CN114725368B - 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 material for secondary battery, negative electrode and secondary battery

The present invention is a divisional application of the invention patent application with the application number 202010057891.X and the invention name "Anode Material for Secondary Battery, Anode and Secondary Battery" filed on January 16, 2020.

technical field

The 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 with the characteristics of light weight, high voltage value and high energy density, which can be repeatedly charged and discharged, is increasing day by day. Therefore, the performance requirements for secondary lithium batteries such as light weight and durability, high voltage, high energy density and high safety are becoming higher and higher. 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 the battery made from it is limited. Therefore, finding a secondary battery electrode material with high stability and high capacity is one of the goals that those skilled in the art want to achieve.

Contents of the invention

In view of this, the present invention provides a negative electrode material and a negative electrode used in a secondary battery and enabling the secondary battery to have good capacity and stability.

The secondary battery negative electrode material provided by one embodiment of the present invention comprises cobalt copper tin oxide represented by one of the following formula (1) to formula (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),

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

Another embodiment of the present invention provides a secondary battery negative electrode material comprising 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 them, 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 secondary battery negative electrode material comprising silicon tin iron oxide represented by one of the following formula (4) to formula (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),

Wherein x4 is 21～34, x4 is 3～5, x6 is 6～11.5, 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 atomic number of elements other than oxygen in the silicon-tin-iron oxide represented by formula (5) or formula (6), the atomic number ratio of M is 10atomic% or less.

Another embodiment of the present invention provides a negative electrode material for a secondary battery comprising 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. The oxide mixture obtained by mixing at least one of them, 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 secondary battery negative electrode material comprising copper manganese silicon oxide represented by the following formula (7):

Cu _x7 Mn _7-x7 SiMO ₁₂ formula (7),

Wherein x7 is greater than 0 to 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 ratio of M are 10 atomic % or less.

Another embodiment of the present invention provides a secondary battery negative electrode material comprising 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 performing a mixing step on at least one of ₃ O ₄ , 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 secondary battery negative electrode material comprising tin manganese nickel oxide represented by one of the following formula (8) to formula (11):

Sn ₁ Mn ₂ Ni ₁ MO _x8 formula (8),

Sn ₁ Mn ₁ Ni ₂ MO _x9 formula (9),

Sn ₂ Mn ₁ Ni ₁ MO _x10 formula (10),

Sn ₁ Mn ₁ Ni ₁ MO _x11 formula (11),

Wherein x8 is 4-7, x9 is 4-7, x10 is 4-7, x11 is 3-6, and M is at least one element selected from Cr, Mn, Zn, Al, Ti, In, Mo and W , and 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), the atomic ratio of M is 10atomic% or less.

Another embodiment of the present invention provides a secondary battery negative electrode material comprising 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 _Ni2O3 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 secondary battery negative electrode material comprising 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 number of atoms of the 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 secondary battery negative electrode material comprising 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 _Ni2O3 , wherein the atomic ratio of manganese, copper, and nickel in _the oxide mixture is 3:2:1, 2:1:1, or 1:1:1.

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

NiCuSn ₂ MO _x15 formula (15),

Ni ₂ CuSn ₃ MO _x16 formula (16),

NiCu ₂ Sn ₃ MO _x17 formula (17),

Wherein x15 is 3, 6 or 9, x16 is 4, 6 or 9, x17 is 4, 6 or 9, and M is at least one selected from Cr, Mn, Zn, Al, Ti, In, Mo, W and Co An element, and the atomic number ratio of M is 10 atomic% or less with respect to the total atomic number 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 secondary battery negative electrode material comprising 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.

A negative electrode for a secondary battery provided by an embodiment of the present invention includes a current collector and a negative electrode material layer. The negative electrode material layer is disposed on the current collector and includes any negative electrode material for secondary batteries as described above.

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 is arranged separately from the positive electrode, and the negative electrode is the above-mentioned negative electrode for a secondary battery. The electrolyte is disposed between the positive electrode and the negative electrode. The encapsulation structure covers the positive electrode, the negative electrode and the electrolyte.

Based on the above, the negative electrode material for secondary batteries of the present invention includes a metal oxide represented by one of formula (1) to formula (17), or a metal oxide containing cobalt, copper and tin with a specific ratio of atomic number of elements. oxide mixtures containing silicon, oxide mixtures of tin and iron, oxide mixtures containing copper, manganese and silicon, oxide mixtures containing tin, manganese and nickel, oxide mixtures containing manganese, copper and nickel, or The oxide mixture containing nickel, copper and tin makes it applicable to secondary batteries, and makes the secondary batteries have good capacity, stability and charge-discharge cycle life.

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

Description of 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 principles of the invention.

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

Fig. 2 is the cycle life graph of the secondary battery of embodiment 1 and comparative example 1;

Fig. 3 is the cycle life graph of the secondary battery of embodiment 2 and comparative example 1;

Fig. 4 is the cycle life graph of the secondary battery of embodiment 3 and comparative example 1;

Fig. 5 is the cycle life graph of the secondary battery of embodiment 4 and comparative example 2～4;

Fig. 6 is the cycle life graph of the secondary battery of embodiment 5 and comparative examples 4-6;

Fig. 7 is the cycle life graph of the secondary battery of embodiment 6 and comparative example 4～6;

Fig. 8 is the cycle life graph of the secondary battery of embodiment 7;

Fig. 9 is the cycle life graph of the secondary battery of embodiment 8 and comparative examples 3, 5, 7;

Fig. 10 is the cycle life graph of the secondary battery of embodiment 9 and comparative examples 4, 8-9;

Fig. 11 is the cycle life graph of the secondary battery of embodiment 10 and comparative examples 4, 8-9;

Fig. 12 is the cycle life graph of the secondary battery of embodiment 11;

Fig. 13 is the cycle life graph of the secondary battery of embodiment 12 and comparative examples 3, 8-9;

Fig. 14 is the cycle life graph of the secondary battery of embodiment 13 and comparative examples 3-4, 9;

FIG. 15 is a graph showing the cycle life of the secondary battery of Example 14. FIG.

Explanation of reference numbers

100: secondary battery;

102: negative pole;

102a, 104a: current collectors;

102b: negative electrode material layer;

104: positive pole;

104b: positive electrode material layer;

106: isolation film;

108: electrolyte;

110: accommodation area;

112: encapsulation structure.

Detailed ways

Herein, a range indicated by "one value to another value" is a general representation to avoid enumerating all values in the range in the specification. Therefore, the description of a specific numerical range covers any numerical value in the numerical range and the smaller numerical range bounded by any numerical value in the numerical range, as if the arbitrary numerical value and the smaller numerical value are expressly written in the specification. same range.

As used herein, "about," "approximately," "essentially," or "essentially" includes the stated value and the average within an acceptable range of deviation from the particular value as determined by one of ordinary skill in the art, taking into account the The measurement in question and the specific amount of error associated with the measurement (ie, limitations of the measurement system). For example, "about" can mean within one or more standard deviations of the stated value, or for example within ±30%, ±20%, ±15%, ±10%, ±5%. Furthermore, "about", "approximately", "essentially" or "substantially" used herein can select a more acceptable range of deviation or standard deviation according to the nature of measurement or other properties, instead of using a standard deviation Applies to all properties.

In order to prepare the negative electrode material that can be applied to the negative electrode of the secondary battery and make the secondary battery have good stability and capacity, the present invention proposes the negative electrode material that can achieve the above advantages. Hereinafter, specific embodiments are given as descriptions of how the present invention can be reliably implemented.

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

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

cobalt copper tin oxide

In this embodiment, the cobalt-copper-tin oxide can 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 _x3 formula (3).

