CN114725373B - Negative electrode material for secondary battery, negative electrode, and secondary battery - Google Patents

Abstract

The invention provides a negative electrode material for a secondary battery, a negative electrode and a secondary battery. The negative electrode material for a secondary battery of the present invention comprises a metal oxide containing four or more elements or an oxide mixture containing four or more elements. The metal oxide includes cobalt copper tin oxide, silicon tin iron oxide, copper manganese silicon oxide, tin manganese nickel oxide, manganese copper nickel oxide, or nickel copper tin oxide. The oxide mixture includes an oxide mixture containing cobalt, copper and tin, an oxide mixture containing silicon, tin and iron, an oxide mixture containing copper, manganese and silicon, an oxide mixture containing tin, manganese and nickel, an oxide mixture containing manganese, copper and nickel, or an oxide mixture containing nickel, copper and tin. The negative electrode material for a secondary battery of the present invention provides a secondary battery with good capacity and stability.

Description

Negative electrode materials for secondary batteries, negative electrodes and secondary batteries

This invention is a divisional application of the invention patent application filed on January 16, 2020 with the application number 202010057891.

Technical field

The present invention relates to an electrode material, an electrode and a battery, and in particular to a negative electrode material for a secondary battery, a negative electrode for a secondary battery and a secondary battery.

Background technique

In recent years, the market demand for secondary lithium batteries that can be repeatedly charged and discharged and have the characteristics of light weight, high voltage value and high energy density has been increasing day by day. Therefore, today's requirements for secondary lithium batteries such as lightweight, durable, high voltage, high energy density and high safety are becoming increasingly high. The application and expansion potential of secondary lithium batteries, especially in light electric vehicles, electric vehicles, and large-scale power storage industries, is quite high. Generally, the most common commercial electrode material is graphite, but the capacitance of graphite (theoretical value is 372mAh/g) is low, so the performance of batteries made from it is limited. Therefore, finding an electrode material for secondary batteries with high stability and high capacity is currently one of the goals that those skilled in the field want to achieve.

Contents of the invention

In view of this, the present invention provides a negative electrode material and a negative electrode that are used in secondary batteries and enable the secondary batteries to have good capacitance and stability.

An embodiment of the present invention provides a negative electrode material for a secondary battery including cobalt copper tin oxide represented by one 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),

Where x1 is 8, 9 or 14, x2 is 4, 6 or 8, x3 is 3, 4 or 5, M is at least one selected from Ni, Cr, Mn, Zn, Al, Ti, In, Mo and W element, and the atomic number ratio of M is 10 atomic% or less relative to the total number of atoms of the metal elements in the cobalt copper tin oxide represented by formula (1), formula (2) or formula (3).

Another embodiment of the present invention provides a negative electrode material for a secondary battery including Co ₃ O ₄ , at least one of Co ₂ O ₃ and CoO, at least one of CuO and Cu ₂ O, and SnO and SnO ₂ An oxide mixture obtained by performing a mixing step on at least one of the oxide mixtures, wherein the atomic ratio of cobalt, copper and tin in the oxide mixture is 5:1:3, 2:1:1 or 1:1:1 .

Another embodiment of the present invention provides a negative electrode material for a secondary battery including silicon tin iron oxide represented by one 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),

Where x4 is 21 to 34, x4 is 3 to 5, x6 is 6 to 11.5, M is at least one element selected from Cr, Mn, Zn, Al, Ti, In, Mo and W, and relative to the formula ( 4) The total number of atoms of elements other than oxygen in the silicon-tin-iron oxide represented by formula (5) or formula (6), and the atomic number ratio of M is 10 atomic% or less.

Another embodiment of the present invention provides a negative electrode material for a secondary battery including at least one of SiO ₂ and SiO, at least one of SnO and SnO ₂ , and one of Fe ₂ O ₃ , Fe ₃ O ₄ and FeO. The oxide mixture obtained by performing the mixing step on at least one of the oxide mixtures, wherein the atomic ratio of silicon, tin and iron in the oxide mixture is 4:1:16, 1:1:1 or 4:1:1.

Another embodiment of the present invention provides a negative electrode material for secondary batteries including copper manganese silicon oxide represented by the following formula (7):

Cu _x7 Mn _7-x7 SiMO ₁₂ formula (7),

where x7 is greater than 0 and less than or equal to 1, M is at least one element selected from Cr, Sn, Ni, Co, Zn, Al, Ti, In, Mo and W, and relative to the formula (7) The total atomic number of elements other than oxygen in the copper-manganese-silicon oxide and the atomic number ratio of M are 10 atomic% or less.

Another embodiment of the present invention provides a negative electrode material for a secondary battery including 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 An oxide mixture obtained by subjecting at least one of ₃ O ₄ to a mixing step, wherein the atomic ratios of copper, manganese and silicon in the oxide mixture are 1:1:1, 1:4:1, 4: 1:1 or 1:1:4.

Another embodiment of the present invention provides a negative electrode material for secondary batteries including tin manganese nickel oxide represented by one of the following formulas (8) to formula (11):

Sn ₁ Mn ₂ Ni ₁ MO _x8Equation (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 _x11Equation (11),

Where x8 is 4 to 7, x9 is 4 to 7, x10 is 4 to 7, x11 is 3 to 6, and M is at least one element selected from Cr, Mn, Zn, Al, Ti, In, Mo and W , and the atomic number ratio of M is 10atomic% or less relative to the total number of atoms of metal elements in the tin-manganese nickel oxide represented by formula (8), formula (9), formula (10) or formula (11).

Another embodiment of the present invention provides a negative electrode material for a secondary battery including 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 subjecting at least one of Ni ₂ O ₃ to a mixing step, wherein the atomic ratios of tin, manganese and nickel in the oxide mixture are 1:2:1, 1:1:1, 1 :1:2 or 2:1:1.

Another embodiment of the present invention provides a negative electrode material for a secondary battery including manganese copper nickel oxide represented by one 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),

Wherein M is at least one element selected from Fe, Cr, Zn, Al, Ti, In, Mo, W and Si, and relative to the manganese represented by formula (12), formula (13) or formula (14) The total atomic number of metal elements in the copper-nickel oxide and the atomic number ratio of M are 10 atomic% or less.

Another embodiment of the present invention provides a negative electrode material for a secondary battery including 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 An oxide mixture obtained by performing a mixing step with at least one of Ni ₂ O ₃ , wherein the atomic ratio of manganese, copper and nickel in the oxide mixture is 3:2:1, 2:1:1 or 1:1:1.

Another embodiment of the present invention provides a negative electrode material for a secondary battery including nickel copper tin oxide represented by one of the following formulas (15) to (17):

NiCuSn ₂ MO _x15 formula (15),

Ni ₂ CuSn ₃ MO _x16 formula (16),

NiCu ₂ Sn ₃ MO _x17 formula (17),

Where x15 is 3, 6 or 9, x16 is 4, 6 or 9, x17 is 4, 6 or 9, M is at least one selected from Cr, Mn, Zn, Al, Ti, In, Mo, W and Co element, and the atomic number ratio of M is 10 atomic% or less relative to the total number of atoms of metal elements in the nickel copper tin oxide represented by formula (15), formula (16) or formula (17).

Another embodiment of the present invention provides a negative electrode material for a secondary battery including at least one of Ni ₂ O ₃ and NiO, at least one of CuO and Cu ₂ O, and at least one of SnO and SnO ₂ The oxide mixture obtained by performing the mixing step, wherein the atomic ratio of cobalt, copper and tin in the oxide mixture is 1:1:2, 2:1:3 or 1:2:3.

An embodiment of the present invention provides a negative electrode for a secondary battery including a current collector and a negative electrode material layer. The negative electrode material layer is disposed on the current collector and includes any of the above-mentioned negative electrode materials for secondary batteries.

A secondary battery provided by an embodiment of the present invention includes a positive electrode, a negative electrode, an electrolyte and a packaging structure. The negative electrode and the positive electrode are arranged separately, and the negative electrode is the negative electrode for a secondary battery as described above. The electrolyte is placed between the positive electrode and the negative electrode. The packaging structure covers the positive electrode, negative electrode and electrolyte.

Based on the above, the negative electrode material for secondary batteries of the present invention includes a metal oxide represented by one of the formulas (1) to (17), or includes cobalt, copper and tin with a specific ratio of atomic numbers of elements. or The oxide mixture containing nickel, copper and tin can be used in secondary batteries, and the secondary batteries have good capacity, stability and charge and discharge cycle life.

In order to make the above-mentioned features and advantages of the present invention more obvious and understandable, the following embodiments are specifically described in detail with reference to the accompanying drawings.

Description of the drawings

The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.

Figure 1 is a schematic cross-sectional view of a secondary battery according to an embodiment of the present invention;

Figure 2 is a cycle life curve diagram of the secondary batteries of Example 1 and Comparative Example 1;

Figure 3 is a cycle life curve diagram of the secondary batteries of Example 2 and Comparative Example 1;

Figure 4 is a cycle life curve diagram of the secondary batteries of Example 3 and Comparative Example 1;

Figure 5 is a cycle life curve diagram of the secondary batteries of Example 4 and Comparative Examples 2 to 4;

Figure 6 is a cycle life curve diagram of the secondary batteries of Example 5 and Comparative Examples 4 to 6;

Figure 7 is a cycle life curve diagram of the secondary batteries of Example 6 and Comparative Examples 4 to 6;

Figure 8 is a cycle life curve diagram of the secondary battery of Example 7;

Figure 9 is a cycle life curve diagram of the secondary batteries of Example 8 and Comparative Examples 3, 5, and 7;

Figure 10 is a cycle life curve diagram of the secondary batteries of Example 9 and Comparative Examples 4, 8-9;

Figure 11 is a cycle life curve diagram of the secondary batteries of Example 10 and Comparative Examples 4, 8-9;

Figure 12 is a cycle life curve diagram of the secondary battery of Example 11;

Figure 13 is a cycle life curve diagram of the secondary batteries of Example 12 and Comparative Examples 3, 8-9;

Figure 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.

Explanation of reference numbers

100: Secondary battery;

102: Negative pole;

102a, 104a: current collector;

102b: negative electrode material layer;

104: positive pole;

104b: positive electrode material layer;

106: Isolation film;

108: Electrolyte;

110: Accommodation area;

112: Package structure.

