CN114725359B - Negative electrode material for secondary battery, negative electrode, and secondary battery - Google Patents

Negative electrode material for secondary battery, negative electrode, and secondary battery Download PDF

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CN114725359B
CN114725359B CN202210497314.1A CN202210497314A CN114725359B CN 114725359 B CN114725359 B CN 114725359B CN 202210497314 A CN202210497314 A CN 202210497314A CN 114725359 B CN114725359 B CN 114725359B
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oxide
copper
tin
secondary battery
manganese
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CN114725359A (en
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游萃蓉
蓝凯威
何俊德
郭家彤
冀天齐
李羿廷
蔡昀真
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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 invention is a divisional application of patent application of 202010057891.X, the invention name of which is "negative electrode material for secondary battery, negative electrode and secondary battery" filed on 16 th month of 2020.
Technical Field
The present invention relates to an electrode material, an electrode, and a battery, and in particular, to a negative electrode material for a secondary battery, a negative electrode for a secondary battery, and a secondary battery.
Background
In recent years, the market demand and the daily increase of secondary lithium batteries capable of being repeatedly charged and discharged have the characteristics of light weight, high voltage value, high energy density and the like. Accordingly, there is an increasing demand for performance of secondary lithium batteries such as light weight, durability, high voltage, high energy density, and high safety. The application and expansion potential of the secondary lithium battery in light electric vehicles, electric vehicles and large-scale electricity storage industry are quite high. The most common commercial electrode material is graphite, but the capacity of graphite (theoretical value 372 mAh/g) is low, so the performance of the battery manufactured by the electrode material is limited. Therefore, it is one of the objects to be achieved by those skilled in the art to find an electrode material for secondary batteries having high stability and high capacity.
Disclosure of Invention
In view of this, the present invention provides a negative electrode material and a negative electrode for a secondary battery, which provide the secondary battery with good capacity and stability.
An embodiment of the present invention provides a negative electrode material for a secondary battery, comprising cobalt copper tin oxide represented by one of the following formulas (1) to (3):
Co 5 Cu 1 Sn 3 MO x1 (1),
Co 2 Cu 1 Sn 1 MO x2 (2),
Co 1 Cu 1 Sn 1 MO x3 (3),
wherein x1 is 8, 9 or 14, x2 is 4, 6 or 8, x3 is 3, 4 or 5, M is at least one element selected from Ni, cr, mn, zn, al, ti, in, mo and W, and the atomic number ratio of M is 10atomic% or less relative to the total atomic number of the metal elements in the cobalt copper tin oxide represented by formula (1), formula (2) or formula (3).
Another embodiment of the present invention provides a negative electrode material for a secondary battery comprising a material composed of Co 3 O 4 、Co 2 O 3 At least one of CoO, cuO and Cu 2 At least one of O, and SnO 2 An oxide mixture obtained by performing a mixing step, wherein the atomic number ratio of cobalt, copper and tin in the oxide mixture is 5:1: 3. 2:1:1 or 1:1:1.
another embodiment of the present invention provides a negative electrode material for a secondary battery, comprising a silicon tin iron oxide represented by one of the following formulas (4) to (6):
Si 4 Sn 1 Fe 16 MO x4 (4) a step of,
Si 1 Sn 1 Fe 1 MO x5 (5),
Si 4 Sn 1 Fe 1 MO x6 (6),
wherein x4 is 21 to 34, x4 is 3 to 5, x6 is 6 to 11.5, M is at least one element selected from Cr, mn, zn, al, ti, in, mo and W, and the atomic number ratio of M is 10atomic% or less relative 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).
Another embodiment of the present invention provides a negative electrode material for a secondary battery comprising a material composed of SiO 2 At least one of SiO, snO and SnO 2 At least one of (1) and Fe 2 O 3 、Fe 3 O 4 An oxide mixture obtained by performing a mixing step with at least one of FeO, wherein the atomic number ratio of silicon, tin, and iron in the oxide mixture is 4:1: 16. 1:1:1 or 4:1:1.
another embodiment of the present invention provides a negative electrode material for a secondary battery, comprising a copper-manganese-silicon oxide represented by the following formula (7):
Cu x7 Mn 7-x7 SiMO 12 (7),
wherein x7 is more than 0 and equal to or less than 1, M is at least one element selected from Cr, sn, ni, co, zn, al, ti, in, mo and W, and the atomic number ratio of M is 10atomic% or less relative to the total atomic number of elements other than oxygen in the copper-manganese-silicon oxide represented by formula (7).