In formula (1), x1 is 8, 9 or 14. In formula (2), x2 is 4, 6 or 8. In formula (3), x3 is 3, 4 or 5. If x1, x2, and x3 respectively meet the specific values listed above, the secondary battery using the negative electrode material comprising the cobalt-copper-tin oxide has excellent capacity, increased 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 atomic number ratio of M is 10 atomic % or less with respect to the total atomic number of metal elements in the cobalt copper tin oxide represented by formula (1), formula (2) or formula (3). In other words, the cobalt-copper-tin oxide represented by formula (1), formula (2) or formula (3) may not contain the element M, but only include four elements, namely cobalt, copper, tin and oxygen. It is worth mentioning that, compared with the cobalt copper tin oxide not containing the element M, the cobalt copper tin oxide containing the atomic number ratio greater than 0 and less than or equal to 10atomic% M has an increase in electrical conductivity of about 10% or more. In addition, in the present embodiment, in the case of the cobalt-copper-tin oxide containing the element M, M may substitute a part of cobalt, copper, and/or tin. For example, in one embodiment, M can replace a part of cobalt; in another embodiment, M can replace a part of cobalt and a part of copper; in yet another embodiment, M can replace a part of cobalt, a part of Copper and a part of tin, but the present invention is not limited thereto. It should be noted that in this embodiment, the number of atoms 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% margin of error.

In this embodiment, the cobalt copper tin oxide represented by formula (1), formula (2) or formula (3) may have a spinel structure (Spinel structure), perovskite structure (Perovskite structure), chloride Sodium chloride structure or Chalcopyrite structure. It is worth mentioning that the cobalt-copper-tin oxide represented by formula (1), formula (2) or formula (3) allows more oxygen vacancies by having the above-mentioned structure. In the secondary battery of tin oxide negative electrode material, lithium ions can enter and exit conveniently and quickly, thus effectively improving the lithium ion diffusion rate and ion conductivity. In addition, the cobalt-copper-tin oxide represented by formula (1), formula (2) or formula (3) can not easily collapse during charging and discharging by having the above-mentioned structure, thereby applying the The secondary battery of the negative electrode material can maintain a 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-mentioned range, it is advantageous to form a negative electrode with good characteristics. In the embodiment of producing cobalt-copper-tin oxide by solid-state method, in order to obtain the above-mentioned cobalt-copper-tin oxide with a specific average particle size range, mortar, ball mill (ball mill), sand grinder, vibrating ball mill or planetary type ball mill (planet ball mill) for grinding, 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 _x6 formula (6).

In formula (4), x4 is 21 to 34. In formula (5), x5 is 3 to 5. In formula (6), x6 is 6 to 11.5. If x4, x5, and x6 are respectively within the above ranges, the secondary battery to which the negative electrode material including the silicon tin iron oxide is applied has excellent capacity and improved capacity retention.

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 atomic ratio of M to the total atomic number of elements other than oxygen in the silicon tin iron oxide represented by formula (4), formula (5) or formula (6) is 10 atomic % or less. In other words, the silicon-tin-iron oxide represented by formula (4), formula (5) or formula (6) may not contain the element M, but only include four elements, namely silicon, tin, iron and oxygen. It is worth mentioning that, compared with silicon-tin-iron oxides not containing element M, silicon-tin-iron oxides containing M with an atomic number ratio greater than 0 and less than or equal to 10atomic% have conductivity increased by more than about 10%. In addition, in the present embodiment, in the case of the silicon-tin-iron oxide containing the element M, M may substitute a part of silicon, tin, and/or iron. For example, in one embodiment, M can replace a portion of silicon; in another embodiment, M can replace a portion of silicon and a portion of tin; in yet another embodiment, M can replace a portion of silicon, a portion of tin and a part of iron, but the present invention is not limited thereto. It should be noted that in this embodiment, the number of atoms 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% margin of error.

In this embodiment, the silicon tin iron oxide represented by formula (4), formula (5) or formula (6) may have a rhombohedral structure, a cubic ferromanganese 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 more oxygen vacancies by having the above-mentioned structure. In the secondary battery of the negative electrode material of iron oxide, lithium ions can enter and exit conveniently and quickly, thus effectively improving the diffusion rate of lithium ions and the ion conductivity. In addition, the silicon-tin-iron oxide represented by formula (4), formula (5) or formula (6) can not easily collapse during charging and discharging by having the above-mentioned structure, thereby applying the silicon-tin-iron oxide The secondary battery of the negative electrode material can maintain a 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-mentioned range, it is advantageous to form a negative electrode with good characteristics. In the embodiment of producing silicon tin iron oxide by solid state method, in order to obtain the silicon tin iron oxide having the above-mentioned specific average particle size range, can use mortar, ball mill (ball mill), sand grinder, vibration ball mill or planetary type ball mill (planet ball mill) for grinding, 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 to which the negative electrode material including the copper manganese silicon oxide is applied has excellent capacity and improved capacity retention.

In formula (7), M may be at least one element selected from Cr, Sn, Ni, Co, Zn, Al, Ti, In, Mo, and W. The atomic ratio of M to the total atomic number 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 the formula (7) may not contain the element M, but only include four elements, namely copper, manganese, silicon and oxygen. It is worth mentioning that, compared with copper-manganese-silicon oxides that do not contain element M, copper-manganese-silicon oxides containing M with an atomic number ratio greater than 0 and less than or equal to 10atomic% have electrical conductivity increased by more than about 10%. In addition, in the present embodiment, in the case of copper-manganese-silicon oxide containing the element M, M may substitute for a part of copper, manganese, and/or silicon. For example, in one embodiment, M can replace a part of copper; in another embodiment, M can replace a part of copper and a part of manganese; in yet another embodiment, M can replace a part of copper, a part of manganese and a part of silicon, but the present invention is not limited thereto. It should be noted that in this embodiment, the atomic number value 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 the 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 the formula (7) has the above-mentioned structure, whereby in a secondary battery using a negative electrode material including the copper-manganese-silicon oxide, the overpotential (overpotential) The resulting energy loss can be reduced, the lithium ion diffusion rate and ion conductivity can be improved, and the charge-discharge cycle life can be improved.

In this embodiment, the average particle size of the copper-manganese-silicon oxide is, for example, between about 10 nm and about 1 mm. If the average particle size of the copper manganese silicon oxide falls within the above range, it will be advantageous to form a negative electrode with good characteristics. In the embodiment of producing copper-manganese-silicon oxide by 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 (ball mill), sand grinder, vibrating ball mill or planetary type ball mill (planet ball mill) for grinding, 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 _x8 formula (8),

Sn ₁ Mn ₁ Ni ₂ MO _x9 formula (9),

Sn ₂ Mn ₁ Ni ₁ MO _x10 formula (10),

Sn ₁ Mn ₁ Ni ₁ MO _x11 formula (11).

In formula (8), x8 is 4 to 7. In formula (9), x9 is 4 to 7. In formula (10), x10 is 4 to 7. In formula (11), x11 is 3 to 6. If x8, x9, x10, and x11 are respectively within the above ranges, a secondary battery to which the negative electrode material including the tin-manganese-nickel oxide is applied has excellent capacity and improved capacity retention.