Detailed ways

As used herein, a range expressed by “one value to another value” is a summary expression that avoids enumerating all the values in the range one by one in the specification. Therefore, the description of a specific numerical range covers any numerical value within the numerical range and the smaller numerical range defined by any numerical value within the numerical range, as if the arbitrary numerical value and the smaller numerical value were expressly written in the description. The range is the same.

As used herein, "about," "approximately," "substantially," or "substantially" includes the stated value and an average within an acceptable range of deviations from the particular value as determined by one of ordinary skill in the art, taking into account that Discuss the specific quantities of measurements and errors associated with the measurements (i.e., limitations of the measurement system). For example, "about" may mean within one or more standard deviations of the stated value, or within ±30%, ±20%, ±15%, ±10%, ±5%, for example. Furthermore, the terms "about", "approximately", "substantially" or "substantially" used in this article can be used to select a more acceptable deviation range or standard deviation based on the measurement properties or other properties, rather than using a single standard deviation. Applies to all properties.

In order to prepare a negative electrode material that can be applied to the negative electrode of secondary batteries and enable the secondary battery to have good stability and capacity, the present invention proposes a negative electrode material that can achieve the above advantages. Hereinafter, embodiments are specifically mentioned as descriptions on which the present invention can be implemented reliably.

One embodiment of the present invention provides a negative electrode material, which may include a metal oxide containing more than four elements, or an oxide mixture containing more than four elements. In this embodiment, the negative electrode material may be powder, film or block.

In this embodiment, the preparation method of the metal oxide containing four or more elements includes, for example, hydrothermal method, co-precipitation method, sol-gel method, solid-state method, evaporation method, sputtering method or vapor deposition method, However, the present invention is not limited to this. In an embodiment where a hydrothermal method is used to prepare the metal oxide containing more than four elements, the temperature may be about 200°C or more, the temperature holding time may be about 5 hours or more, and the ambient pressure may be about 10 ^-2 Torr above. In an embodiment where a coprecipitation method is used to prepare the metal oxide containing four or more elements, coprecipitation is first carried out, the reaction temperature can be about 200°C or above, and the solution pH can be about 2 to about 12, The temperature holding time can be about 1 hour or more; after the reaction is completed, a calcining process is performed, the calcining temperature can be about 300°C or more, and the temperature holding time can be about 1 hour or more. In an embodiment where the sol-gel method is used to prepare the metal oxide containing more than four elements, the temperature may be above about 100°C, the pH value of the solution may be about 2 to about 12, and the temperature holding time may be about 5 hours or more. In addition, in an embodiment in which a solid-state method is used to prepare the metal oxide containing more than four elements, the temperature may be about 100°C or more, and the temperature holding time may be about 8 hours or more. In an embodiment where an evaporation method is used to prepare the metal oxide containing four or more elements, the temperature may be about 25°C or more, the evaporation time may be about 1 hour or more, and the ambient pressure may be about 10 ^-3 Torr above. In an embodiment where a sputtering method is used to prepare the metal oxide containing more than four elements, the temperature may be about 25°C or more, the sputtering time may be about 0.5 hours or more, and the ambient pressure may be about 10 ^-3 Torr above. In an embodiment where a vapor deposition method is used to prepare the metal oxide containing more than four elements, the temperature may be above about 25°C, the deposition time may be above about 1 hour, and the ambient pressure may be above about 10 ^-3 Torr .

In this embodiment, the metal oxide containing more than four elements may include cobalt copper tin oxide, silicon tin iron oxide, copper manganese silicon oxide, tin manganese nickel oxide, manganese copper nickel oxide, or Nickel copper tin oxide. Below, each of the above-mentioned oxides will be described in detail.

cobalt copper tin oxide

In this embodiment, the cobalt copper tin oxide may be represented by one 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 _x3Equation (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. If x1, x2 and x3 respectively meet the specific values listed above, the secondary battery using the negative electrode material including the cobalt copper tin oxide has excellent capacity, improved capacity retention and excellent cycle life. .

In each of Formula (1), Formula (2) and Formula (3), M may be at least one element selected from Ni, Cr, Mn, Zn, Al, Ti, In, Mo and W. The ratio of the atomic number of M to the total number of atoms of the metal elements in the cobalt copper tin oxide represented by the formula (1), the formula (2) or the formula (3) is 10 atomic% or less. In other words, the cobalt-copper-tin oxide represented by formula (1), formula (2) or formula (3) may not contain element M, but only include four elements, namely cobalt, copper, tin and oxygen. It is worth mentioning that compared with cobalt copper-tin oxide that does not contain element M, cobalt-copper-tin oxide containing M with an atomic number ratio greater than 0 and less than or equal to 10 atomic% has an increase in conductivity of about 10% or more. In addition, in this embodiment, in the case of cobalt-copper-tin oxide containing element M, M may replace part of the cobalt, copper and/or tin. For example, in one embodiment, M can replace part of the cobalt; in another embodiment, M can replace part of the cobalt and part of the copper; in yet another embodiment, M can replace part of the cobalt, part of the copper copper and a part of tin, but the invention is not limited thereto. It should be noted that in this embodiment, the atomic number value in the cobalt-copper-tin oxide represented by formula (1), formula (2) or formula (3) may vary due to the formation of oxygen vacancies or uneven diffusion. ±10% error margin.

In this embodiment, the cobalt copper tin oxide represented by formula (1), formula (2) or formula (3) may have a spinel structure (Spinel structure), a perovskite structure (Perovskite structure), or a chloride structure. Sodium structure (Sodiumchloride structure) or chalcopyrite structure (Chalcopyrite structure). It is worth mentioning that the cobalt-copper-tin oxide represented by formula (1), formula (2) or formula (3) has the above-mentioned structure and allows the existence of more oxygen vacancies, thereby in the application of the cobalt-copper tin oxide In secondary batteries made of tin oxide negative electrode materials, lithium ions can enter and exit easily and quickly, thus effectively increasing the lithium ion diffusion rate and ionic conductivity. In addition, the cobalt copper tin oxide represented by formula (1), formula (2) or formula (3) has the above-mentioned structure and is less likely to collapse during the charge and discharge process, thereby applying the cobalt copper tin oxide including the cobalt copper tin oxide Secondary batteries made of negative electrode materials can maintain good charge and 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. If the average particle size of the cobalt-copper-tin oxide falls within the above range, a negative electrode with good characteristics can be formed. In an embodiment of producing cobalt copper tin oxide by a solid-state method, in order to obtain the cobalt copper tin oxide with a specific average particle size range, a mortar, ball mill, sand grinder, vibrating ball mill or planetary grinder can be used. Grinding is performed using a planet ball mill, but the present invention is not limited thereto.

silicon tin iron oxide

In this embodiment, the silicon-tin-iron oxide may be represented by one 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 _x6Equation (6).

In equation (4), x4 ranges from 21 to 34. In equation (5), x5 is 3 to 5. In equation (6), x6 ranges from 6 to 11.5. If x4, x5 and x6 are respectively within the above range, the secondary battery using the negative electrode material including the silicon tin iron oxide has excellent capacitance and improved capacitance retention rate.

In each of Formula (4), Formula (5), and Formula (6), M may be at least one element selected from Cr, Mn, Zn, Al, Ti, In, Mo, and W. The ratio of the atomic number of M to the total number of atoms of elements other than oxygen in the silicon-tin-iron oxide represented by Formula (4), Formula (5) or Formula (6) is 10atomic% or less. In other words, the silicon-tin-iron oxide represented by formula (4), formula (5) or formula (6) may not contain element M, but only include four elements, namely silicon, tin, iron and oxygen. It is worth mentioning that compared with silicon-tin-iron oxide that does not contain element M, silicon-tin-iron oxide containing M with an atomic number ratio greater than 0 and less than or equal to 10 atomic% has an increase in conductivity of about 10% or more. In addition, in this embodiment, in the case of silicon-tin-iron oxide containing element M, M may replace part of silicon, tin and/or iron. For example, in one embodiment, M can replace part of the silicon; in another embodiment, M can replace part of the silicon and part of the tin; in yet another embodiment, M can replace part of the silicon, part of the tin tin and a part of iron, but the invention is not limited thereto. It should be noted that in this embodiment, the atomic number value in the silicon-tin-iron oxide represented by formula (4), formula (5) or formula (6) may vary due to the formation of oxygen vacancies or uneven diffusion. ±10% error margin.

In this embodiment, the silicon-tin-iron oxide represented by Formula (4), Formula (5) or Formula (6) may have an orthorhombic structure (Rhombohedral structure), a cubic Bixbyite structure (Cubic Bixbyite structure), Spinel structure or Orthorhombic structure. It is worth mentioning that the silicon-tin-iron oxide represented by formula (4), formula (5) or formula (6) allows the presence of more oxygen vacancies by having the above-mentioned structure, thereby in applications including the silicon-tin In secondary batteries made of iron oxide negative electrode materials, lithium ions can enter and exit easily and quickly, thus effectively increasing the lithium ion diffusion rate and ionic conductivity. In addition, the silicon-tin-iron oxide represented by formula (4), formula (5) or formula (6) has the above-mentioned structure and is less likely to collapse during the charge and discharge process, thereby applying the silicon-tin-iron oxide including the above-mentioned structure. Secondary batteries made of negative electrode materials can maintain good charge and 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. If the average particle size of the silicon-tin-iron oxide falls within the above range, a negative electrode with good characteristics can be formed. In an embodiment where the silicon-tin iron oxide is produced by a solid-state method, in order to obtain the above-mentioned silicon-tin iron oxide with a specific average particle size range, a mortar, a ball mill, a sand grinder, a vibrating ball mill or a planet can be used. Grinding is performed using a planet ball mill, but the present invention is not limited thereto.

Copper manganese silicon oxide

In this embodiment, the copper manganese silicon oxide can be represented by the following formula (7): Cu _x7 Mn _7-x7 SiMO ₁₂ formula (7). In formula (7), x7 is greater than 0 and less than or equal to 1. If x7 is within the above range, the secondary battery using the negative electrode material including the copper-manganese-silicon oxide has excellent electric capacity and improved electric capacity retention rate.