Another embodiment of the present invention provides a negative electrode material for a secondary battery comprising a mixture of CuO and Cu 2 At least one of O, siO 2 At least one of SiO, mnO 2 、Mn 2 O 3 With Mn 3 O 4 An oxide mixture obtained by performing a mixing step, wherein the atomic number ratio of copper, manganese and silicon in the oxide mixture is 1:1: 1. 1:4: 1. 4:1:1 or 1:1:4.
Another embodiment of the present invention provides a negative electrode material for a secondary battery, comprising a tin-manganese-nickel oxide represented by one of the following formulas (8) to (11):
Sn 1 Mn 2 Ni 1 MO x8 (8),
Sn 1 Mn 1 Ni 2 MO x9 (9),
Sn 2 Mn 1 Ni 1 MO x10 (10),
Sn 1 Mn 1 Ni 1 MO x11 (11),
wherein x8 is 4 to 7, x9 is 4 to 7, x10 is 4 to 7, x11 is 3 to 6, M is at least one element selected from Cr, mn, zn, al, ti, in, mo and W, and the atomic number ratio of M is 10atomic% or less relative to the total atomic number of the metal elements in the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10) or formula (11).
Another embodiment of the present invention provides a negative electrode material for a secondary battery comprising a material composed of SnO and SnO 2 At least one of them, mnO 2 、Mn 2 O 3 With Mn 3 O 4 At least one of NiO and Ni 2 O 3 An oxide mixture obtained by performing a mixing step, wherein the atomic number ratio of tin, manganese and nickel in the oxide mixture is 1:2: 1. 1:1: 1. 1:1:2 or 2:1:1.
another embodiment of the present invention provides a negative electrode material for a secondary battery, comprising a manganese copper nickel oxide represented by one of the following formulas (12) to (14):
Mn 3 Cu 2 Ni 1 MO 8 (12),
Mn 2 Cu 1 Ni 1 MO 4 (13),
Mn 1 Cu 1 Ni 1 MO 4 (14),
wherein M is at least one element selected from Fe, cr, zn, al, ti, in, mo, W and Si, and the atomic number ratio of M is 10atomic% or less relative to the total atomic number of the metal elements in the manganese copper nickel oxide represented by the formula (12), the formula (13) or the formula (14).
Another embodiment of the present invention provides a negative electrode material for a secondary battery comprising a metal oxide semiconductor (MnO), a metal oxide semiconductor (MnO) 2 、Mn 2 O 3 With Mn 3 O 4 At least one of CuO and Cu 2 At least one of O, niO and Ni 2 O 3 An oxide mixture obtained by performing a mixing step, wherein the atomic number ratio of manganese, copper and nickel in the oxide mixture is 3:2: 1. 2:1:1 or 1:1:1.
another embodiment of the present invention provides a negative electrode material for a secondary battery, comprising a nickel-copper-tin oxide represented by one of the following formulas (15) to (17):
NiCuSn 2 MO x15 (15),
Ni 2 CuSn 3 MO x16 (16) the process is carried out,
NiCu 2 Sn 3 MO x17 (17),
wherein x15 is 3, 6 or 9, x16 is 4, 6 or 9, x17 is 4, 6 or 9,M is at least one element selected from Cr, mn, zn, al, ti, in, mo, W and Co, and the atomic number ratio of M is 10atomic% or less relative to the total atomic number of the metal elements in the nickel-copper-tin oxide represented by formula (15), formula (16) or formula (17).
Another embodiment of the present invention provides a negative electrode material for a secondary battery comprising a metal alloy consisting of Ni 2 O 3 At least one of NiO, cuO and Cu 2 At least one of O, and SnO 2 An oxide mixture obtained by performing a mixing step, wherein the atomic number ratio of cobalt, copper and tin in the oxide mixture is 1:1: 2. 2:1:3 or 1:2:3.
An embodiment of the present invention provides a negative electrode for a secondary battery including a current collector and a negative electrode material layer. The negative electrode material layer is disposed on the current collector and includes any of the negative electrode materials for secondary batteries described above.
An embodiment of the present invention provides a secondary battery including a positive electrode, a negative electrode, an electrolyte, and a package structure. The negative electrode is disposed separately from the positive electrode, and the negative electrode is a negative electrode for a secondary battery as described above. The electrolyte is disposed between the positive electrode and the negative electrode. The packaging structure wraps the anode, the cathode and the electrolyte.
Based on the above, the anode material for a secondary battery of the present invention makes it possible to be applied to a secondary battery by including a metal oxide represented by one of the formulas (1) to (17), or 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 in a specific ratio of the atomic numbers of elements, and makes the secondary battery have good capacity, stability, and charge-discharge cycle life.