In each of formula (8), formula (9), formula (10) and formula (11), M can be at least one selected from Cr, Mn, Zn, Al, Ti, In, Mo and W kind of element. The atomic number ratio of M is 10 atomic % or less with respect to the total atomic number 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 the tin-manganese-nickel oxide not containing the element M, the tin-manganese-nickel oxide containing M with an atomic number ratio greater than 0 and less than or equal to 10atomic% has a conductivity increased by more than about 10%. In addition, in the present embodiment, in the case of the tin-manganese-nickel oxide containing the element M, M may substitute a part of tin, manganese, and/or nickel. For example, in one embodiment, M can replace a part of tin; in another embodiment, M can replace a part of tin and a part of manganese; in yet another embodiment, M can replace a part of tin, a part of manganese and a part of nickel, but the present 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 vary due to the formation of oxygen vacancies or Diffusion is not uniform with a margin of error 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 red gold structure (Rtile structure) ), Rock salt structure. 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 by having the above-mentioned structure, thereby being used in In the secondary battery comprising the negative electrode material of tin-manganese-nickel oxide, lithium ions can enter and exit conveniently and quickly, thus effectively improving the diffusion rate of lithium ions and the ion conductivity. In addition, the tin-manganese-nickel oxide represented by the formula (8), the formula (9), the formula (10) or the formula (11) can not easily collapse during the charging and discharging process by having the above-mentioned structure, thereby applying the The secondary battery made of tin-manganese-nickel oxide negative electrode material can maintain a good charge-discharge cycle life.

In this embodiment, the average particle size of the tin-manganese-nickel oxide is, for example, between about 10 nm and about 1 mm. If the average particle size of the tin-manganese-nickel oxide falls within the above-mentioned range, it is advantageous to form a negative electrode with good characteristics. In the embodiment of producing tin-manganese-nickel oxide by solid-state method, in order to obtain the above-mentioned tin-manganese-nickel oxide with a specific average particle size range, mortar, ball mill (ball mill), sand grinder, vibration ball mill or planetary type ball mill (planet ball mill) for grinding, 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 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 comprising the manganese-copper-nickel oxide has excellent High capacity and improved capacity 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 atomic number ratio of M is 10 atomic % or less with respect to the total atomic number of metal elements in the manganese-copper-nickel oxide represented by formula (12), formula (13) or formula (14). In other words, the manganese-copper-nickel oxide represented by formula (12), formula (13) or formula (14) may not contain the element M, but only include four elements, namely manganese, copper, nickel and oxygen. It is worth mentioning that, compared with the manganese-copper-nickel oxide not containing the element M, the manganese-copper-nickel oxide containing M with an atomic number ratio greater than 0 and less than or equal to 10atomic% has a conductivity increased by more than about 10%. In addition, in the present embodiment, in the case of the manganese-copper-nickel oxide containing the element M, M may substitute a part of manganese, copper, and/or nickel. For example, in one embodiment, M can replace a part of manganese; in another embodiment, M can replace a part of manganese and a part of copper; in yet another embodiment, M can replace a part of manganese, a part of Copper and a part of nickel, but the present invention is not limited thereto. It should be noted that, in this embodiment, the number of atoms 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% margin of error.

In this embodiment, the manganese-copper-nickel oxide represented by formula (12), formula (13) or formula (14) may have a tetragonal structure, a spinel structure, a perovskite 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) allows more oxygen vacancies by having the above-mentioned structure. In the secondary battery of the negative electrode material of nickel oxide, lithium ions can enter and exit conveniently and quickly, thus effectively improving the diffusion rate of lithium ions and the ion conductivity. In addition, the manganese-copper-nickel oxide represented by formula (12), formula (13) or formula (14) can not easily collapse during the charging and discharging process by having the above-mentioned structure, thereby applying the The secondary battery of the negative electrode material can maintain a 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-mentioned range, it is advantageous to form a negative electrode with good characteristics. In the embodiment of producing the manganese-copper-nickel oxide by the solid state method, in order to obtain the above-mentioned manganese-copper-nickel oxide with a specific average particle size range, a mortar, a ball mill (ball mill), a sand grinder, a vibrating ball mill or a planetary type ball mill (planet ball mill) for grinding, but the present invention is not limited thereto.

nickel copper tin oxide

In this embodiment, the nickel-copper-tin oxide may 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 formula (15), x15 is 3, 6 or 9. In formula (16), x16 is 4, 6 or 9. In formula (17), x17 is 4, 6 or 9. If x15, x16 and x17 respectively meet the specified values listed above, the secondary battery using the negative electrode material including the nickel-copper-tin oxide has excellent capacity and enhanced capacity retention.

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 atomic number ratio of M is 10 atomic % or less with respect to the total atomic number of metal elements in the nickel-copper-tin oxide represented by formula (15), formula (16), or formula (17). In other words, the nickel-copper-tin oxide represented by formula (15), formula (16) or formula (17) may not contain the element M, but only include four elements, namely nickel, copper, tin and oxygen. It is worth mentioning that, compared with nickel-copper-tin oxides that do not contain element M, nickel-copper-tin oxides containing M with an atomic number ratio greater than 0 and less than or equal to 10atomic% have electrical conductivity increased by more than about 15%. In addition, in the present embodiment, in the case of the nickel-copper-tin oxide containing the element M, M may substitute a part of nickel, copper, and/or tin. For example, in one embodiment, M can replace a part of nickel; in another embodiment, M can replace a part of nickel and a part of copper; in yet another embodiment, M can replace a part of nickel, a part of Copper and a part of tin, but the present invention is not limited thereto. It should be noted that in this embodiment, the number of atoms 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% margin of error.

In this embodiment, the nickel copper tin oxide represented by formula (15), formula (16) or formula (17) may have a perovskite structure (Perovskite structure), sodium chloride structure (Sodium chloride structure) or yellow Chalcopyrite structure. It is worth mentioning that the nickel-copper-tin oxide represented by formula (15), formula (16) or formula (17) allows more oxygen vacancies by having the above-mentioned structure, thereby applying In the secondary battery of tin oxide negative electrode material, lithium ions can enter and exit conveniently and quickly, thus effectively improving the lithium ion diffusion rate and ion conductivity. In addition, the nickel-copper-tin oxide represented by the formula (15), the formula (16) or the formula (17) can not easily collapse during the charging and discharging process by having the above-mentioned structure, thereby applying the The secondary battery of the negative electrode material can maintain a 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. When the average particle size of the nickel-copper-tin oxide falls within the above-mentioned range, it is advantageous to form a negative electrode with good characteristics. In the embodiment of producing nickel-copper-tin oxide by solid-state method, in order to obtain the above-mentioned nickel-copper-tin oxide with a specific average particle size range, a mortar, a ball mill (ball mill), a sand grinder, a vibration ball mill or a planetary type ball mill (planet ball mill) for grinding, but the present invention is not limited thereto.

In addition, in this embodiment, the preparation method of the oxide mixture containing four or more elements includes, for example, a mixing step. The mixing step is, for example, performed 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 the oxide mixture containing more than four elements is prepared by using a physical dry mixing method, the mixing temperature may be room temperature, for example, about 25° C. or higher. In the embodiment of using a physical wet mixing method to prepare the oxide mixture containing more than four elements, the mixing temperature may be room temperature, for example, above about 25° C., 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, an oxide mixture 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. Hereinafter, the above various oxide mixtures will be described in detail.

Oxide mixture containing cobalt, copper and tin

In this embodiment, the oxide mixture containing cobalt, copper and tin can 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 mixing 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 number ratio of cobalt, copper and tin meets the specific ratios listed above, the secondary battery using the negative electrode material comprising the oxide mixture containing cobalt, copper and tin has excellent electric capacity and improved electric capacity. capacity retention.

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

In this embodiment, the negative electrode is made by using a negative electrode material including an oxide mixture containing cobalt, copper and tin, so that lithium ions can move in and out through different paths, so that the polarization effect can be slowed down. And the charge-discharge cycle life can be improved. In this way, the capacity of the secondary battery using the negative electrode material comprising the oxide mixture containing cobalt, copper and tin can be significantly increased. In addition, tin oxide as the negative electrode material can achieve high capacity performance, copper oxide as the negative electrode material can achieve good cycle life, and cobalt oxide as the negative electrode material can achieve good lithium ion conductivity, so the application includes The secondary battery of the negative electrode material of the oxide mixture obtained by mixing cobalt oxide, copper oxide, and tin oxide can have excellent performance and is safe.