In formula (7), M may be at least one element selected from Cr, Sn, Ni, Co, Zn, Al, Ti, In, Mo and W. The ratio of the atomic number of M to the total number of atoms of elements other than oxygen in the copper-manganese-silicon oxide represented by formula (7) is 10 atomic% or less. In other words, the copper-manganese-silicon oxide represented by formula (7) may not contain element M, but only four elements, namely copper, manganese, silicon and oxygen. It is worth mentioning that compared with copper-manganese-silicon oxide that does not contain element M, copper-manganese-silicon oxide containing M with an atomic number ratio greater than 0 and less than or equal to 10 atomic% has an increase in conductivity of about 10% or more. In addition, in this embodiment, in the case of copper-manganese-silicon oxide containing element M, M may replace part of copper, manganese and/or silicon. For example, in one embodiment, M can replace part of copper; in another embodiment, M can replace part of copper and part of manganese; in yet another embodiment, M can replace part of copper, part of manganese and a part of silicon, but the invention is not limited thereto. It should be noted that in this embodiment, the atomic number values of copper and manganese in the copper-manganese-silicon oxide represented by formula (7) will have an error range of ±10% due to uneven diffusion or the formation of oxygen vacancies. , thereby forming non-integer ratio compounds.

In this embodiment, the copper-manganese-silicon oxide represented by Formula (7) may have an Abswurmbachite structure, a Pyroxmangite structure, or a Braunite structure. It is worth mentioning that the copper manganese silicon oxide represented by formula (7) has the above structure, whereby in a secondary battery using the negative electrode material including the copper manganese silicon oxide, the overpotential The energy loss caused can be reduced, the lithium ion diffusion rate and ion conductivity can be increased, and the charge and 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. If the average particle size of the copper-manganese-silicon oxide falls within the above range, a negative electrode with good characteristics can be formed. In an embodiment of producing copper-manganese-silicon oxide by a solid-state method, in order to obtain the above-mentioned copper-manganese-silicon oxide with a specific average particle size range, a mortar, ball mill, sand grinder, vibrating ball mill or planetary grinder can be used. Grinding is performed using a planet ball mill, but the present invention is not limited thereto.

Tin manganese nickel oxide

In this embodiment, the tin-manganese-nickel oxide may be represented by one of the following formulas (8) to (11):

Sn ₁ Mn ₂ Ni ₁ MO _x8Equation (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 _x11Equation (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 equation (11), x11 is 3 to 6. If x8, x9, x10 and x11 are respectively within the above ranges, the secondary battery using the negative electrode material including the tin-manganese nickel oxide has excellent capacitance and improved capacitance retention rate.

In each of Formula (8), Formula (9), Formula (10) and Formula (11), M may be at least one selected from Cr, Mn, Zn, Al, Ti, In, Mo and W. elements. The atomic number ratio of M is 10 atomic% or less relative to the total number of atoms of metal elements in the tin-manganese nickel oxide represented by Formula (8), Formula (9), Formula (10) or Formula (11). In other words, the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10) or formula (11) may not contain element M, but only include four elements, namely tin, manganese, nickel and oxygen. It is worth mentioning that compared with tin-manganese-nickel oxide that does not contain element M, tin-manganese-nickel oxide containing M with an atomic number ratio greater than 0 and less than or equal to 10 atomic% has an increase in conductivity of about 10% or more. In addition, in this embodiment, in the case of tin-manganese-nickel oxide containing element M, M may replace part of tin, manganese and/or nickel. For example, in one embodiment, M can replace part of tin; in another embodiment, M can replace part of tin and part of manganese; in yet another embodiment, M can replace part of tin, part of manganese and a part of nickel, but the invention is not limited thereto. It should be noted that in this embodiment, the number of atoms in the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10) or formula (11) may be affected by the formation of oxygen vacancies or Diffusion is not uniform with an error margin of ±10%.

In this embodiment, the tin-manganese nickel oxide represented by formula (8), formula (9), formula (10) or formula (11) may have a spinel structure (Spinel structure), a rubble structure (Rutile structure) ), rock salt structure (Rock saltstructure). It is worth mentioning that the tin-manganese nickel oxide represented by formula (8), formula (9), formula (10) or formula (11) allows more oxygen vacancies to exist by having the above-mentioned structure, thereby in the application In the secondary battery including the negative electrode material of the tin-manganese nickel oxide, lithium ions can enter and exit easily and quickly, thereby effectively improving the lithium ion diffusion rate and ion conductivity. In addition, the tin manganese nickel oxide represented by formula (8), formula (9), formula (10) or formula (11) has the above structure and is less likely to collapse during the charge and discharge process, thereby applying the above-mentioned Secondary batteries made of tin-manganese-nickel oxide negative electrode materials can maintain 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. If the average particle size of the tin-manganese-nickel oxide falls within the above range, a negative electrode with good characteristics can be formed. In an embodiment of producing tin-manganese nickel oxide by a solid-state method, in order to obtain the above-mentioned tin-manganese nickel oxide with a specific average particle size range, a mortar, ball mill, sand grinder, vibrating ball mill or planetary grinder can be used. Grinding is performed using a planet ball mill, but the present invention is not limited thereto.

Manganese copper nickel oxide

In this embodiment, the manganese copper nickel oxide can be represented by one 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 to say, in this embodiment, the atomic ratio of manganese, copper, nickel and oxygen in the manganese-copper-nickel oxide can be 3:2:1:8, 2:1:1:4, or 1:1 :1:4. It is worth mentioning that the manganese copper nickel oxide is represented by one of the formulas (12) to (14), whereby the secondary battery using the negative electrode material including the manganese copper nickel oxide has excellent capacitance and improved capacitance retention.

In each of Formula (12), Formula (13), and Formula (14), M may be at least one element selected from Fe, Cr, Zn, Al, Ti, In, Mo, W, and Si. The ratio of the atomic number of M to the total number of atoms of the metal elements in the manganese copper nickel oxide represented by the formula (12), the formula (13) or the formula (14) is 10 atomic% or less. In other words, the manganese-copper-nickel oxide represented by formula (12), formula (13) or formula (14) may not contain element M, but only include four elements, namely manganese, copper, nickel and oxygen. It is worth mentioning that compared with manganese copper nickel oxide that does not contain element M, manganese copper nickel oxide containing M with an atomic number ratio greater than 0 and less than or equal to 10 atomic% has an increase in conductivity of about 10% or more. In addition, in this embodiment, in the case of manganese-copper-nickel oxide containing element M, M may replace part of the manganese, copper and/or nickel. For example, in one embodiment, M can replace part of manganese; in another embodiment, M can replace part of manganese and part of copper; in yet another embodiment, M can replace part of manganese, part of copper and a part of nickel, but the invention is not limited thereto. It should be noted that in this embodiment, the atomic number value in the manganese copper nickel oxide represented by formula (12), formula (13) or formula (14) may vary due to the formation of oxygen vacancies or uneven diffusion. ±10% error margin.

In this embodiment, the manganese copper nickel oxide represented by formula (12), formula (13) or formula (14) may have an orthorhombic structure (Tetragonal structure), a spinel structure (Spinel structure), or a perovskite structure. Structure (Perovskitestructure), chalcopyrite structure (Chalcopyrite structure). It is worth mentioning that the manganese copper nickel oxide represented by formula (12), formula (13) or formula (14) has the above structure and allows the existence of more oxygen vacancies, thereby in applications including the manganese copper In secondary batteries made of nickel oxide negative electrode materials, lithium ions can enter and exit easily and quickly, thus effectively increasing the lithium ion diffusion rate and ion conductivity. In addition, the manganese-copper-nickel oxide represented by formula (12), formula (13) or formula (14) has the above-mentioned structure and is less likely to collapse during the charge and discharge process, thereby applying the manganese-copper-nickel oxide including the above-mentioned structure. Secondary batteries made of negative electrode materials can maintain good charge and 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. If the average particle size of the manganese-copper-nickel oxide falls within the above range, a negative electrode with good characteristics can be formed. In an embodiment in which manganese copper nickel oxide is produced by a solid-state method, in order to obtain the manganese copper nickel oxide with a specific average particle size range, a mortar, ball mill, sand grinder, vibrating ball mill or planetary grinder can be used. Grinding is performed using a planet ball mill, but the present invention is not limited thereto.

Nickel copper tin oxide

In this embodiment, the nickel copper tin oxide can be represented by one of the following formulas (15) to (17):

NiCuSn ₂ MO _x15 formula (15),

Ni ₂ CuSn ₃ MO _x16 formula (16),

NiCu ₂ Sn ₃ MO _x17 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. If x15, x16 and x17 respectively meet the specific values listed above, the secondary battery using the negative electrode material including the nickel copper tin oxide has excellent capacitance and improved capacitance retention rate.

In each of Formula (15), Formula (16), and Formula (17), M may be at least one element selected from Cr, Mn, Zn, Al, Ti, In, Mo, W, and Co. The ratio of the atomic number of M to the total number of atoms of the metal elements in the nickel-copper-tin oxide represented by Formula (15), Formula (16) or Formula (17) is 10atomic% or less. In other words, the nickel-copper-tin oxide represented by formula (15), formula (16) or formula (17) may not contain element M, but only include four elements, namely nickel, copper, tin and oxygen. It is worth mentioning that compared with nickel copper-tin oxide that does not contain element M, nickel-copper-tin oxide containing M with an atomic number ratio greater than 0 and less than or equal to 10 atomic% has an increase in conductivity of about 15% or more. In addition, in this embodiment, in the case of nickel-copper-tin oxide containing element M, M may replace part of nickel, copper and/or tin. For example, in one embodiment, M can replace part of nickel; in another embodiment, M can replace part of nickel and part of copper; in yet another embodiment, M can replace part of nickel, part of copper and a part of tin, but the invention is not limited thereto. It should be noted that in this embodiment, the atomic number value in the nickel-copper-tin oxide represented by formula (15), formula (16) or formula (17) may vary due to the formation of oxygen vacancies or uneven diffusion. ±10% error margin.