In order to make the above features and advantages of the present invention more comprehensible, embodiments accompanied with figures are described in detail below.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
Fig. 1 is a schematic cross-sectional view of a secondary battery according to an embodiment of the present invention;
fig. 2 is a cycle life graph of the secondary batteries of example 1 and comparative example 1;
fig. 3 is a cycle life graph of the secondary batteries of example 2 and comparative example 1;
fig. 4 is a cycle life graph of the secondary batteries of example 3 and comparative example 1;
fig. 5 is a cycle life graph of the secondary batteries of example 4 and comparative examples 2 to 4;
fig. 6 is a cycle life graph of the secondary batteries of example 5 and comparative examples 4 to 6;
fig. 7 is a cycle life graph of the secondary batteries of example 6 and comparative examples 4 to 6;
fig. 8 is a cycle life graph of the secondary battery of example 7;
fig. 9 is a cycle life graph of the secondary batteries of example 8 and comparative examples 3, 5, and 7;
fig. 10 is a cycle life graph of the secondary battery of example 9 and comparative examples 4, 8 to 9;
fig. 11 is a cycle life graph of the secondary batteries of example 10 and comparative examples 4, 8 to 9;
Fig. 12 is a cycle life graph of the secondary battery of example 11;
fig. 13 is a cycle life graph of the secondary batteries of example 12 and comparative examples 3, 8 to 9;
fig. 14 is a cycle life graph of the secondary batteries of example 13 and comparative examples 3 to 4, 9;
fig. 15 is a cycle life graph of the secondary battery of example 14.
Description of the reference numerals
100: a secondary battery;
102: a negative electrode;
102a, 104a: a current collector;
102b: a negative electrode material layer;
104: a positive electrode;
104b: a positive electrode material layer;
106: a separation film;
108: an electrolyte;
110: a receiving area;
112: and (5) packaging the structure.
Detailed Description
In this document, a range from "one value to another value" is a shorthand way of referring individually to all the values in the range, which are avoided in the specification. Thus, recitation of a particular numerical range includes any numerical value within that range, as well as the smaller numerical range bounded by any numerical value within that range, as if the any numerical value and the smaller numerical range were written in the specification in the clear.
As used herein, "about," "approximately," "essentially," or "substantially" includes both the values and average values within an acceptable deviation of the particular values as determined by one of ordinary skill in the art, taking into account the particular number of measurements and errors associated with the measurements (i.e., limitations of the measurement system) in question. For example, "about" may mean within one or more standard deviations of the stated values, or within, for example, ±30%, ±20%, ±15%, ±10%, ±5%. Further, as used herein, "about," "approximately," "essentially," or "substantially" may be used to select a more acceptable range of deviation or standard deviation based on measured or other properties, rather than one standard deviation for all properties.
In order to prepare a negative electrode material applicable to a negative electrode of a secondary battery and providing the secondary battery with good stability and capacity, the present invention proposes a negative electrode material that can achieve the above-mentioned advantages. The following description will be made with reference to specific embodiments as a matter of course to which the present invention can be applied.
An embodiment of the present invention provides a negative electrode material that may include a metal oxide containing four or more elements, or an oxide mixture containing four or more elements. In this embodiment, the anode material may be a powder, a film, or a bulk material.
In the present embodiment, the method for producing a metal oxide containing four or more elements includes, for example, a hydrothermal method, a coprecipitation 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 embodiments where the hydrothermal process is used to prepare the four or more element-containing metal oxide, the temperature may be about 200 ℃ or higher, the holding time may be about 5 hours or higher, and the ambient pressure may be about 10 -2 And Torr or above. In embodiments in which the four or more element-containing metal oxide is prepared using a coprecipitation process, coprecipitation may be first performed, the reaction temperature thereof may be about 200 ℃ or more, the pH of the solution may be about 2 to about 12, and the holding time may be about 1 hour or more; after the reaction is completed, the calcination treatment is performed, and the calcination temperature may be about 300 ℃ or higher and the holding time may be about 1 hour or longer. In embodiments where the four or more element-containing metal oxide is prepared using a sol-gel process, the temperature may be about 100 ℃ or higher, the solution pH may be about 2 to about 12, and the holding time may be about 5 hours or longer. In addition, in embodiments where the metal oxide containing four or more elements is prepared using a solid state process, the temperature may be about 100 ℃ or higher and the holding time may be about 8 hours or higher. In embodiments in which the four or more element-containing metal oxide is prepared using a vapor deposition process, the temperature may be about 25 ℃ or higher, the vapor deposition time may be about 1 hour or longer, and the ambient pressure may be about 10 -3 And Torr or above. In embodiments where the four or more element-containing metal oxide is prepared using sputtering, the temperature may be about 25 ℃ or higher, the sputtering time may be about 0.5 hours or longer, and the ambient pressure may be about 10 -3 And Torr or above. In embodiments where the four or more element-containing metal oxide is prepared using vapor deposition, the temperature may be about 25 ℃ or higher, the deposition time may be about 1 hour or higher, and the ambient pressure may be about 10 -3 And Torr or above.