A mixture of oxides containing silicon, tin and iron

In this embodiment, the oxide mixture containing silicon, tin and iron can 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 is obtained by performing a mixing step. That is, the oxide mixture containing silicon, tin, and iron can be obtained by mixing 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 number ratio of silicon, tin and iron meets the specific ratios listed above, the secondary battery using the negative electrode material comprising the oxide mixture containing silicon, tin and iron has excellent electric capacity and improved electric capacity. capacity retention.

In this embodiment, at least one of SiO ₂ and SiO, at least one of SnO and SnO ₂ , and at least one of Fe ₂ O ₃ , Fe ₃ O ₄ and FeO can be selectively mixed during the mixing step. At least one of is mixed with an oxide containing M, wherein M is at least one element selected from 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 ratio of the atomic number of M is greater than 0 to less than or equal to 10atomic%. It is worth mentioning that, compared with oxide mixtures containing silicon, tin and iron that are not mixed with M-containing oxides, mixed with M-containing oxides and the atomic number ratio of M is greater than 0 to less than or equal to 10atomic % oxide mixtures containing silicon, tin and iron have an increase in electrical conductivity of more than about 10%. It should be noted that, in this embodiment, the value of the atomic number ratio of elements in the oxide mixture containing silicon, tin and iron may have an error range of ±10% due to the formation or uneven diffusion of oxygen vacancies.

In this embodiment, the negative electrode is fabricated by using a negative electrode material including an oxide mixture containing silicon, tin and iron, so that lithium ions can move in and out through different paths, so that the polarization effect can be slowed down. And the charge-discharge cycle life can be improved. In this way, the 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 as a negative electrode material can achieve high capacity performance, iron oxide as a negative electrode material can achieve good cycle life, and silicon oxide as a negative electrode material can achieve good lithium ion conductivity, so applications including The secondary battery of the negative electrode material of the oxide mixture obtained by mixing silicon oxide, tin oxide, and iron oxide can have excellent performance and is safe.

Oxide mixture containing copper, manganese and silicon

In this embodiment, the oxide mixture containing copper, manganese and silicon may be 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 At least one of ₃ O ₄ is obtained through a mixing step. That is, the oxide mixture containing copper, manganese, and silicon can be obtained by mixing 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 may be 1:1:1, 1:4:1, 4:1:1 or 1 :1:4. If the atomic number ratio of copper, manganese and silicon meets the specific ratios listed above, the secondary battery using the negative electrode material comprising the oxide mixture containing copper, manganese and silicon has excellent electric capacity and improved electric capacity. capacity retention.

In this embodiment, during 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 At least one of ₃ O ₄ is mixed with an oxide containing M, wherein M is 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 except oxygen in the oxide mixture containing copper, manganese and silicon, the atomic number ratio of M is greater than 0 to less than or equal to 10atomic%. It is worth mentioning that, compared with the oxide mixture containing copper, manganese and silicon that is not mixed with the oxide containing M, the oxide containing M is mixed and the atomic number ratio of M is greater than 0 to less than or equal to 10atomic % oxide mixtures containing copper, manganese and silicon have an increase in electrical conductivity of more than about 10%. It should be noted that, in this embodiment, the value of the atomic number ratio of the elements in the oxide mixture containing copper, manganese and silicon may have an error range of ±10% due to the formation or uneven diffusion of oxygen vacancies.

In this embodiment, the oxide mixture containing copper, manganese, and silicon obtained by mixing copper oxide, manganese oxide, and silicon oxide is due to the interaction between the various oxides. The resulting synergistic effect makes it possible to significantly increase the capacity of the secondary battery using the negative electrode material comprising the oxide mixture containing copper, manganese and silicon. In addition, in this embodiment, the negative electrode is fabricated by using a negative electrode material including an oxide mixture containing copper, manganese and silicon, so that lithium ions can move in and out through different paths, so that the polarization effect can be Slow down, and the charge-discharge cycle life can be improved. In addition, copper oxide can achieve good cycle life as a negative electrode material, manganese oxide can achieve low overpotential as a negative electrode material, and silicon oxide can achieve good lithium ion conductivity as a negative electrode material. 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.

Mixture of oxides containing tin, manganese and nickel

In this embodiment, the oxide mixture containing tin, manganese and nickel can 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 is obtained through a mixing step. That is to say, the oxide mixture containing tin, manganese and nickel can be obtained by mixing 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 may be 1:2:1, 1:1:1, 1:1:2 or 2 :1:1. If the atomic number ratio of tin, manganese and nickel meets the specific ratios listed above, the secondary battery using the negative electrode material comprising the oxide mixture containing tin, manganese and nickel has excellent electric capacity and improved electric capacity. capacity retention.

In this embodiment, 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, wherein M is 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 the element M. Relative to the total number of atoms of metal elements in the oxide mixture containing tin, manganese and nickel, the atomic number ratio of M is greater than 0 to less than or equal to 10atomic%. 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 greater than 0 to less than or equal to 10atomic % oxide mixtures containing tin, manganese and nickel have an increase in electrical conductivity of about 10% or more. It should be noted that, in this embodiment, the value of the atomic number ratio of the elements in the oxide mixture containing tin, manganese and nickel may 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 mixing tin oxide, manganese oxide, and nickel oxide is due to the interaction between the various oxides. The resulting synergistic effect makes it possible to significantly increase the capacity of the secondary battery using the negative electrode material comprising the oxide mixture containing tin, manganese and nickel. In addition, in the present embodiment, the negative electrode is fabricated by using a negative electrode material including an oxide mixture containing tin, manganese and nickel, so that lithium ions can move in and out through different paths, so that the polarization effect can be Slow down, and the charge-discharge cycle life can be improved. In addition, tin oxide as negative electrode material can achieve high capacity performance, manganese oxide as negative electrode material can achieve low overpotential, and nickel oxide as negative electrode material can achieve good lithium ion conductivity, so applications including The secondary battery of the negative electrode material of the oxide mixture obtained by mixing tin oxide, manganese oxide, and nickel oxide has excellent performance and is safe.

Mixture of oxides containing manganese, copper and nickel

In this embodiment, the oxide mixture containing manganese, copper and nickel can 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, the oxide mixture containing manganese, copper, and nickel can be obtained by mixing 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 number ratio of manganese, copper and nickel meets the specific ratios listed above, the secondary battery using the negative electrode material comprising the oxide mixture containing manganese, copper and nickel has excellent electric capacity and improved electric capacity. capacity retention.

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 Mix with at least one of Ni ₂ O ₃ and an oxide containing M, wherein M is 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 number of atoms of metal elements in the oxide mixture containing manganese, copper and tin, the atomic number ratio of M is greater than 0 to less than or equal to 10atomic%. It is worth mentioning that, compared with the oxide mixture containing manganese, copper 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 greater than 0 to less than or equal to 10atomic % oxide mixtures containing manganese, copper and nickel have an increase in electrical conductivity of about 5% or more. It should be noted that, in this embodiment, the value of the atomic ratio of the elements in the oxide mixture containing manganese, copper and nickel may have an error range of ±10% due to the formation or uneven diffusion of oxygen vacancies.

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

Mixture of oxides containing nickel, copper and tin

In this embodiment, the oxide mixture containing nickel, copper and tin can be 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, the oxide mixture containing nickel, copper, and tin can be obtained by mixing 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 number ratio of nickel, copper and tin meets the specific ratios listed above, the secondary battery using the negative electrode material comprising the oxide mixture containing nickel, copper and tin has excellent electric capacity and improved electric capacity. capacity retention.