In this embodiment, the nickel copper tin oxide represented by formula (15), formula (16) or formula (17) may have a perovskite structure (Perovskite structure), a sodium chloride structure (Sodium chloride structure) or a yellow Chalcopyrite structure. It is worth mentioning that the nickel-copper-tin oxide represented by formula (15), formula (16) or formula (17) allows the presence of more oxygen vacancies by having the above-mentioned structure, thereby in applications including the nickel-copper In secondary batteries made of tin oxide negative electrode materials, lithium ions can enter and exit easily and quickly, thus effectively increasing the lithium ion diffusion rate and ionic conductivity. In addition, the nickel copper tin oxide represented by formula (15), formula (16) or formula (17) has the above structure and is less likely to collapse during the charge and discharge process, thereby applying the nickel copper tin oxide including the above Secondary batteries made of negative electrode materials can maintain good charge and 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. If the average particle size of the nickel-copper-tin oxide falls within the above range, a negative electrode with good characteristics can be formed. In an embodiment of producing nickel copper tin oxide by a solid-state method, in order to obtain the above-mentioned nickel copper tin oxide with a specific average particle size range, a mortar, ball mill, sand grinder, vibrating ball mill or planetary grinder can be used. Grinding is performed using a planet ball mill, but the present invention is not limited thereto.

Furthermore, in this embodiment, the method for preparing the oxide mixture containing four or more elements includes, for example, a mixing step. 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 an embodiment in which a physical dry mixing method is used to prepare the oxide mixture containing more than four elements, the mixing temperature may be room temperature, for example, about 25° C. or above. In an embodiment in which a physical wet mixing method is used to prepare the oxide mixture containing more than four elements, the mixing temperature may be room temperature, for example, about 25° C. or above, and the solvent may be water, alcohol, acetone, or methanol.

In this embodiment, the oxide mixture containing more than four elements may include an oxide mixture containing cobalt, copper and tin, an oxide mixture containing silicon, tin and iron, or an oxide containing copper, manganese and silicon. mixtures, oxide mixtures containing tin, manganese and nickel, oxide mixtures containing manganese, copper and nickel, or oxide mixtures containing nickel, copper and tin. Below, the various oxide mixtures mentioned above will be described in detail.

Mixture of oxides containing cobalt, copper and tin

In this embodiment, the oxide mixture containing cobalt, copper and tin may be composed of Co ₃ O ₄ , at least one of Co ₂ O ₃ and CoO, at least one of CuO and Cu ₂ O, and SnO and SnO ₂ At least one of them is obtained by performing a mixing step. That is, the oxide mixture containing cobalt, copper and tin can be obtained by performing a mixing step of cobalt oxide, copper oxide, and tin oxide. In addition, in this embodiment, the atomic ratio of cobalt, copper and 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 ratio of cobalt, copper and tin meets the specific ratio listed above, the secondary battery using the negative electrode material including the oxide mixture containing cobalt, copper and tin will have excellent electric capacity and improved electric capacity. Capacity retention rate.

In this embodiment, when performing the mixing step, 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 SnO ₂ can be selectively mixed. At least one of is mixed with an oxide containing M, wherein M is selected from at least one element among Ni, Cr, Mn, Zn, Al, Ti, In, Mo and W. That is, the oxide mixture containing cobalt, copper and tin may optionally include element M. Relative to the total atomic number of metal elements in the oxide mixture containing cobalt, copper and tin, the atomic number ratio of M ranges from greater than 0 to less than or equal to 10 atomic%. It is worth mentioning that compared with the oxide mixture containing cobalt, copper and tin without mixing the oxide containing M, the oxide containing M is mixed and the atomic number ratio of M is between greater than 0 and less than or equal to 10atomic % of the oxide mixture containing cobalt, copper and tin has an increase in conductivity of about 8% or more. It should be noted that in this embodiment, the value of the element atomic number ratio in the oxide mixture containing cobalt, copper and tin will have an error range of ±10% due to the formation of oxygen vacancies or uneven diffusion.

In this embodiment, the negative electrode is made of a negative electrode material including an oxide mixture containing cobalt, copper and tin, whereby lithium ions can move in and out through different paths, so that the polarization effect can be slowed down. And the charge and discharge cycle life can be improved. As a result, the electric capacity of the secondary battery using the negative electrode material including the oxide mixture containing cobalt, copper and tin can be significantly increased. In addition, tin oxide can be used as anode material to achieve high capacitance performance, copper oxide can be used as anode material to achieve good cycle life, and cobalt oxide can be used as anode material to achieve good lithium ion conductivity. Therefore, applications include The negative electrode material of the oxide mixture obtained by the mixing step of cobalt oxide, copper oxide, and tin oxide can have excellent performance and be safe for secondary batteries.

A mixture of oxides containing silicon, tin and iron

In this embodiment, the oxide mixture containing silicon, tin and iron may be composed of at least one of SiO ₂ and SiO, at least one of SnO and SnO ₂ , and Fe ₂ O ₃ , Fe ₃ O ₄ and FeO. At least one of them undergoes a mixing step. That is to say, the oxide mixture containing silicon, tin and iron can be obtained by performing a mixing step of silicon oxide, tin oxide, and iron oxide. In addition, in this embodiment, the atomic ratio of silicon, tin and iron in the oxide mixture containing silicon, tin and iron may be 4:1:16, 1:1:1 or 4:1:1. If the atomic ratio of silicon, tin and iron meets the specific ratio listed above, the secondary battery using the negative electrode material including the oxide mixture containing silicon, tin and iron will have excellent electric capacity and improved electric capacity. Capacity retention rate.

In this embodiment, when performing the mixing step, at least one of SiO ₂ and SiO, at least one of SnO and SnO ₂ , and Fe ₂ O ₃ , Fe ₃ O ₄ and FeO can be selectively mixed. At least one of is mixed with an oxide containing M, wherein M is selected from at least one element among Cr, Mn, Zn, Al, Ti, In, Mo and W. That is, the oxide mixture containing silicon, tin, and iron may optionally include the element M. Relative to the total atomic number of elements other than oxygen in the oxide mixture containing silicon, tin and iron, the atomic number ratio of M ranges from greater than 0 to less than or equal to 10 atomic%. It is worth mentioning that compared with the oxide mixture containing silicon, tin and iron that is not mixed with the M-containing oxide, the M-containing oxide is mixed and the atomic number ratio of M is between greater than 0 and less than or equal to 10atomic % of the oxide mixture containing silicon, tin and iron has an increase in conductivity of about 10% or more. It should be noted that in this embodiment, the value of the element atomic number ratio in the oxide mixture containing silicon, tin and iron will have an error range of ±10% due to the formation of oxygen vacancies or uneven diffusion.

In this embodiment, by using a negative electrode material including an oxide mixture containing silicon, tin and iron to make the negative electrode, lithium ions can move in and out through different paths, so that the polarization effect can be slowed down. And the charge and discharge cycle life can be improved. As a result, the electric capacity of the secondary battery using the negative electrode material including the oxide mixture containing silicon, tin and iron can be significantly increased. In addition, tin oxide can be used as anode material to achieve high capacitance performance, iron oxide can be used as anode material to achieve good cycle life, and silicon oxide can be used as anode material to achieve good lithium ion conductivity. Therefore, applications include The negative electrode material of the oxide mixture obtained by the mixing step of silicon oxide, tin oxide, and iron oxide can have excellent performance and be safe for secondary batteries.

Mixture of oxides containing copper, manganese and silicon

In this embodiment, the oxide mixture containing copper, manganese and silicon may be composed of 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 Obtained by subjecting at least one of ₃ O ₄ to a mixing step. That is, the oxide mixture containing copper, manganese and silicon can be obtained by performing a mixing step of copper oxide, manganese oxide, and silicon oxide. In addition, in this embodiment, the atomic ratio of copper, manganese and silicon in the oxide mixture containing copper, manganese and silicon can be 1:1:1, 1:4:1, 4:1:1 or 1 :1:4. If the atomic ratio of copper, manganese and silicon meets the specific ratio listed above, the secondary battery using the negative electrode material including the oxide mixture containing copper, manganese and silicon will have excellent electric capacity and improved electric capacity. Capacity retention rate.

In this embodiment, when performing the mixing step, 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 can be selectively mixed. At least one of ₃ O ₄ is mixed with an oxide containing M, wherein M is selected from at least one element selected from Cr, W, Sn, Ni, Zn, Al, Ti, In and Mo. That is, the oxide mixture containing copper, manganese and silicon may optionally include the element M. Relative to the total atomic number of elements other than oxygen in the oxide mixture containing copper, manganese and silicon, the atomic number ratio of M ranges from greater than 0 to less than or equal to 10 atomic%. It is worth mentioning that, compared with the oxide mixture containing copper, manganese and silicon that is not mixed with the M-containing oxide, the M-containing oxide is mixed and the atomic number ratio of M is between greater than 0 and less than or equal to 10atomic % of the oxide mixture containing copper, manganese and silicon has an increase in conductivity of about 10% or more. It should be noted that in this embodiment, the value of the element atomic number ratio in the oxide mixture containing copper, manganese and silicon will have an error range of ±10% due to the formation of oxygen vacancies or uneven diffusion.

In this embodiment, the oxide mixture containing copper, manganese and silicon obtained by performing a mixing step of copper oxide, manganese oxide and silicon oxide is caused by the interaction between the plurality of oxides. The synergistic effect brought about allows the electric capacity of the secondary battery using the negative electrode material including the oxide mixture containing copper, manganese and silicon to be significantly increased. In addition, in this embodiment, a negative electrode material including an oxide mixture containing copper, manganese and silicon is used to make the negative electrode, whereby lithium ions can move in and out through different paths, so that the polarization effect can be achieved. can be slowed down and the charge-discharge cycle life can be improved. In addition, copper oxide can achieve good cycle life as anode material, manganese oxide can achieve low overpotential as anode material, and silicon oxide can achieve good lithium ion conductivity as anode material. Therefore, applications including The secondary battery of the negative electrode material of the oxide mixture obtained by mixing copper oxide, manganese oxide, and silicon oxide can have excellent performance and is safe.

Mixtures of oxides containing tin, manganese and nickel

In this embodiment, the oxide mixture containing tin, manganese and nickel may be composed of 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 At least one of Ni ₂ O ₃ undergoes a mixing step. That is to say, the oxide mixture containing tin, manganese and nickel can be obtained by performing a mixing step of tin oxide, manganese oxide, and nickel oxide. In addition, in this embodiment, the atomic ratio of tin, manganese and nickel in the oxide mixture containing tin, manganese and nickel can be 1:2:1, 1:1:1, 1:1:2 or 2 :1:1. If the atomic ratio of tin, manganese and nickel meets the specific ratio listed above, the secondary battery using the negative electrode material including the oxide mixture containing tin, manganese and nickel will have excellent electric capacity and improved electric capacity. Capacity retention rate.