In this embodiment, the metal oxide containing four or more 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-described various oxides will be described in detail.
Cobalt copper tin oxide
In this embodiment, cobalt copper tin oxide may be represented by one of the following formulas (1) to (3):
Co 5 Cu 1 Sn 3 MO x1 (1),
Co 2 Cu 1 Sn 1 MO x2 (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 correspond to the specific values listed above, the secondary battery to which the anode material including the cobalt copper tin oxide is applied has excellent capacity, improved capacity retention, and excellent cycle life.
In each of the formula (1), the formula (2), and the 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 10atomic% or less relative to the total atomic number of the metal elements in the cobalt copper tin oxide represented by the formula (1), the formula (2) or the 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 include only four elements, i.e., cobalt, copper, tin and oxygen. It is noted that cobalt copper tin oxide containing M in an atomic ratio of more than 0 and 10atomic% or less has conductivity increased by about 10% or more as compared with cobalt copper tin oxide containing no element M. In addition, in the present embodiment, in the case of cobalt copper tin oxide containing the element M, M may replace a part of cobalt, copper, and/or tin. For example, in one embodiment, M may replace a portion of cobalt; in another embodiment, M may replace a portion of cobalt and a portion of copper; in yet another embodiment, M may replace a portion of cobalt, a portion of copper, and a portion of tin, although the invention is not limited thereto. Note that in this embodiment, the number of atoms in the cobalt copper tin oxide represented by the formula (1), the formula (2), or the formula (3) may have an error range of ±10% due to formation or non-uniformity of diffusion of oxygen vacancies.
In this embodiment, the cobalt copper tin oxide represented by formula (1), formula (2), or formula (3) may have a Spinel structure (Spinel structure), a perovskite structure (Perovskite structure), a sodium chloride structure (Sodium chloride structure), or a chalcopyrite structure (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, thereby lithium ions can be conveniently and rapidly introduced and discharged in the secondary battery using the anode material including the cobalt copper tin oxide, thereby effectively improving the diffusion rate of lithium ions and the ion conductivity. In addition, the cobalt copper tin oxide represented by the formula (1), the formula (2) or the formula (3) has the above structure and is not likely to collapse during charge and discharge, whereby a secondary battery using a negative electrode material including the cobalt copper tin oxide 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 10nm and about 1 mm. When the average particle diameter of the cobalt copper tin oxide falls within the above range, it is advantageous to form a negative electrode having good characteristics. In the embodiment in which cobalt copper tin oxide is produced by the solid state method, grinding may be performed using a mortar, a ball mill (ball mill), a sand grinder, a vibration ball mill, or a planetary ball mill (planet ball mill) in order to obtain cobalt copper tin oxide having the above-described specific average particle size range, but the present invention is not limited thereto.
Silicon tin iron oxide
In the present 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 (4) a step of,
Si 1 Sn 1 Fe 1 MO x5 (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 each 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 the formula (4), the formula (5) and the formula (6), M may be at least one element selected from Cr, mn, zn, al, ti, in, mo and W. The atomic number ratio of M is 10atomic% or less relative to the total atomic number of elements other than oxygen in the silicon tin iron oxide represented by the formula (4), the formula (5) or the formula (6). In other words, the silicon tin iron oxide represented by formula (4), formula (5) or formula (6) may not contain the element M, but include only four elements, i.e., silicon, tin, iron and oxygen. It is noted that the silicon tin iron oxide containing M in an atomic ratio of more than 0 and 10atomic% or less has conductivity increased by about 10% or more as compared with the silicon tin iron oxide containing no element M. In addition, in the present embodiment, in the case of a silicon tin iron oxide containing the element M, M may replace a part of silicon, tin, and/or iron. For example, in one embodiment, M may replace a portion of silicon; in another embodiment, M may replace a portion of silicon and a portion of tin; in yet another embodiment, M may replace a portion of silicon, a portion of tin, and a portion of iron, but the invention is not limited thereto. Note that in this embodiment, the atomic number value in the silicon tin iron oxide represented by the formula (4), the formula (5), or the formula (6) has an error range of ±10% due to formation or non-uniformity of diffusion of oxygen vacancies.
