture containing nickel, copper and tin has an atomic ratio of nickel, copper and tin of 2:1. It should be understood that a secondary battery comprising an oxide mixture that is 1:3 or 1:2:3 may 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 conducted on a secondary battery containing a nickel-copper-tin oxide represented by formula (15), where x15 is 3 or 9; According to the description and the test results of Example 14, those skilled in the art can understand that the secondary battery containing the nickel-copper-tin oxide represented by formula (15) and in which x15 is 3 or 9 has good capacity and capacity retention. It should be understood that it can have a sexual nature.

Although the above-mentioned test was not conducted on a secondary battery containing the nickel-copper-tin oxide represented by formula (16) or formula (17), the above-mentioned description and implementation of the nickel-copper-tin oxide According to the test results of Example 14, those skilled in the art can understand that the secondary battery containing the nickel-copper-tin oxide represented by formula (16) or formula (17) can have good capacity and capacity retention. You should understand that.

From the above test results, it has been found that by producing an anode using the anode material for secondary batteries of the present invention, a secondary battery to which the anode is applied has good capacity, stability, and charge/discharge cycle life. It has been confirmed that you can get it.

In addition, since a secondary battery using an anode made of the anode material for secondary batteries of the present invention has a larger capacity than commercially available graphite (theoretical capacity value 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 may 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 foregoing detailed description.

According to the disclosure herein, the anode material and anode of the present invention can be applied to a secondary battery, and as a result, the capacity and stability of the secondary battery are improved.

100: Secondary battery 102: Anode 102a, 104a: Current collector 102b: Anode material layer 104: Cathode 104b: Cathode material layer 106: Separator 108: Electrolyte 110: Accommodation area 112: Package structure

Claims (5)

An oxide mixture formed by mixing at least one of SiO ₂ and SiO, at least one of SnO and SnO ₂ , and at least one of Fe ₂ O ₃ , Fe ₃ O ₄ and FeO, the oxide mixture An anode material for a secondary battery, comprising an oxide mixture in which the atomic ratio of silicon, tin, and iron is 4:1:16, 1:1:1, or 4:1:1. The oxide mixture further includes an oxide containing M, where M is at least one element selected from the group consisting of Cr, Mn, Zn, Al, Ti, In, Mo, and W, and an atom of M The anode material for a secondary battery according to claim 1, wherein the ratio is 10 at % or less based on the total number of atoms of elements other than oxygen in the oxide mixture. An anode for a secondary battery, comprising: a current collector; and an anode material layer disposed on the current collector and comprising the anode material for a secondary battery according to claim 1. cathode;
An anode disposed separately from the cathode, the anode being the anode for a secondary battery according to claim 3;
A secondary battery comprising: an electrolyte provided between the cathode and the anode; and a package structure that packs the cathode, the anode, and the electrolyte. further comprising a separator disposed between the cathode and the anode,
the separator, the cathode and the anode define a containment area of a storage system;
The secondary battery according to claim 4, wherein the electrolyte is arranged in the storage area.