In this embodiment, during the mixing step, at least one of _Ni2O3 and NiO, at least one of CuO and _Cu2O , and at least one of _SnO and _SnO2 can be selectively mixed with M-containing oxides are mixed together, wherein M is at least one element selected from Cr, Mn, Zn, Al, Ti, In, Mo, W and Co. That is, the oxide mixture containing nickel, copper and tin may optionally include the element M. Relative to the total number of atoms of metal elements in the oxide mixture containing nickel, copper and tin, the atomic number ratio of M is greater than 0 to less than or equal to 10atomic%. It is worth mentioning that, compared with the oxide mixture containing nickel, 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 % oxide mixtures containing nickel, copper, and tin have an increase in electrical conductivity of about 8% or more. It should be noted that, in this embodiment, the value of the atomic number ratio of elements in the oxide mixture containing nickel, copper and tin may have an error range of ±10% due to the formation or uneven diffusion of oxygen vacancies.

In this embodiment, the negative electrode is fabricated by using a negative electrode material including an oxide mixture containing nickel, copper and tin, so that lithium ions can move in and out through different paths, so that the polarization effect can be slowed down. And the charge-discharge cycle life can be improved. In this way, the 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 as negative electrode material can achieve high capacity performance, copper oxide as negative electrode material can achieve good cycle life, and nickel oxide as negative electrode material can achieve good lithium ion conductivity, so the application includes The secondary battery of the negative electrode material of the oxide mixture obtained by mixing nickel oxide, copper oxide, and tin oxide has excellent performance and is safe.

Another embodiment of the present invention also proposes a secondary battery, which uses any one of the negative electrode materials proposed in the foregoing embodiments.

FIG. 1 is a schematic cross-sectional view of a secondary battery according to an embodiment of the present invention. Referring to FIG. 1 , a secondary battery 100 may include a negative electrode 102 , a positive electrode 104 , an electrolyte 108 and an encapsulation 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 can be metal foil, such as copper foil, nickel foil or high-conductivity stainless steel foil. In this embodiment, the thickness of the current collector 102a may be between about 5 μm and about 300 μm.

In this embodiment, the negative electrode material layer 102b includes any one of the negative electrode materials proposed in the foregoing 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 coconductor and a binder. In this embodiment, the co-conducting agent can be natural graphite, artificial graphite, carbon black (carbon black), conductive carbon (such as VGCF, Super P, KS4, KS6 or ECP), acetylene black (acetylene black), Ketjen Black (Ketjen black), carbon whisker (carbon whisker), carbon fiber, metal powder, metal fiber or conductive ceramics material. In detail, the co-conductor is used to improve the electrical contact between the negative electrode materials. In this embodiment, the adhesive may be polyvinyl difluoride (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 is arranged separately from the negative electrode 102 . 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 can be metal foil, such as copper foil, nickel foil, aluminum foil or high-conductivity stainless steel foil. In this embodiment, the thickness of the current collector 104a may be between about 5 μm and about 300 μm.

In this embodiment, the positive electrode material layer 104b includes a positive electrode material. In this embodiment, the positive electrode material may include lithium cobalt oxide (LiCoO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), lithium nickelate (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 104 a 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 a binder. In this embodiment, the adhesive may be polyvinyl difluoride (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 provided between the negative electrode 102 and the positive electrode 104 . The electrolyte 108 may include a liquid electrolyte, a gel electrolyte, a molten salt electrolyte, or a solid electrolyte.

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

In this embodiment, the secondary battery 100 includes a separator 106 to isolate the negative electrode 102 from the positive electrode 104 and allow ions to penetrate, but the present invention is not limited thereto. In other embodiments, the electrolyte 108 is a solid electrolyte, and the 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 package structure 112 is, for example, aluminum foil or stainless steel.

In this embodiment, the structure of the secondary battery 100 is not limited to that shown in FIG. 1 . In other embodiments, the secondary battery 100 may have the following structure: a winding structure made by winding the negative electrode, positive electrode, and a separator provided if necessary, or a laminated structure made by laminating them in a flat plate shape. layered structure. In addition, in this embodiment, the secondary battery 100 is, for example, a paper battery, a button battery, a coin battery, a laminate battery, a cylindrical battery, or a square battery.

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

Hereinafter, the features of the present invention will be described more specifically with reference to Examples 1-14 and Comparative Examples 1-9. Although the following Examples 1 to 14 are described, the materials used, their amounts and ratios, processing details, processing flow, and the like can be appropriately changed without departing from the scope of the present invention. Therefore, the present invention should not be limitedly interpreted by the Examples described below.

Example 1

Preparation of negative electrode materials

At room temperature, CoO powder (precursor containing cobalt), CuO powder (precursor containing copper), SnO powder (precursor containing tin), and W oxide powder (precursor containing element M) were separately mixed by ball mill. After grinding, the powders were mixed and pressed into green pellets with a diameter of about 1 cm. The green body is placed in a high-temperature furnace to obtain the cobalt-copper-tin oxide bulk material (i.e. the negative electrode material of Example 1) shown by the aforementioned formula (1), wherein x1 is 8, the element M is W, and the element M is The atomic number ratio is about 1-10 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 binder (that is, sodium carboxymethylcellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Then, add zirconia balls and mix the slurry for about 30 minutes to form the negative electrode slurry. Then, use a scraper (100 μm) to coat the slurry on the copper foil (the aforementioned current collector) and make it uniform After scraping, place the copper foil coated with slurry in a vacuum oven and dry it at about 110°C for about 12 hours. After that, cut the dried copper foil into a diameter of about 12.8mm with a cutting machine The negative electrode of Example 1.

Assemble a button cell (model: CR2032), wherein the negative electrode of Example 1 is used as a working electrode, lithium metal is used as a counter electrode, _1M LiPF is added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, Calgard (Celgard) company) as the isolation membrane and stainless steel 304 or 316 cover as the package structure. So far, the secondary battery of Example 1 was produced.

Example 2

Preparation of negative electrode materials

At room temperature, CoO powder (precursor containing cobalt), CuO powder (precursor containing copper), SnO powder (precursor containing tin), and W oxide powder (precursor containing element M) were separately mixed by ball mill. After grinding, the powders were mixed and pressed into green pellets with a diameter of about 1 cm. The green body is placed in a high-temperature furnace to obtain the cobalt-copper-tin oxide block (i.e. the negative electrode material of Example 2) shown by the aforementioned formula (2), wherein x2 is 4, the element M is W, and the element M is The atomic number ratio is about 1-10 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 battery

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

Assemble a button cell (model: CR2032), wherein the negative electrode of Example 2 is used as a working electrode, lithium metal is used as a counter electrode, _1M LiPF is added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, Calgard (Celgard) company) as the isolation membrane and stainless steel 304 or 316 cover as the package structure. So far, the secondary battery of Example 2 was produced.

Example 3

Preparation of negative electrode materials

At room temperature, CoO powder (precursor containing cobalt), CuO powder (precursor containing copper), SnO powder (precursor containing tin), and W oxide powder (precursor containing element M) were separately mixed by ball mill. After grinding, the powders were mixed and pressed into green pellets with a diameter of about 1 cm. The green body is placed in a high-temperature furnace to obtain the cobalt-copper-tin oxide block (i.e. the negative electrode material of Example 3) shown by the aforementioned formula (3), wherein x3 is 4, the element M is W, and the element M is The atomic number ratio is about 1-10 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 battery

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

Assemble button cell (type: CR2032), wherein use the negative electrode of embodiment 3 as working electrode, lithium metal as opposite electrode, 1M LiPF ₆ add in the organic solvent as electrolyte, polypropylene film (trade name: Celgard#2400, Karl Gerde (Celgard) company) as the isolation film and stainless steel 304 or 316 cover as the package structure. So far, the secondary battery of Example 3 was produced.