In this embodiment, the silicon tin iron oxide represented by formula (4), formula (5), or formula (6) may have an orthorhombic structure (Rhombohedral structure), a cubic iron manganese ore structure (Cubic Bixbyite structure), a Spinel structure (Spinel structure), or an orthorhombic structure (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, thereby lithium ions can be conveniently and rapidly introduced and withdrawn in the secondary battery to which the negative electrode material including the silicon tin iron oxide is applied, thereby effectively improving the diffusion rate of lithium ions and the ion conductivity. Further, the silicon tin iron oxide represented by the formula (4), the formula (5) or the formula (6) has the above-described structure and is not likely to collapse during charge and discharge, whereby a secondary battery to which a negative electrode material comprising the silicon tin iron oxide is applied 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 10nm and about 1 mm. If the average particle diameter of the silicon tin iron oxide falls within the above range, it is advantageous to form a negative electrode having good characteristics. In the embodiment in which the silicon tin iron oxide is produced by the solid state method, grinding may be performed using a mortar, a ball mill (ball mill), a sand grinder, a vibration ball mill, or a planetary ball mill (planet ball mill) in order to obtain the silicon tin iron oxide having the specific average particle size range, 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 (Cu) x7 Mn 7-x7 SiMO 12 Formula (7). In formula (7), x7 is greater than 0 and equal to or less than 1. If x7 is within the above range, the secondary battery to which the anode 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 number ratio of M is 10atomic% or less relative to the total atomic number of elements other than oxygen in the copper-manganese-silicon oxide represented by formula (7). In other words, the copper-manganese-silicon oxide represented by formula (7) may not contain the element M, but include only four elements, i.e., copper, manganese, silicon and oxygen. It is noted that the copper-manganese-silicon oxide containing M in an atomic ratio of more than 0 and 10atomic% or less has conductivity increased by about 10% or more as compared with the copper-manganese-silicon oxide containing no element M. In addition, in the present embodiment, in the case of copper-manganese-silicon oxide containing the element M, M may replace a part of copper, manganese, and/or silicon. For example, in one embodiment, M may replace a portion of copper; in another embodiment, M may replace a portion of copper and a portion of manganese; in yet another embodiment, M may replace a portion of copper, a portion of manganese, and a portion of silicon, although the invention is not so limited. Note that in this embodiment, the atomic number values of copper and manganese in the copper-manganese-silicon oxide represented by the formula (7) have an error range of ±10% due to uneven diffusion or formation of oxygen vacancies, thereby forming a non-integer ratio compound.
In this embodiment, the copper-manganese-silicon oxide represented by formula (7) may have a brown copper-manganese ore structure (Abswurmbachite structure), a manganese pyroxene structure (Pyroxmangite structure), or a brown manganese ore structure (Braunite structure). It is noted that the copper-manganese-silicon oxide represented by formula (7) has the above-described structure, whereby in a secondary battery to which a negative electrode material including the copper-manganese-silicon oxide is applied, the energy loss due to the overpotential (overpotential) can be reduced, the lithium ion diffusion rate and the 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 10nm and about 1 mm. When the average particle diameter of the copper-manganese-silicon oxide falls within the above range, it is advantageous to form a negative electrode having good characteristics. In the embodiment in which the copper-manganese-silicon oxide is produced by the solid-state method, grinding may be performed using a mortar, a ball mill (ball mill), a sand grinder, a vibration ball mill, or a planetary ball mill (planet ball mill) in order to obtain the copper-manganese-silicon oxide having the specific average particle size range, but the present invention is not limited thereto.
Tin manganese nickel oxide
In the present 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 (8),
Sn 1 Mn 1 Ni 2 MO x9 (9),
Sn 2 Mn 1 Ni 1 MO x10 (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, the secondary battery to which the anode 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 may be at least one element selected from Cr, mn, zn, al, ti, in, mo and W. The atomic number ratio of M is 10atomic% or less relative to the total atomic number of the metal elements in the tin-manganese-nickel oxide represented by the formula (8), the formula (9), the formula (10) or the formula (11). In other words, the tin-manganese-nickel oxide represented by the formula (8), the formula (9), the formula (10) or the formula (11) may not contain the element M, but include only four elements, i.e., tin, manganese, nickel and oxygen. It is noted that the tin-manganese-nickel oxide containing M in an atomic ratio of more than 0 and 10atomic% or less has a conductivity increased by about 10% or more as compared with the tin-manganese-nickel oxide containing no element M. In addition, in the present embodiment, in the case of tin-manganese-nickel oxide containing the element M, M may replace a part of tin, manganese, and/or nickel. For example, in one embodiment, M may replace a portion of tin; in another embodiment, M may replace a portion of tin and a portion of manganese; in yet another embodiment, M may replace a portion of tin, a portion of manganese, and a portion of nickel, although the invention is not limited thereto. Note that in this embodiment, the number of atoms in the tin-manganese-nickel oxide represented by the formula (8), the formula (9), the formula (10) or the formula (11) may have an error range of ±10% due to formation or non-uniformity of diffusion of oxygen vacancies.