In this embodiment, when performing the mixing step, 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 At least one of Ni ₂ O ₃ is mixed with an oxide containing M, where M is selected from at least one element selected from Cr, W, Si, Cu, Zn, Al, Ti, In and Mo. That is, the oxide mixture containing tin, manganese and nickel may optionally include element M. Relative to the total atomic number of metal elements in the oxide mixture containing tin, manganese and nickel, the atomic number ratio of M ranges from greater than 0 to less than or equal to 10 atomic%. It is worth mentioning that compared with the oxide mixture containing tin, manganese and nickel that is not mixed with the oxide containing M, the oxide containing M is mixed and the atomic number ratio of M is between greater than 0 and less than or equal to 10atomic % of the oxide mixture containing tin, manganese and nickel has an increase in conductivity of about 10% or more. It should be noted that in this embodiment, the value of the element atomic number ratio in the oxide mixture containing tin, manganese and nickel will have an error range of ±10% due to the formation or uneven diffusion of oxygen vacancies.

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 is caused by the interaction between the plurality of oxides. The synergistic effect brought about allows the electric capacity of the secondary battery using the negative electrode material including the oxide mixture containing tin, manganese and nickel to be significantly increased. In addition, in this embodiment, a negative electrode material including an oxide mixture containing tin, manganese and nickel is used to make the negative electrode, whereby lithium ions can move in and out through different paths, so that the polarization effect can be achieved. can be slowed down and the charge-discharge cycle life can be improved. In addition, tin oxide can be used as a negative electrode material to achieve high capacitance performance, manganese oxide can be used as a negative electrode material to achieve low overpotential, and nickel oxide can be used as a negative electrode material to achieve good lithium ion conductivity. Therefore, applications include The negative electrode material of the oxide mixture obtained by the mixing step of tin oxide, manganese oxide, and nickel oxide can have excellent performance and be safe for secondary batteries.

Mixture of oxides containing manganese, copper and nickel

In this embodiment, the oxide mixture containing manganese, copper and nickel may be composed of 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 Obtained by performing a mixing step with at least one of Ni ₂ O ₃ . That is to say, the oxide mixture containing manganese, copper and nickel can be obtained by performing a mixing step of manganese oxide, copper oxide, and nickel oxide. In addition, in this embodiment, the atomic ratio of manganese, copper and nickel in the oxide mixture containing manganese, copper and nickel may be 3:2:1, 2:1:1 or 1:1:1. If the atomic ratio of manganese, copper and nickel meets the specific ratio listed above, the secondary battery using the negative electrode material including the oxide mixture containing manganese, copper and nickel will have excellent electric capacity and improved electric capacity. Capacity retention rate.

In this embodiment, when performing the mixing step, 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 can be selectively mixed. Mix with at least one of Ni ₂ O ₃ and an oxide containing M, where M is selected from at least one element selected from Fe, Cr, Zn, Al, Ti, In, Mo, W and Si. That is, the oxide mixture containing manganese, copper and nickel may optionally include the element M. Relative to the total atomic number of metal elements in the oxide mixture containing manganese, copper and tin, the atomic number ratio of M ranges from greater than 0 to less than or equal to 10 atomic%. It is worth mentioning that compared with the oxide mixture containing manganese, copper and nickel that is not mixed with the M-containing oxide, the M-containing oxide is mixed and the atomic number ratio of M is between greater than 0 and less than or equal to 10atomic % of the oxide mixture containing manganese, copper and nickel has an increase in conductivity of about 5% or more. It should be noted that in this embodiment, the value of the element atomic number ratio in the oxide mixture containing manganese, copper and nickel will have an error range of ±10% due to the formation or uneven diffusion of oxygen vacancies.

In this embodiment, the negative electrode is made of a negative electrode material including an oxide mixture containing manganese, copper and nickel, whereby lithium ions can move in and out through different paths, so that the polarization effect can be slowed down. And the charge and discharge cycle life can be improved. In addition, manganese oxide can be used as anode material to achieve low overpotential, copper oxide can be used as anode material to achieve good cycle life, and nickel oxide can be used as anode material to achieve high capacitance performance, so applications including manganese The secondary battery of the negative electrode material of the oxide mixture obtained by mixing the oxide, copper oxide, and nickel oxide can have excellent performance and is safe.

Oxide mixture containing nickel, copper and tin

In this embodiment, the oxide mixture containing nickel, copper and tin may be composed of at least one of Ni ₂ O ₃ and NiO, at least one of CuO and Cu ₂ O, and at least one of SnO and SnO ₂ Obtained by performing a mixing step. That is to say, the oxide mixture containing nickel, copper and tin can be obtained by performing a mixing step of nickel oxide, copper oxide and tin oxide. In addition, in this embodiment, the atomic ratio of nickel, copper and tin in the oxide mixture containing nickel, copper and tin may be 1:1:2, 2:1:3 or 1:2:3. If the atomic ratio of nickel, copper and tin meets the specific ratio listed above, the secondary battery using the negative electrode material including the oxide mixture containing nickel, copper and tin will have excellent electric capacity and improved electric capacity. Capacity retention rate.

In this embodiment, when performing the mixing step, at least one of Ni ₂ O ₃ and NiO, at least one of CuO and Cu ₂ O, and at least one of SnO and SnO ₂ can be selectively mixed with M-containing oxides are mixed together, wherein M is selected from at least one element among Cr, Mn, Zn, Al, Ti, In, Mo, W and Co. That is, the oxide mixture containing nickel, copper and tin may optionally include element M. Relative to the total atomic number of metal elements in the oxide mixture containing nickel, copper and tin, the atomic number ratio of M ranges from greater than 0 to less than or equal to 10 atomic%. It is worth mentioning that, compared with the oxide mixture containing nickel, copper and tin that is not mixed with the M-containing oxide, the M-containing oxide is mixed and the atomic number ratio of M is between greater than 0 and less than or equal to 10atomic % of the oxide mixture containing nickel, copper and tin has an increase in conductivity of about 8% or more. It should be noted that in this embodiment, the value of the element atomic number ratio in the oxide mixture containing nickel, copper and tin will have an error range of ±10% due to the formation or uneven diffusion of oxygen vacancies.

In this embodiment, the negative electrode is made of a negative electrode material including an oxide mixture containing nickel, copper and tin, whereby lithium ions can move in and out through different paths, so that the polarization effect can be slowed down. And the charge and discharge cycle life can be improved. As a result, the electric capacity of the secondary battery using the negative electrode material including the oxide mixture containing nickel, copper and tin can be significantly increased. In addition, tin oxide can be used as anode material to achieve high capacitance performance, copper oxide can be used as anode material to achieve good cycle life, and nickel oxide can be used as anode material to achieve good lithium ion conductivity. Therefore, applications include The negative electrode material of the oxide mixture obtained by performing a mixing step of nickel oxide, copper oxide, and tin oxide can have excellent performance and be safe for secondary batteries.

Another embodiment of the present invention also provides a secondary battery that uses any of the negative electrode materials proposed in the previous 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 , the secondary battery 100 may include a negative electrode 102 , a positive electrode 104 , an electrolyte 108 and a packaging structure 112 . In this embodiment, the secondary battery 100 may further include a separator 106 . In addition, in this embodiment, the secondary battery 100 may be a lithium ion battery.

In this embodiment, the negative electrode 102 may include a current collector 102a and a negative electrode 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 stainless steel foil. In this embodiment, the thickness of the current collector 102a may range from about 5 μm to about 300 μm.

In this embodiment, the negative electrode material layer 102b includes any of the negative electrode materials proposed in the previous embodiments. In this embodiment, the negative electrode material can be disposed on the current collector 102a by, for example, coating, sputtering, hot pressing, sintering, physical vapor deposition or chemical vapor deposition. In addition, in this embodiment, the negative electrode material layer 102b may further include a conductive agent and an adhesive. In this embodiment, the guide agent can be natural graphite, artificial graphite, carbon black, conductive carbon (such as VGCF, Super P, KS4, KS6 or ECP), acetylene black (acetylene black), Ketjen Ketjen black, carbon whisker, carbon fiber, metal powder, metal fiber or conductive ceramics material. Specifically, the conductive agent is used to improve the electrical contact between negative electrode materials. In this embodiment, the adhesive may be polyvinylidene fluoride (PVDF), styrene butadiene rubber (SBR), polyamide, melamine resin or a combination thereof. In detail, the negative electrode material may be adhered to the current collector 102a through an adhesive.

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

In this embodiment, the positive electrode material layer 104b includes a positive electrode material. In this embodiment, the cathode material may include 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. In this embodiment, the positive electrode material can be disposed on the current collector 104a by, for example, coating, sputtering, hot pressing, sintering, physical vapor deposition or chemical vapor deposition. In addition, in this embodiment, the positive electrode material layer 104b may further include an adhesive. In this embodiment, the adhesive may be polyvinylidene fluoride (PVDF), styrene butadiene rubber (SBR), polyamide, melamine resin or a combination thereof. In detail, the positive electrode material may be adhered to the current collector 104a through an adhesive.

In this embodiment, the electrolyte 108 is disposed between the negative electrode 102 and the positive electrode 104 . The electrolyte 108 may include a liquid electrolyte, a colloidal electrolyte, a molten salt electrolyte, or a solid electrolyte.

In this embodiment, the isolation film 106 is disposed between the negative electrode 102 and the positive electrode 104 , the isolation film 106 , the negative electrode 102 and the positive electrode 104 define an accommodation area 110 , and the electrolyte 108 is arranged in the accommodation area 110 . In this embodiment, the material of the isolation film 106 may be an insulating material, such as polyethylene (PE), polypropylene (PP), or a composite structure composed of the above materials (such as PE/PP/PE).

In this embodiment, the secondary battery 100 includes an isolation film 106 to isolate the negative electrode 102 and the positive electrode 104 and allow ions to penetrate, but the 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, the packaging structure 112 covers the negative electrode 102 , the positive electrode 104 and the electrolyte 108 . In this embodiment, the material of the packaging structure 112 is, for example, aluminum foil or stainless steel.

In this embodiment, the structure of the secondary battery 100 is not limited to that shown in FIG. 1 . In other embodiments, the secondary battery 100 may have the following structure: a roll-type structure in which a negative electrode, a positive electrode, and a separator film are wound as necessary, or a roll-type structure in which flat plates are laminated. Layered structure. In addition, in this embodiment, the secondary battery 100 is, for example, a paper battery, a button battery, a coin battery, a laminated battery, a cylindrical battery, or a prismatic battery.