Example 4

Preparation of negative electrode materials

At room temperature, use a ball mill to grind CoO powder (cobalt oxide), CuO powder (copper oxide), _SnO2 powder (tin oxide), W oxide powder (oxide containing element M) respectively. After mixing, the oxide mixture containing cobalt, copper and tin (i.e. the negative electrode material of embodiment 4) is obtained, wherein the atomic number ratio of cobalt, copper and tin is 1:1:1, element M is W, and element M The atomic number ratio is about 1 to 10 atomic%.

Preparation of secondary batteries

The negative electrode material of embodiment 4, Super P conductive carbon and binder (i.e. sodium carboxymethylcellulose (CMC) dissolved in water are mixed with a weight ratio of 7:2:1. Then, add zirconium dioxide balls Carry out slurry mixing for about 30 minutes to form negative electrode slurry. Then, use a scraper (100 μm) to coat the slurry on the copper foil (aforesaid current collector), and after making it evenly scrape off, 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 the negative electrode of Example 4 with a diameter of about 12.8 mm by a cutting machine.

Assemble a coin cell (model: CR2032), wherein the negative electrode of Example 4 is used as a working electrode, lithium metal is used as a counter electrode, _1M LiPF is added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, Calgard (Celgard) company) as the isolation membrane and stainless steel 304 or 316 cover as the package structure. So far, the secondary battery of Example 4 was produced.

Example 5

Preparation of negative electrode materials

At room temperature, 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 powders are mixed and pressed into a green pellet with a diameter of about 1 cm. The green body is placed in a high-temperature furnace to obtain the silicon-tin-iron oxide block material (i.e. the negative electrode material of embodiment 4) shown by the aforementioned formula (4), wherein x4 is 21, the element M is Ti, and the element M is 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 binder (that is, sodium carboxymethylcellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Then, add zirconia balls and mix the slurry for about 30 minutes to form the negative electrode slurry. Then, use a scraper (100 μm) to coat the slurry on the copper foil (the aforementioned current collector) and make it uniform After scraping, place the copper foil coated with slurry in a vacuum oven and dry it at about 110°C for about 12 hours. After that, cut the dried copper foil into a diameter of about 12.8mm with a cutting machine The negative electrode of Example 5.

Assemble button cell (model: CR2032), wherein use the negative pole of embodiment 5 as working electrode, lithium metal as opposite pole, 1M LiPF ₆ add in the organic solvent as electrolyte, polypropylene film (trade name: Celgard#2400, Karl Gerde (Celgard) company) as the isolation film and stainless steel 304 or 316 cover as the package structure. So far, the secondary battery of Example 5 was produced.

Example 6

Preparation of negative electrode materials

At room temperature, SiO ₂ powder (oxide of silicon), SnO ₂ powder (oxide of tin), Fe ₂ O ₃ powder (oxide of iron), TiO ₂ powder (oxide of ) after grinding and mixing to obtain an oxide mixture containing silicon, tin and iron (i.e. the negative electrode material of embodiment 6), wherein the atomic number ratio of silicon, tin and iron is 4:1:16, the element M is Ti, In addition, the atomic number ratio of the element M is about 1 to 10 atomic%.

Preparation of secondary batteries

The negative electrode material of embodiment 6, Super P conductive carbon and adhesive (i.e. sodium carboxymethylcellulose (CMC) dissolved in water are mixed with a weight ratio of 7:2:1. Then, add zirconium dioxide balls Carry out slurry mixing for about 30 minutes to form negative electrode slurry. Then, use a scraper (100 μm) to coat the slurry on the copper foil (aforesaid current collector), and after making it evenly scrape off, apply The copper foil with 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 the negative electrode of Example 6 with a diameter of about 12.8 mm by a cutting machine.

Assemble a button cell (model: CR2032), wherein the negative electrode _of Example 6 is used as a working electrode, lithium metal is used as a counter electrode, 1M LiPF is added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, Calgard (Celgard) company) as the isolation membrane and stainless steel 304 or 316 cover as the package structure. So far, the secondary battery of Example 6 was produced.

Example 7

Preparation of negative electrode materials

At room temperature, CuO powder (precursor containing copper), MnO powder (precursor containing manganese), _SiO2 powder (precursor containing silicon), _TiO2 powder (precursor containing element M) were separately mixed by ball mill After grinding, the powders were mixed and pressed into green pellets with a diameter of about 1 cm. The green body is placed in a high-temperature furnace to obtain the copper-manganese-silicon oxide bulk material (i.e. the negative electrode material of Example 7) shown by the aforementioned formula (7), wherein x7 is 1, the element M is Ti, and the element M is The atomic number ratio is about 1 to 10 atomic%, and the average particle diameter of the copper manganese silicon oxide is about 0.1 μm to about 10 μm.

Preparation of secondary battery

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

Assemble a button cell (model: CR2032), wherein the negative electrode of Example 7 is used as a working electrode, lithium metal is used as a counter electrode, _1M LiPF is added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, Calgard (Celgard) company) as the isolation membrane and stainless steel 304 or 316 cover as the package structure. So far, 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 (copper oxide), MnO powder (manganese oxide), _SiO2 powder (silicon oxide), and _TiO2 powder (oxide containing element M) Afterwards, to obtain the oxide mixture containing copper, manganese and silicon (i.e. the negative electrode material of embodiment 8), wherein the atomic number ratio of copper, manganese and silicon is 1:4:1, the element M is Ti, and the element M The atomic number ratio is about 1 to 10 atomic%.

Preparation of secondary batteries

The negative electrode material of embodiment 8, Super P conductive carbon and binder (i.e. sodium carboxymethyl cellulose (CMC) dissolved in water are mixed with a weight ratio of 7:2:1. Then, add zirconium dioxide balls Carry out slurry mixing for about 30 minutes to form negative electrode slurry. Then, use a scraper (100 μm) to coat the slurry on the copper foil (aforesaid current collector), and after making it evenly scrape off, apply The copper foil with the slurry was placed in a vacuum oven and dried at about 110° C. for about 12 hours. After that, the dried copper foil was cut into the negative electrode of Example 8 with a diameter of about 12.8 mm by a cutting machine.

Assemble a button cell (model: CR2032), wherein the negative electrode of Example 8 is used as a working electrode, lithium metal is used as a counter electrode, _1M LiPF is added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, Calgard (Celgard) company) as the isolation membrane and stainless steel 304 or 316 cover as the package structure. So far, 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), Mo oxide powder (precursor containing After grinding, the powders were mixed and pressed into green pellets with a diameter of about 1 cm. The green body is placed in a high-temperature furnace to obtain the tin-manganese-nickel oxide bulk material (i.e. the negative electrode material of Example 9) shown by the aforementioned formula (8), wherein x8 is 7, the element M is Mo, and the element M is The atomic number 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 binder (that is, sodium carboxymethylcellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Then, add zirconia balls and mix the slurry for about 30 minutes to form the negative electrode slurry. Then, use a scraper (100 μm) to coat the slurry on the copper foil (the aforementioned current collector) and make it uniform After scraping, place the copper foil coated with slurry in a vacuum oven and dry it at about 110°C for about 12 hours. After that, cut the dried copper foil into a diameter of about 12.8mm with a cutting machine The negative electrode of Example 9.

Assemble a coin cell (model: CR2032), wherein the negative electrode of Example 9 is used as a working electrode, lithium metal is used as a counter electrode, _1M LiPF is added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, Calgard (Celgard) company) as the isolation membrane and stainless steel 304 or 316 cover as the package structure. Thus far, the secondary battery of Example 9 was produced.