In this embodiment, the tin-manganese-nickel oxide represented by the formula (8), the formula (9), the formula (10), or the formula (11) may have a Spinel structure (Spinel structure), a rubble structure (rubble structure), or a rock salt 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 facilitating rapid ingress and egress of lithium ions in a secondary battery to which a negative electrode material including the tin-manganese-nickel oxide is applied, and thus effectively improving the diffusion rate of lithium ions and ion conductivity. Further, the tin-manganese-nickel oxide represented by the formula (8), the formula (9), the formula (10) or the formula (11) has the above-described structure and is less likely to collapse during charge and discharge, whereby a secondary battery using a negative electrode material comprising the tin-manganese-nickel oxide can maintain a good charge and discharge cycle life.
In this embodiment, the average particle size of the tin-manganese-nickel oxide is, for example, between about 10nm and about 1 mm. When the average particle diameter of the tin-manganese-nickel oxide falls within the above range, it is advantageous to form a negative electrode having good characteristics. In the embodiment in which the tin-manganese-nickel oxide is produced by the solid state method, grinding may be performed using a mortar, a ball mill (ball mill), a sand grinder, a vibration ball mill, or a planetary ball mill (planet ball mill) in order to obtain the tin-manganese-nickel oxide having the specific average particle size range, but the present invention is not limited thereto.
Manganese copper nickel oxide
In the present embodiment, the manganese copper nickel oxide may be represented by one of the following formulas (12) to (14):
Mn 3 Cu 2 Ni 1 MO 8 (12),
Mn 2 Cu 1 Ni 1 MO 4 (13),
Mn 1 Cu 1 Ni 1 MO 4 formula (14). That is, in the present embodiment, the atomic ratio of manganese, copper, nickel, and oxygen in the manganese-copper-nickel oxide may be 3:2:1: 8. 2:1:1: 4. or 1:1:1:4. it is worth mentioning that the secondary battery, which is represented by one of formulas (12) to (14) through the manganese copper nickel oxide, whereby the anode material including the manganese copper nickel oxide is applied, has excellent capacity and improved capacity retention.
In each of the formula (12), the formula (13) and the 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 10atomic% or less relative to the total atomic number of the metal elements in the manganese copper nickel oxide represented by the formula (12), the formula (13) or the formula (14). In other words, the manganese copper nickel oxide represented by the formula (12), the formula (13) or the formula (14) may not contain the element M, but include only four elements, i.e., manganese, copper, nickel and oxygen. It is noted that the manganese copper nickel oxide containing M in an atomic ratio of more than 0 and 10atomic% or less has conductivity increased by about 10% or more as compared with the manganese copper nickel oxide containing no element M. In addition, in the present embodiment, in the case of a manganese copper nickel oxide containing an element M, M may replace a part of manganese, copper, and/or nickel. For example, in one embodiment, M may replace a portion of manganese; in another embodiment, M may replace a portion of the manganese and a portion of the copper; in yet another embodiment, M may replace a portion of manganese, a portion of copper, and a portion of nickel, although the invention is not so limited. Note that in this embodiment, the atomic number value in the manganese copper nickel oxide represented by the formula (12), the formula (13), or the formula (14) has an error range of ±10% due to formation or non-uniformity of diffusion of oxygen vacancies.
In this embodiment, the manganese copper nickel oxide represented by the formula (12), the formula (13) or the formula (14) may have an orthorhombic structure (Tetragonal structure), a Spinel structure (Spinel structure), a perovskite structure (Perovskite structure) or a 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, thereby lithium ions can be conveniently and rapidly introduced and discharged in the secondary battery to which the anode material including the manganese copper nickel oxide is applied, thereby effectively improving the diffusion rate of lithium ions and the ion conductivity. Further, the manganese copper nickel oxide represented by the formula (12), the formula (13) or the formula (14) has the above-described structure and is less likely to collapse during charge and discharge, whereby a secondary battery using a negative electrode material comprising the manganese copper nickel oxide 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 10nm and about 1 mm. When the average particle diameter of the manganese copper nickel oxide falls within the above range, it is advantageous to form a negative electrode having good characteristics. In the embodiment in which the manganese copper nickel oxide is produced in a solid state, grinding may be performed using a mortar, a ball mill (ball mill), a sand grinder, a vibratory ball mill, or a planetary ball mill (planet ball mill) in order to obtain the manganese copper nickel oxide having the specific average particle size range described above, but the present invention is not limited thereto.