In particular, the negative electrode 102 of the secondary battery 100 uses any of the negative electrode materials proposed in the previous embodiments. Therefore, as mentioned above, the secondary battery 100 can have good capacitance, stability, and charge-discharge cycle life. .

The features of the present invention will be described in more detail below with reference to Examples 1 to 14 and Comparative Examples 1 to 9. Although the following Examples 1 to 14 are described, the materials used, their amounts and ratios, processing details, processing procedures, and the like may be appropriately changed without exceeding the scope of the present invention. Therefore, the present invention should not be interpreted restrictively by the examples described below.

Example 1

Preparation of negative electrode materials

At room temperature, use a ball mill to separate CoO powder (precursor containing cobalt), CuO powder (precursor containing copper), SnO powder (precursor containing tin), and W oxide powder (precursor containing element M) After grinding, the powders are mixed and pressed into a green pellet with a diameter of about 1 cm. The green embryo is placed in a high-temperature furnace to obtain a cobalt-copper-tin oxide block represented by the aforementioned formula (1) (i.e., the negative electrode material of Example 1), where x1 is 8, element M is W, and element M is The atomic number ratio is about 1 to 10 atomic%, and the average particle size of the cobalt copper tin oxide is between about 0.1 μm and about 10 μm.

Preparation of secondary batteries

The crushed and ground negative electrode material of Example 1, Super P conductive carbon and adhesive (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Next, add zirconium dioxide balls and mix for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector) and make it uniform After scraping, the copper foil coated with the slurry is placed in a vacuum oven and dried at about 110° C. for about 12 hours. After that, the dried copper foil is cut into a diameter of about 12.8 mm using a cutting machine. The negative electrode of Example 1.

A button battery (model: CR2032) was assembled, in which the negative electrode of Example 1 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ was added to the organic solvent as the electrolyte, and a polypropylene film (trade name: Celgard #2400, Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 1 was produced.

Example 2

Preparation of negative electrode materials

At room temperature, use a ball mill to separate CoO powder (precursor containing cobalt), CuO powder (precursor containing copper), SnO powder (precursor containing tin), and W oxide powder (precursor containing element M) After grinding, the powders are mixed and pressed into a green pellet with a diameter of about 1 cm. The green embryo is placed in a high-temperature furnace to obtain a cobalt-copper-tin oxide block represented by the aforementioned formula (2) (i.e., the negative electrode material of Example 2), where x2 is 4, element M is W, and element M is The atomic number ratio is about 1 to 10 atomic%, and the average particle size of the cobalt copper tin oxide is between about 0.1 μm and about 10 μm.

Preparation of secondary batteries

The crushed and ground negative electrode material of Example 2, Super P conductive carbon and adhesive (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Next, add zirconium dioxide balls and mix for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector) and make it uniform After scraping, the copper foil coated with the slurry is placed in a vacuum oven and dried at about 110° C. for about 12 hours. After that, the dried copper foil is cut into a diameter of about 12.8 mm using a cutting machine. The negative electrode of Example 2.

A button battery (model: CR2032) was assembled, in which the negative electrode of Example 2 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ was added to the organic solvent as the electrolyte, and a polypropylene film (trade name: Celgard #2400, Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 2 was produced.

Example 3

Preparation of negative electrode materials

At room temperature, use a ball mill to separate CoO powder (precursor containing cobalt), CuO powder (precursor containing copper), SnO powder (precursor containing tin), and W oxide powder (precursor containing element M) After grinding, the powders are mixed and pressed into a green pellet with a diameter of about 1 cm. The green embryo is placed in a high-temperature furnace to obtain a cobalt-copper-tin oxide block represented by the aforementioned formula (3) (i.e., the negative electrode material of Embodiment 3), where x3 is 4, element M is W, and element M is The atomic number ratio is about 1 to 10 atomic%, and the average particle size of the cobalt copper tin oxide is between about 0.1 μm and about 10 μm.

Preparation of secondary batteries

The crushed and ground negative electrode material of Example 3, Super P conductive carbon and adhesive (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Next, add zirconium dioxide balls and mix for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector) and make it uniform After scraping, the copper foil coated with the slurry is placed in a vacuum oven and dried at about 110° C. for about 12 hours. After that, the dried copper foil is cut into a diameter of about 12.8 mm using a cutting machine. The negative electrode of Example 3.

Assemble a button battery (model: CR2032), using the negative electrode of Example 3 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to the organic solvent as the electrolyte, and polypropylene membrane (trade name: Celgard #2400, Carl Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 3 was produced.

Example 4

Preparation of negative electrode materials

At room temperature, CoO powder (cobalt oxide), CuO powder (copper oxide), SnO ₂ powder (tin oxide), and W oxide powder (oxide containing element M) were ground using a ball mill. After mixing, an oxide mixture containing cobalt, copper and tin (ie, the negative electrode material of Embodiment 4) is obtained, in which the atomic ratio of cobalt, copper and tin is 1:1:1, the element M is W, and the element M The atomic number ratio is about 1 to 10atomic%.

Preparation of secondary batteries

The negative electrode 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. Then, zirconium dioxide balls were added Mix the slurry for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector), and smooth it evenly, and then apply The copper foil with the slurry was placed in a vacuum oven and dried at about 110° C. for about 12 hours. Afterwards, the dried copper foil was cut into negative electrodes of Example 4 with a diameter of about 12.8 mm using a cutting machine.

Assemble a button battery (model: CR2032), in which the negative electrode of Example 4 is used as the working electrode, lithium metal is used as the counter electrode, 1M LiPF ₆ is added to the organic solvent as the electrolyte, and a polypropylene film (trade name: Celgard #2400, Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 4 was produced.

Example 5

Preparation of negative electrode materials

At room temperature, use a ball mill to separate SiO ₂ powder (silicon-containing precursor), SnO ₂ powder (tin-containing precursor), Fe ₂ O ₃ powder (iron-containing precursor), TiO ₂ powder (containing element M After grinding the precursors, the powders are mixed and pressed into a green pellet with a diameter of about 1 cm. The green embryo is placed in a high-temperature furnace to obtain a silicon-tin-iron oxide block represented by the aforementioned formula (4) (i.e., the negative electrode material of Embodiment 4), where x4 is 21, element M is Ti, and The atomic number ratio is about 1 to 10 atomic%, and the average particle size of the silicon-tin-iron oxide is about 0.1 μm to about 10 μm.

Preparation of secondary batteries

The crushed and ground negative electrode material of Example 5, Super P conductive carbon and adhesive (i.e., sodium carboxymethylcellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Next, add zirconium dioxide balls and mix for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector) and make it uniform After scraping, the copper foil coated with the slurry is placed in a vacuum oven and dried at about 110° C. for about 12 hours. After that, the dried copper foil is cut into a diameter of about 12.8 mm using a cutting machine. The negative electrode of Example 5.

Assemble a button battery (model: CR2032), using the negative electrode of Example 5 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to the organic solvent as the electrolyte, and polypropylene membrane (trade name: Celgard #2400, Carl Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 5 was produced.

Example 6

Preparation of negative electrode materials

At room temperature, use a ball mill to separate SiO ₂ powder (oxide of silicon), SnO ₂ powder (oxide of tin), Fe ₂ O ₃ powder (oxide of iron), and TiO ₂ powder (oxide containing element M). ) are ground and mixed to obtain an oxide mixture containing silicon, tin and iron (i.e., the negative electrode material of Example 6), in which the atomic ratio of silicon, tin and iron is 4:1:16, and the element M is Ti, And the atomic number ratio of the element M is approximately 1 to 10 atomic%.

Preparation of secondary batteries

The negative electrode 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. Then, zirconium dioxide balls were added Mix the slurry for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector), and smooth it evenly, and then apply The copper foil with the slurry was placed in a vacuum oven and dried at about 110° C. for about 12 hours. Afterwards, the dried copper foil was cut into negative electrodes of Example 6 with a diameter of about 12.8 mm using a cutting machine.

A button battery (model: CR2032) was assembled, in which the negative electrode of Example 6 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ was added to the organic solvent as the electrolyte, and a polypropylene film (trade name: Celgard #2400, Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 6 was produced.

Example 7

Preparation of negative electrode materials

At room temperature, use a ball mill to separate CuO powder (precursor containing copper), MnO powder (precursor containing manganese), SiO ₂ powder (precursor containing silicon), and TiO ₂ powder (precursor containing element M) After grinding, the powders are mixed and pressed into a green pellet with a diameter of about 1 cm. The green embryo is placed in a high-temperature furnace to obtain a copper-manganese-silicon oxide block represented by the aforementioned formula (7) (i.e., the negative electrode material of Embodiment 7), where x7 is 1, element M is Ti, and The atomic number ratio is about 1 to 10 atomic%, and the average particle size of the copper manganese silicon oxide is about 0.1 μm to about 10 μm.

Preparation of secondary batteries

The crushed and ground negative electrode material of Example 7, Super P conductive carbon and adhesive (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Next, add zirconium dioxide balls and mix for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector) and make it uniform After scraping, the copper foil coated with the slurry is placed in a vacuum oven and dried at about 110° C. for about 12 hours. After that, the dried copper foil is cut into a diameter of about 12.8 mm using a cutting machine. The negative electrode of Example 7.

Assemble a button cell (model: CR2032), in which the negative electrode of Example 7 is used as the working electrode, lithium metal is used as the counter electrode, 1M LiPF ₆ is added to the organic solvent as the electrolyte, and a polypropylene film (trade name: Celgard #2400, Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 7 was produced.

Example 8

Preparation of negative electrode materials

At room temperature, use a ball mill to grind and mix CuO powder (oxide of copper), MnO powder (oxide of manganese), SiO ₂ powder (oxide of silicon), and TiO ₂ powder (oxide containing element M) respectively. After that, an oxide mixture containing copper, manganese and silicon (i.e., the negative electrode material of Example 8) is obtained, in which the atomic ratio of copper, manganese and silicon is 1:4:1, the element M is Ti, and the element M is The atomic number ratio is approximately 1 to 10 atomic%.

Preparation of secondary batteries

The negative electrode 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. Then, zirconium dioxide balls were added Mix the slurry for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector), and smooth it evenly, and then apply The copper foil with the slurry was placed in a vacuum oven and dried at about 110° C. for about 12 hours. Afterwards, the dried copper foil was cut into negative electrodes of Example 8 with a diameter of about 12.8 mm using a cutting machine.