Example 10

Preparation of negative electrode materials

At room temperature, SnO ₂ powder (oxide of tin), MnO ₂ powder (oxide of manganese), NiO powder (oxide of nickel), Mo oxide powder (oxide containing element M) were processed by ball mill respectively. After grinding and mixing, an oxide mixture containing tin, manganese and nickel (i.e. the negative electrode material of Example 10) is obtained, wherein the atomic ratio of tin, manganese and nickel is 1:2:1, the element M is Mo, and the element The atomic ratio of M is about 1 to 10 atomic%.

manufacturing of secondary batteries

The negative electrode material of embodiment 10, Super P conductive carbon and binder (that is, sodium carboxymethyl cellulose (CMC) dissolved in water are mixed with a weight ratio of 7:2:1. Then, add zirconium dioxide balls Carry out slurry mixing for about 30 minutes to form negative electrode slurry. Then, use a scraper (100 μm) to coat the slurry on the copper foil (aforesaid current collector), and after making it evenly scrape off, apply The copper foil with 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 the negative electrode of Example 10 with a diameter of about 12.8 mm by a cutting machine.

Assemble a coin cell (model: CR2032), wherein the negative electrode of Example 10 is used as a working electrode, lithium metal is used as a counter electrode, 1M _LiPF is added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, Calgard (Celgard) company) as the isolation membrane and stainless steel 304 or 316 cover as the package structure. So far, the secondary battery of Example 10 was produced.

Example 11

Preparation of negative electrode materials

At room temperature, _MnO2 powder (precursor containing manganese), CuO powder (precursor containing copper), NiO powder (precursor containing nickel), Mo oxide powder (precursor containing ) after grinding, the powders were mixed and pressed into green pellets with a diameter of about 1 cm. The green body is placed in a high-temperature furnace to obtain the manganese-copper-nickel oxide bulk material (i.e. the negative electrode material of Example 11) shown by the aforementioned formula (13), wherein the element M is Mo, and the atomic number ratio of the element M is about 1-10 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 11, Super P conductive carbon and binder (that is, sodium carboxymethylcellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1. Then, add zirconia balls and mix the slurry for about 30 minutes to form the negative electrode slurry. Then, use a scraper (100 μm) to coat the slurry on the copper foil (the aforementioned current collector) and make it uniform After scraping, place the copper foil coated with slurry in a vacuum oven and dry it at about 110°C for about 12 hours. After that, cut the dried copper foil into a diameter of about 12.8mm with a cutting machine The negative electrode of Example 11.

Assemble a coin cell (model: CR2032), wherein the negative electrode of Example 11 is used as a working electrode, lithium metal is used as a counter electrode, 1M _LiPF is added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, Calgard (Celgard) company) as the isolation membrane and stainless steel 304 or 316 cover as the package structure. So far, the secondary battery of Example 11 was produced.

Example 12

Preparation of negative electrode materials

At room temperature, _MnO2 powder (manganese oxide), CuO powder (copper oxide), NiO powder (nickel oxide), and Mo oxide powder (oxide containing element M) were processed by ball mill respectively. After grinding and mixing, an oxide mixture containing manganese, copper and nickel (i.e. the negative electrode material of Example 12) is obtained, wherein the atomic ratio of manganese, copper and nickel is 2:1:1, the element M is Mo, and the element The atomic ratio of M is about 1 to 10 atomic%.

Preparation of secondary batteries

The negative electrode material of embodiment 12, Super P conductive carbon and binder (i.e. sodium carboxymethylcellulose (CMC) dissolved in water are mixed with a weight ratio of 7:2:1. Then, add zirconium dioxide balls Carry out slurry mixing for about 30 minutes to form negative electrode slurry. Then, use a scraper (100 μm) to coat the slurry on the copper foil (aforesaid current collector), and after making it evenly scrape off, apply The copper foil with 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 the negative electrode of Example 12 with a diameter of about 12.8 mm by a cutting machine.

Assemble a coin cell (model: CR2032), wherein the negative electrode of Example 12 is used as a working electrode, lithium metal is used as a counter electrode, 1M _LiPF is added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, Calgard (Celgard) company) as the isolation membrane and stainless steel 304 or 316 cover as the package structure. So far, the secondary battery of Example 12 was produced.

Example 13

Preparation of negative electrode materials

At room temperature, use a ball mill to grind NiO powder (oxide of nickel), CuO powder (oxide of copper), _SnO powder (oxide of tin), and W oxide powder (oxide containing element M) respectively. After mixing, an oxide mixture containing nickel, copper and tin (i.e. the negative electrode material of Example 13) is obtained, wherein 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 10 atomic%.

Preparation of secondary batteries

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

Assemble a button cell (model: CR2032), wherein the negative electrode of Example 13 is used as a working electrode, lithium metal is used as a counter electrode, 1M _LiPF is added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, Calgard (Celgard) company) as the isolation membrane and stainless steel 304 or 316 cover as the package structure. Thus far, the secondary battery of Example 13 was produced.

Example 14

Preparation of negative electrode materials

At room temperature, NiO powder (precursor containing nickel), CuO powder (precursor containing copper), _SnO2 powder (precursor containing tin), W oxide powder (precursor containing ) after grinding, the powders were mixed and pressed into green pellets with a diameter of about 1 cm. The green body is placed in a high-temperature furnace to obtain the nickel-copper-tin oxide bulk material (i.e. the negative electrode material of Example 14) shown by the aforementioned formula (15), wherein x15 is 6, the element M is W, and the 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 battery

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

Assemble a coin cell (model: CR2032), wherein the negative electrode of Example 14 is used as a working electrode, lithium metal is used as a counter electrode, 1M _LiPF is added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, Calgard (Celgard) company) as the isolation membrane and stainless steel 304 or 316 cover as the package structure. Thus far, 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 that of Example 1, and the difference was mainly in that: in the secondary battery of Example 1, the working electrode was the negative electrode of Example 1; and 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 battery

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

Comparative example 3

Preparation of secondary battery

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

Comparative example 4

Preparation of secondary battery

The secondary battery of Comparative Example 4 was made according to the same manufacturing procedure as that of Example 1, and the difference was mainly in that: in the secondary battery of Example 1, the working electrode was the negative electrode of Example 1; and in Comparative Example 4 In the secondary battery, the material of the working electrode is SnO ₂ .

Comparative Example 5

Preparation of secondary battery

The secondary battery of Comparative Example 5 was made according to the same manufacturing procedure as that of Example 1, and the difference was mainly in that: in the secondary battery of Example 1, the working electrode used the negative electrode of Example 1; and 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 that of Example 1, and the difference was mainly in that: in the secondary battery of Example 1, the working electrode was the negative electrode of Example 1; and 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 that of Example 1, and the difference was mainly in that: in the secondary battery of Example 1, the working electrode was the negative electrode of Example 1; and 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 that of Example 1, and the difference was mainly in that: in the secondary battery of Example 1, the working electrode was the negative electrode of Example 1; and 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 that of Example 1, and the difference was mainly in that: in the secondary battery of Example 1, the working electrode was the negative electrode of Example 1; and in Comparative Example 9 In the secondary battery, the material of the working electrode is NiO.

After preparing the secondary batteries of Examples 1-14 and the secondary batteries of Comparative Examples 1-9, the secondary batteries of Examples 1-14 and the secondary batteries of Comparative Examples 1-9 were respectively subjected to a charge-discharge cycle test .

Charge and discharge cycle test

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

It can be seen from Figures 2 to 4 that, compared with the secondary battery of Comparative Example 1, after a high number of cycles (>250), the secondary batteries of Examples 1 to 3 have better capacity and Capacity retention.