Nickel copper tin oxide
In the present embodiment, the nickel copper tin oxide may be represented by one of the following formulas (15) to (17):
NiCuSn 2 MO x15 (15),
Ni 2 CuSn 3 MO x16 (16) the process is carried out,
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 correspond to the specific values listed above, the secondary battery to which the anode material including the nickel copper tin oxide is applied has excellent capacity and improved 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 10atomic% or less relative to the total atomic number of the metal elements in the nickel-copper-tin oxide represented by the formula (15), the formula (16) or the 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 include only four elements, i.e., nickel, copper, tin and oxygen. It is noted that the nickel-copper-tin oxide containing M in an atomic ratio of more than 0 and 10atomic% or less has a conductivity increased by about 15% or more as compared with the nickel-copper-tin oxide containing no element M. In addition, in the present embodiment, in the case of nickel copper tin oxide containing the element M, M may replace a part of nickel, copper, and/or tin. For example, in one embodiment, M may replace a portion of nickel; in another embodiment, M may replace a portion of the nickel and a portion of the copper; in yet another embodiment, M may replace a portion of nickel, a portion of copper, and a portion of tin, although the invention is not limited thereto. Note that in this embodiment, the number of atoms in the nickel-copper-tin oxide represented by the formula (15), the formula (16) or the formula (17) may have an error range of ±10% due to formation or non-uniformity of diffusion of oxygen vacancies.
In this embodiment, the nickel copper tin oxide represented by formula (15), formula (16) or formula (17) may have a perovskite structure (Perovskite structure), a sodium chloride structure (Sodium chloride structure) or a chalcopyrite structure (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, whereby lithium ions can be conveniently and rapidly introduced and withdrawn in a secondary battery to which a negative electrode material including the nickel-copper-tin oxide is applied, thereby effectively improving the diffusion rate of lithium ions and the ion conductivity. In addition, the nickel-copper-tin oxide represented by the formula (15), the formula (16) or the formula (17) has the above structure and is not likely to collapse during charge and discharge, whereby a secondary battery using a negative electrode material including the nickel-copper-tin oxide 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 10nm and about 1 mm. When the average particle diameter of the nickel-copper-tin oxide falls within the above range, it is advantageous to form a negative electrode having good characteristics. In the embodiment in which the nickel copper tin oxide is produced in a solid state method, in order to obtain the nickel copper tin oxide having the above-described specific average particle diameter range, grinding may be performed using a mortar, a ball mill (ball mill), a sand grinder, a vibration ball mill, or a planetary ball mill (planet ball mill), but the present invention is not limited thereto.
In addition, in the present embodiment, the method for producing an oxide mixture containing four or more elements includes, for example, performing a mixing step. The mixing step is performed by, for example, a physical dry mixing method or a physical wet mixing method, but the present invention is not limited thereto. In embodiments where the physical dry mixing method is used to prepare the oxide mixture containing more than four elements, the mixing temperature may be room temperature, for example, above about 25 ℃. In embodiments where the physical wet mixing process is used to prepare the oxide mixture containing more than four elements, the mixing temperature may be room temperature, e.g., about 25 ℃ or more, and the solvent may be water, alcohol, acetone, or methanol.
In this embodiment, the oxide mixture containing four or more 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, 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. Hereinafter, the above-described various oxide mixtures will be described in detail.
Oxide mixtures containing cobalt, copper and tin
In the present embodiment, the oxide mixture containing cobalt, copper and tin may be formed of Co 3 O 4 、Co 2 O 3 At least one of CoO, cuO and Cu 2 At least one of O, and SnO 2 At least one of them is subjected to a mixing step. That is, the mixture of cobalt, copper and tin-containing oxides may be obtained by a mixing step of cobalt oxide, copper oxide, and tin oxide. In addition, in the present 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 is in accordance with the specific ratios listed above, a secondary battery, to which the anode material including the oxide mixture containing cobalt, copper and tin is applied, has excellent capacity and improved capacity retention.