A button battery (model: CR2032) was assembled, using the negative electrode of Example 8 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to the organic solvent as the electrolyte, and polypropylene film (trade name: Celgard #2400, Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 8 was produced.

Example 9

Preparation of negative electrode materials

At room temperature, SnO ₂ powder (precursor containing tin), MnO ₂ powder (precursor containing manganese), NiO powder (precursor containing nickel), and Mo oxide powder (precursor containing element M) were separately mixed using a ball mill. After grinding, the powders are mixed and pressed into a green pellet with a diameter of about 1 cm. The green embryo is placed in a high-temperature furnace to obtain a tin-manganese-nickel oxide block represented by the aforementioned formula (8) (i.e., the negative electrode material of Example 9), where x8 is 7, element M is Mo, and The atomic ratio is about 1 to 10 atomic%, and the average particle size of the tin-manganese nickel oxide is about 0.1 μm to about 10 μm.

Preparation of secondary batteries

The crushed and ground negative electrode material of Example 9, Super P conductive carbon and adhesive (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Next, add zirconium dioxide balls and mix for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector) and make it uniform After scraping, the copper foil coated with the slurry is placed in a vacuum oven and dried at about 110° C. for about 12 hours. After that, the dried copper foil is cut into a diameter of about 12.8 mm using a cutting machine. The negative electrode of Example 9.

A button battery (model: CR2032) was assembled, in which the negative electrode of Example 9 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ was added to the organic solvent as the electrolyte, and a polypropylene film (trade name: Celgard #2400, Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 9 was produced.

Example 10

Preparation of negative electrode materials

At room temperature, use a ball mill to grind SnO ₂ powder (tin oxide), MnO ₂ powder (manganese oxide), NiO powder (nickel oxide), and Mo oxide powder (oxide containing element M) respectively. After grinding and mixing, an oxide mixture containing tin, manganese and nickel (i.e., the negative electrode material of Example 10) is obtained, in which the atomic ratio of tin, manganese and nickel is 1:2:1, the element M is Mo, and the element The atomic number ratio of M is approximately 1 to 10 atomic%.

Secondary battery manufacturing

The negative electrode 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. Then, zirconium dioxide balls were added Mix the slurry for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector), and smooth it evenly, and then apply The copper foil with the slurry was placed in a vacuum oven and dried at about 110° C. for about 12 hours. Afterwards, the dried copper foil was cut into negative electrodes of Example 10 with a diameter of about 12.8 mm using a cutting machine.

Assemble a button battery (model: CR2032), in which the negative electrode of Example 10 is used as the working electrode, lithium metal is used as the counter electrode, 1M LiPF ₆ is added to the organic solvent as the electrolyte, and a polypropylene film (trade name: Celgard #2400, Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 10 was produced.

Example 11

Preparation of negative electrode materials

At room temperature, use a ball mill to separate MnO ₂ powder (precursor containing manganese), CuO powder (precursor containing copper), NiO powder (precursor containing nickel), and Mo oxide powder (precursor containing element M). ), the powders are mixed and pressed into a green pellet with a diameter of about 1 cm. The green embryo is placed in a high-temperature furnace to obtain a manganese-copper-nickel oxide block represented by the aforementioned formula (13) (i.e., the negative electrode material of Example 11), in which the element M is Mo and the atomic ratio of the element M is About 1 to 10 atomic%, and the average particle size of manganese copper tin oxide is about 0.1 μm to about 10 μm.

Preparation of secondary batteries

The crushed and ground negative electrode material of Example 11, Super P conductive carbon and adhesive (i.e., sodium carboxymethylcellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Next, add zirconium dioxide balls and mix for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector) and make it uniform After scraping, the copper foil coated with the slurry is placed in a vacuum oven and dried at about 110° C. for about 12 hours. After that, the dried copper foil is cut into a diameter of about 12.8 mm using a cutting machine. The negative electrode of Example 11.

A button battery (model: CR2032) was assembled, in which the negative electrode of Example 11 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ was added to the organic solvent as the electrolyte, and a polypropylene film (trade name: Celgard #2400, Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 11 was produced.

Example 12

Preparation of negative electrode materials

At room temperature, MnO ₂ powder (manganese oxide), CuO powder (copper oxide), NiO powder (nickel oxide), and Mo oxide powder (oxide containing element M) were separately processed using a ball mill. After grinding and mixing, an oxide mixture containing manganese, copper and nickel (i.e., the negative electrode material of Example 12) is obtained, in which the atomic ratio of manganese, copper and nickel is 2:1:1, the element M is Mo, and the element The atomic number ratio of M is approximately 1 to 10 atomic%.

Preparation of secondary batteries

The negative electrode material of Example 12, 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. Then, zirconium dioxide balls were added Mix the slurry for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector), and smooth it evenly, and then apply The copper foil with the slurry was placed in a vacuum oven and dried at about 110° C. for about 12 hours. Afterwards, the dried copper foil was cut into negative electrodes of Example 12 with a diameter of about 12.8 mm using a cutting machine.

A button battery (model: CR2032) was assembled, in which the negative electrode of Example 12 was used as the working electrode, lithium metal was used as the counter electrode, 1M LiPF ₆ was added to the organic solvent as the electrolyte, and a polypropylene film (trade name: Celgard #2400, Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 12 was produced.

Example 13

Preparation of negative electrode materials

At room temperature, NiO powder (nickel oxide), CuO powder (copper oxide), SnO ₂ powder (tin oxide), and W oxide powder (oxide containing element M) were ground using a ball mill. After mixing, an oxide mixture containing nickel, copper and tin (i.e., the negative electrode material of Example 13) is obtained, in which the atomic ratio of nickel, copper and tin is 1:1:2, the element M is W, and the element M The atomic number ratio is about 1 to 10atomic%.

Preparation of secondary batteries

The crushed and ground negative electrode material of Example 13, Super P conductive carbon and adhesive (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Next, add zirconium dioxide balls and mix for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector) and make it uniform After scraping, the copper foil coated with the slurry is placed in a vacuum oven and dried at about 110° C. for about 12 hours. After that, the dried copper foil is cut into a diameter of about 12.8 mm using a cutting machine. The negative electrode of Example 13.

A button battery (model: CR2032) was assembled, using the negative electrode of Example 13 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to the organic solvent as the electrolyte, and polypropylene film (trade name: Celgard #2400, Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 13 was produced.

Example 14

Preparation of negative electrode materials

At room temperature, use a ball mill to separate NiO powder (precursor containing nickel), CuO powder (precursor containing copper), SnO ₂ powder (precursor containing tin), and W oxide powder (precursor containing element M). ), the powders are mixed and pressed into a green pellet with a diameter of about 1 cm. The green embryo is placed in a high-temperature furnace to obtain a nickel-copper-tin oxide block represented by the aforementioned formula (15) (i.e., the negative electrode material of Embodiment 14), where x15 is 6, element M is W, and element M is The atomic number ratio is about 1 to 10 atomic%, and the average particle size of the manganese copper tin oxide is about 0.1 μm to about 10 μm.

Preparation of secondary batteries

The crushed and ground negative electrode material of Example 14, Super P conductive carbon and adhesive (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Next, add zirconium dioxide balls and mix for about 30 minutes to form a negative electrode slurry. Then, use a scraper (100 μm) to apply the slurry on the copper foil (the aforementioned current collector) and make it uniform After scraping, the copper foil coated with the slurry is placed in a vacuum oven and dried at about 110° C. for about 12 hours. After that, the dried copper foil is cut into a diameter of about 12.8 mm using a cutting machine. The negative electrode of Example 14.

A button battery (model: CR2032) was assembled, using the negative electrode of Example 14 as the working electrode, lithium metal as the counter electrode, 1M LiPF ₆ added to the organic solvent as the electrolyte, and polypropylene film (trade name: Celgard #2400, Celgard (manufactured by Celgard) as the isolation membrane and stainless steel 304 or 316 cover as the packaging structure. At this point, the secondary battery of Example 14 was produced.

Comparative example 1

Preparation of secondary batteries

The secondary battery of Comparative Example 1 was produced according to the same manufacturing procedure as Example 1. The main difference lies in that: in the secondary battery of Example 1, the working electrode uses the negative electrode of Example 1; while in Comparative Example 1 In the secondary battery, the material of the working electrode is Co ₂ SnO ₄ .

Comparative example 2

Preparation of secondary batteries

The secondary battery of Comparative Example 2 was produced according to the same manufacturing procedure as that of Example 1. The main difference lies in that: in the secondary battery of Example 1, the working electrode uses the negative electrode of Example 1; while in Comparative Example 2 In the secondary battery, the material of the working electrode is CoO.

Comparative example 3

Preparation of secondary batteries

The secondary battery of Comparative Example 3 was produced according to the same manufacturing procedure as Example 1. The main difference lies in that: in the secondary battery of Example 1, the working electrode uses the negative electrode of Example 1; while in Comparative Example 3 In the secondary battery, the material of the working electrode is CuO.

Comparative example 4

Preparation of secondary batteries

The secondary battery of Comparative Example 4 was produced according to the same manufacturing procedure as Example 1. The main difference lies in that: in the secondary battery of Example 1, the working electrode uses the negative electrode of Example 1; while in Comparative Example 4 In the secondary battery, the material of the working electrode is SnO ₂ .

Comparative example 5

Preparation of secondary batteries

The secondary battery of Comparative Example 5 was produced according to the same manufacturing procedure as Example 1. The main difference lies in that: in the secondary battery of Example 1, the working electrode uses the negative electrode of Example 1; while in Comparative Example 5 In the secondary battery, the material of the working electrode is SiO ₂ .

Comparative example 6

Preparation of secondary batteries

The secondary battery of Comparative Example 6 was produced according to the same manufacturing procedure as Example 1. The main difference lies in that: in the secondary battery of Example 1, the working electrode uses the negative electrode of Example 1; while in Comparative Example 6 In the secondary battery, the material of the working electrode is Fe ₂ O ₃ .

Comparative example 7

Preparation of secondary batteries

The secondary battery of Comparative Example 7 was produced according to the same manufacturing procedure as Example 1. The main difference is that in the secondary battery of Example 1, the working electrode is the negative electrode of Example 1; while in Comparative Example 7 In the secondary battery, the material of the working electrode is MnO.