Although the aforementioned tests were not carried out on secondary batteries comprising cobalt-copper-tin oxides represented by formula (1) with x1 being 9 or 14, according to the previous description about cobalt-copper-tin oxides and the test results of Example 1 , those skilled in the art will understand that the secondary battery comprising the cobalt-copper-tin oxide represented by formula (1) with x1 being 9 or 14 will have good capacity and capacity retention.

Although the aforementioned tests have not been carried out on secondary batteries comprising cobalt-copper-tin oxides represented by formula (2) where x2 is 6 or 8, according to the foregoing description and the test results of Example 2, those skilled in the art should It is understood that a secondary battery including the cobalt-copper-tin oxide represented by the formula (2) where x2 is 6 or 8 will have good capacity and capacity retention.

Although the aforementioned tests were not performed on secondary batteries comprising cobalt-copper-tin oxides represented by formula (3) with x3 being 3 or 5, according to the foregoing description and the test results of Example 1, those skilled in the art should It is understood that a secondary battery including the cobalt-copper-tin oxide represented by formula (3) where x3 is 3 or 5 will have good capacity and capacity retention.

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

Although the aforementioned tests were not performed on secondary batteries comprising oxide mixtures containing cobalt, copper, and tin in an atomic ratio of 5:1:3 or 2:1:1, according to the foregoing description And the test results of Example 4, those skilled in the art should understand that the secondary oxide mixture containing cobalt, copper and tin whose atomic ratio is 5:1:3 or 2:1:1 is understood by those skilled in the art. The battery will have good capacity and capacity retention.

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

Although the foregoing tests have not been carried out on secondary batteries comprising silicon-tin-iron oxides represented by formula (4) with x4 greater than 21 to 34, according to the foregoing description and the test results of Example 5, those skilled in the art It should be understood that the secondary battery including the silicon tin iron oxide represented by the formula (4) with x4 greater than 21 to 34 will have good capacity and capacity retention.

Although the foregoing tests were not performed on the secondary battery comprising the silicon-tin-iron oxide represented by formula (5) or formula (6), according to the foregoing description and the test results of Example 5, those skilled in the art should understand A secondary battery including the silicon tin iron oxide represented by formula (5) or formula (6) will have good capacity and capacity retention.

Although the foregoing tests were not performed on secondary batteries comprising oxide mixtures of silicon, tin and iron in an atomic ratio of 1:1:1 or 4:1:1, according to the foregoing description And the test results of Example 6, those skilled in the art should understand that the secondary oxide mixture containing silicon, tin and iron whose atomic ratio is 1:1:1 or 4:1:1 is understood by those skilled in the art. The battery will have good capacity and capacity retention.

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

Although the aforementioned tests have not been carried out on the secondary battery comprising the copper-manganese-silicon oxide shown in formula (7) where x7 is greater than 0 to less than 1, according to the foregoing description and the test results of Example 7, the technology in the field Personnel should understand that the secondary battery comprising the copper-manganese-silicon oxide represented by formula (7) with x7 greater than 0 to less than 1 will have good capacity and capacity retention.

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

Although the aforementioned tests were not performed on secondary batteries comprising oxide mixtures containing copper, manganese and silicon in an atomic ratio of copper, manganese and silicon 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 number ratio of copper, manganese and silicon is 1:1:1, 4:1:1 or 1:1:4. The secondary battery of the oxide mixture of copper, manganese and silicon has good capacity and capacity retention.

It can be seen from Figure 10 and Figure 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 capacity retention.

Although the foregoing tests have not been carried out on secondary batteries comprising tin-manganese-nickel oxides represented by formula (8) with x8 being 4 to less than 7, according to 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) with x8 ranging from 4 to less than 7 will have good capacity and capacity retention.

Although the foregoing tests were not performed on secondary batteries comprising tin-manganese-nickel oxides 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 will understand that the secondary battery comprising the tin-manganese-nickel oxide represented by formula (9), formula (10) or formula (11) will have good capacity and capacity retention.

Although the foregoing tests were not performed on secondary batteries comprising oxide mixtures containing tin, manganese and nickel in an atomic ratio of tin, manganese and nickel 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. The secondary battery of the oxide mixture of tin, manganese and nickel has good capacity and capacity retention.

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

Although the foregoing tests were not performed on the secondary battery comprising the manganese-copper-nickel oxide represented by formula (12) or formula (14), according to the foregoing description and the test results of Example 11, those skilled in the art should understand A secondary battery including the manganese-copper-nickel oxide represented by formula (12) or formula (14) has good capacity and capacity retention.

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

Although the foregoing tests were not performed on secondary batteries comprising manganese, copper and nickel oxide mixtures containing manganese, copper and nickel in an atomic ratio of 3:2:1 or 1:1:1, according to the foregoing description And the test results of Example 12, those skilled in the art should understand that the secondary oxide mixture containing manganese, copper and nickel with an atomic ratio of 3:2:1 or 1:1:1 is understood by those skilled in the art. The battery will have good capacity and capacity retention.

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

Although the foregoing tests were not performed on secondary batteries comprising nickel, copper and tin oxide mixtures containing nickel, copper and tin in an atomic ratio of 2:1:3 or 1:2:3, according to the foregoing 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 whose atomic ratio is 2:1:3 or 1:2:3 is understood by those skilled in the art. The battery will have good capacity and capacity retention.

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

Although the foregoing tests have not been carried out on secondary batteries comprising nickel-copper-tin oxides represented by formula (15) with x15 being 3 or 9, according to the foregoing description and the test results of Example 14, those skilled in the art should It is understood that a secondary battery including the nickel-copper-tin oxide represented by the formula (15) where x15 is 3 or 9 has good capacity and capacity retention.

Although the foregoing tests were not performed on the secondary battery comprising the nickel-copper-tin oxide represented by formula (16) or formula (17), according to the foregoing description and the test results of Example 14, those skilled in the art should understand A secondary battery including the nickel-copper-tin oxide represented by formula (16) or formula (17) has good capacity and capacity retention.

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

In addition, compared with commercial graphite (theoretical value of electric capacity is 372mAh/g), the secondary battery using the negative electrode made of the secondary battery negative electrode material of the present invention has higher electric capacity, therefore 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 solutions of the present invention, rather than limiting them; 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: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present invention. scope.

Claims (5)

1. A negative electrode material for a secondary battery, characterized in that it comprises: Oxide mixture mixed with 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 at least one of NiO and Ni ₂ O ₃ obtained through steps, wherein the atomic ratio of manganese, copper and tin in the oxide mixture is 3:2:1, 2:1:1 or 1:1:1. 2. The negative electrode material for secondary batteries according to claim 1, wherein the mixing step also includes mixing M-containing oxides, wherein M is selected from Fe, Cr, Zn, Al, Ti, In, Mo , W and at least one element in Si, and relative to the total number of atoms of the metal elements in the oxide mixture, the atomic ratio of M is greater than 0 to less than or equal to 10atomic%. 3. A negative electrode for a secondary battery, characterized in that it comprises: current collectors; and The negative electrode material layer is arranged on the current collector and includes the secondary battery negative electrode material according to any one of claims 1 to 2. 4. A secondary battery, characterized in that it comprises: positive electrode; a negative electrode configured separately from the positive electrode, wherein the negative electrode is the negative electrode for a secondary battery as claimed in claim 3; an electrolyte disposed between the positive electrode and the negative electrode; and The encapsulation structure wraps the positive electrode, the negative electrode and the electrolyte. 5. The secondary battery according to claim 4, further comprising a separator disposed between the positive electrode and the negative electrode, and the separator, the positive electrode and the negative electrode define a capacity The accommodating area, and the electrolyte is arranged in the accommodating area.