Comparative example 8

Preparation of secondary batteries

The secondary battery of Comparative Example 8 was produced according to the same manufacturing procedure as Example 1. The main difference is that in the secondary battery of Example 1, the working electrode is the negative electrode of Example 1; while in Comparative Example 8 In the secondary battery, the material of the working electrode is MnO ₂ .

Comparative example 9

Preparation of secondary batteries

The secondary battery of Comparative Example 9 was produced according to the same manufacturing procedure as Example 1. The main difference is that in the secondary battery of Example 1, the working electrode uses the negative electrode of Example 1; while in Comparative Example 9 In the secondary battery, 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, charge and discharge cycle tests were performed on the secondary batteries of Examples 1 to 14 and the secondary batteries of Comparative Examples 1 to 9 respectively. .

Charge and discharge cycle test

The secondary batteries of Examples 1 to 14 and the secondary batteries of Comparative Examples 1 to 9 were tested for battery cycle life (cycle life) capacity in an environment of about 15°C to about 30°C, respectively, at a voltage of 0.01V to 3V. test. The measurement results are shown in Figures 2 to 15.

As can be seen from Figures 2 to 4, compared with the secondary battery of Comparative Example 1, after a high number of cycles (>250 times), the secondary batteries of Examples 1 to 3 all have better capacitance and Capacity maintenance rate.

Although the aforementioned test was not performed on the secondary battery including the cobalt copper tin oxide represented by formula (1) with x1 being 9 or 14, according to the foregoing description of the cobalt copper tin oxide and the test results of Example 1 , those skilled in the art will understand that a secondary battery including the cobalt copper tin oxide represented by formula (1) with x1 being 9 or 14 will have good capacitance and capacitance maintenance rate.

Although the aforementioned test has not been performed on the secondary battery including the cobalt copper tin oxide represented by formula (2) with x2 being 6 or 8, based on the foregoing description and the test results of Example 2, those skilled in the art should It is understood that the secondary battery including the cobalt copper tin oxide represented by formula (2) with x2 being 6 or 8 will have good capacitance and capacitance maintenance rate.

Although the aforementioned test has not been performed on the secondary battery including the cobalt copper tin oxide represented by formula (3) with x3 being 3 or 5, based on the foregoing description and the test results of Example 1, those skilled in the art should It is understood that the secondary battery including the cobalt copper tin oxide represented by formula (3) with x3 being 3 or 5 will have good capacitance and capacitance maintenance rate.

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

Although the aforementioned test was not conducted on secondary batteries including an oxide mixture 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 previous description, And the test results of Example 4, those skilled in the art should understand that the secondary test of the oxide mixture containing cobalt, copper and tin includes an atomic ratio of cobalt, copper and tin of 5:1:3 or 2:1:1. The battery will have good capacity and capacity retention.

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

Although the aforementioned test has not been performed on the secondary battery including the silicon-tin-iron oxide represented by formula (4) with x4 being greater than 21 to 34, those skilled in the art can, based on the foregoing description and the test results of Example 5, It should be understood that a secondary battery including the silicon tin iron oxide represented by formula (4) in which x4 is greater than 21 to 34 will have good capacitance and capacitance maintenance rate.

Although the aforementioned test has not been performed on the secondary battery including the silicon-tin-iron oxide represented by formula (5) or formula (6), those skilled in the art will understand based on the foregoing description and the test results of Example 5. The secondary battery including the silicon-tin-iron oxide represented by Formula (5) or Formula (6) will have good capacitance and capacitance retention rate.

Although the aforementioned test was not conducted on secondary batteries including an oxide mixture of silicon, tin and iron with an atomic ratio of silicon, tin and iron of 1:1:1 or 4:1:1, according to the previous description And the test results of Example 6, those skilled in the art should understand that the secondary test of the oxide mixture containing silicon, tin and iron includes an atomic ratio of silicon, tin and iron of 1:1:1 or 4:1:1. The battery will have good capacity and capacity retention.

It can be seen from Figure 8 that after a high number of cycles (>250 times), the secondary battery of Example 7 has good capacitance and capacitance retention rate.

Although the aforementioned test has not been performed on the secondary battery including the copper manganese silicon oxide represented by formula (7) with x7 being greater than 0 and less than 1, according to the foregoing description and the test results of Example 7, the technology in the field Personnel should understand that a secondary battery including the copper manganese silicon oxide represented by formula (7) in which x7 is greater than 0 and less than 1 will have good capacitance and capacitance maintenance rate.

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

Although the aforementioned tests were not performed on secondary batteries including an oxide mixture of copper, manganese and silicon in an atomic ratio of 1:1:1, 4:1:1 or 1:1:4, However, according to the foregoing description and the test results of Example 8, those skilled in the art should understand that the atomic ratio of copper, manganese and silicon is 1:1:1, 4:1:1 or 1:1:4. Secondary batteries made of oxide mixtures of copper, manganese and silicon will have good capacitance and capacity retention.

It can be seen from Figures 10 and 11 that compared with the secondary batteries of Comparative Examples 4, 8 and 9, the secondary batteries of Examples 9 and 10 have better capacitance after a high number of cycles (>250 times). and capacitance maintenance rate.

Although the aforementioned test has not been performed on the secondary battery including the tin-manganese nickel oxide represented by formula (8) with x8 ranging from 4 to less than 7, based on the foregoing description and the test results of Example 9, those skilled in the art It should be understood that a secondary battery including the tin-manganese nickel oxide represented by formula (8) in which x8 is 4 to less than 7 will have good capacitance and capacitance maintenance rate.

Although the aforementioned test was not performed on the secondary battery including the tin-manganese nickel oxide represented by formula (9), formula (10) or formula (11), according to the foregoing description and the test results of Example 9, the field Those skilled in the art should understand that a secondary battery including the tin-manganese nickel oxide represented by formula (9), formula (10) or formula (11) will have good capacitance and capacitance maintenance rate.

Although the aforementioned tests were not conducted on secondary batteries including an oxide mixture of tin, manganese and nickel in an atomic ratio of 1:1:1, 1:1:2 or 2:1:1, However, according to the foregoing description and the test results of Example 10, those skilled in the art should understand that the atomic ratio of tin, manganese and nickel is 1:1:1, 1:1:2 or 2:1:1. Secondary batteries using oxide mixtures of tin, manganese and nickel will have good capacity and capacity retention.

It can be seen from Figure 12 that after a high number of cycles (>250 times), the secondary battery of Example 11 has good capacitance and capacitance retention rate.

Although the aforementioned test has not been performed on the secondary battery including the manganese copper nickel oxide represented by formula (12) or formula (14), those skilled in the art will understand based on the foregoing description and the test results of Example 11. The secondary battery including the manganese copper nickel oxide represented by Formula (12) or Formula (14) will have good capacitance and capacitance maintenance rate.

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

Although the aforementioned test was not conducted on secondary batteries including an oxide mixture containing manganese, copper and nickel in an atomic ratio of 3:2:1 or 1:1:1, according to the previous description, And the test results of Example 12, those skilled in the art should understand that the secondary test of the oxide mixture containing manganese, copper and nickel includes an atomic ratio of manganese, copper and nickel of 3:2:1 or 1:1:1. The battery will have good capacity and capacity retention.

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

Although the aforementioned test was not conducted on secondary batteries including an oxide mixture of nickel, copper and tin with an atomic ratio of nickel, copper and tin of 2:1:3 or 1:2:3, according to the previous description And the test results of Example 13, those skilled in the art should understand that the secondary oxide mixture containing nickel, copper and tin has an atomic ratio of nickel, copper and tin of 2:1:3 or 1:2:3. The battery will have good capacity and capacity retention.

It can be seen from Figure 15 that after a high number of cycles (>250 times), the secondary battery of Example 14 has good capacitance and capacitance retention rate.

Although the aforementioned test has not been performed on the secondary battery including the nickel copper tin oxide represented by formula (15) with x15 being 3 or 9, based on the foregoing description and the test results of Example 14, those skilled in the art should It is understood that a secondary battery including a nickel copper tin oxide represented by formula (15) in which x15 is 3 or 9 will have good capacitance and capacitance retention.

Although the aforementioned test was not performed on the secondary battery including the nickel copper tin oxide represented by formula (16) or formula (17), those skilled in the art will understand based on the foregoing description and the test results of Example 14. The secondary battery including the nickel copper tin oxide represented by Formula (16) or Formula (17) will have good capacitance and capacitance maintenance rate.

Based on the above test results, it is confirmed that by using the negative electrode material for secondary batteries of the present invention to prepare the negative electrode, the secondary battery using the negative electrode can have good capacitance, stability and charge and discharge cycle life.

In addition, compared with commercial graphite (theoretical capacitance value is 372 mAh/g), the secondary battery using the negative electrode made of the negative electrode material for secondary batteries of the present invention has a higher electric capacity, so it represents the secondary battery of the present invention. Anode materials for batteries can effectively improve battery performance.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, but not to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features can be equivalently replaced; and these modifications or substitutions do not deviate from the essence of the corresponding technical solutions from the technical solutions of the embodiments of the present invention. scope.

Claims (4)

1. A negative electrode material for secondary batteries, characterized in that it includes: Oxide mixture, a mixing step is performed from 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 at least one of NiO and Ni ₂ O ₃ Obtained, 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, wherein the mixing step It also includes mixing oxides containing M, wherein M is selected from at least one element among Cr, W, Si, Cu, Zn, Al, Ti, In and Mo, and relative to the total atoms of the metal elements in the oxide mixture Number, the atomic number ratio of M ranges from greater than 0 to less than or equal to 10atomic%. 2. A negative electrode for secondary batteries, characterized in that it includes: current collector; and The negative electrode material layer is arranged on the current collector and includes the negative electrode material for secondary batteries according to claim 1. 3. A secondary battery, characterized by comprising: positive electrode; A negative electrode, arranged separately from the positive electrode, wherein the negative electrode is the negative electrode for a secondary battery as claimed in claim 2; An electrolyte is provided between the positive electrode and the negative electrode; and A packaging structure covers the positive electrode, the negative electrode and the electrolyte. 4. The secondary battery according to claim 3, further comprising an isolation film disposed between the positive electrode and the negative electrode, and the isolation film, the positive electrode and the negative electrode define a capacity accommodating area, and the electrolyte is disposed in the accommodating area.