In the present embodiment, co can be selectively used in the mixing step 3 O 4 、Co 2 O 3 At least one of CoO, cuO and Cu 2 At least one of O and SnO 2 Is mixed with an oxide containing M, wherein M is selected from at least one element of Ni, cr, mn, zn, al, ti, in, mo and W. That is, the oxide mixture containing cobalt, copper and tin may optionally include element M. Relative to the metal elements in the oxide mixture containing cobalt, copper and tin The total atomic number of the elements, and the atomic number ratio of M is more than 0 and less than or equal to 10atomic%. It is noted that the mixture of cobalt, copper and tin containing oxides mixed with the M containing oxide and having an atomic number ratio of M of greater than 0 to less than or equal to 10atomic% has an increased conductivity of about 8% or more as compared with the mixture of cobalt, copper and tin containing oxides not mixed with the M containing oxide. It should be noted that in the present embodiment, the numerical value of the atomic ratio of the elements in the oxide mixture containing cobalt, copper and tin may have an error range of ±10% due to formation or non-uniformity of diffusion of oxygen vacancies.
In the present embodiment, by manufacturing the anode using an anode material including a mixture of oxides including cobalt, copper, and tin, the migration of lithium ions therein and the migration thereof can be performed 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 a secondary battery using the anode material including the oxide mixture containing cobalt, copper and tin can be remarkably increased. In addition, tin oxide can achieve high capacity performance as a negative electrode material, copper oxide can achieve good cycle life as a negative electrode material, and cobalt oxide can achieve good lithium ion conductivity as a negative electrode material, so a secondary battery using a negative electrode material including an oxide mixture obtained by mixing cobalt oxide, copper oxide, and tin oxide can have excellent performance and be safe.
Oxide mixtures containing silicon, tin and iron
In the present embodiment, the oxide mixture containing silicon, tin and iron may be formed of SiO 2 At least one of SiO, snO and SnO 2 At least one of (1) and Fe 2 O 3 、Fe 3 O 4 And mixing with at least one of FeO. That is, the mixture of silicon, tin and iron-containing oxides may be obtained by performing a mixing step of silicon oxide, tin oxide, and iron oxide. In addition, in the present embodiment, the atomic number 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 is in accordance with the specific ratios listed above, a secondary battery to which the anode material including the oxide mixture of silicon, tin and iron is applied has excellent capacity and improved capacity retention.
In the present embodiment, siO can be selectively used in the mixing step 2 At least one of SiO, snO and SnO 2 At least one of (1) and Fe 2 O 3 、Fe 3 O 4 Mixed with at least one of FeO and an oxide containing M, wherein M is selected from at least one element of Cr, mn, zn, al, ti, in, mo and W. That is, the oxide mixture containing silicon, tin and iron may optionally include element M. The atomic number ratio of M is from 0 to 10atomic% or more relative to the total atomic number of elements other than oxygen in the oxide mixture containing silicon, tin and iron. It is noted that the mixture of silicon-containing, tin and iron oxides mixed with the M-containing oxide and having an atomic number ratio of M of from more than 0 to 10atomic% has an increased conductivity of about 10% or more, as compared with the mixture of silicon-containing, tin and iron oxides not mixed with the M-containing oxide. It should be noted that in the present embodiment, the numerical value of the atomic ratio of the elements in the oxide mixture containing silicon, tin and iron may have an error range of ±10% due to formation or non-uniformity of diffusion of oxygen vacancies.
In the present embodiment, by manufacturing the anode using an anode material including an oxide mixture containing silicon, tin, and iron, the migration of lithium ions into and out of the anode material can be performed 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 a secondary battery using the anode material including the oxide mixture of silicon, tin and iron can be remarkably increased. In addition, tin oxide can achieve high capacity performance as a negative electrode material, iron oxide can achieve good cycle life as a negative electrode material, and silicon oxide can achieve good lithium ion conductivity as a negative electrode material, so a secondary battery using a negative electrode material including an oxide mixture obtained by mixing silicon oxide, tin oxide, and iron oxide can have excellent performance and safety.
Oxide mixtures containing copper, manganese and silicon
In the present embodiment, the oxide mixture containing copper, manganese and silicon may be composed of CuO and Cu 2 At least one of O, siO 2 At least one of SiO, mnO 2 、Mn 2 O 3 With Mn 3 O 4 At least one of them is subjected to a mixing step. That is, the copper, manganese and silicon containing oxide mixture may be obtained by performing a mixing step of copper oxide, manganese oxide, and silicon oxide. In addition, in the present embodiment, the atomic number 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 is in accordance with the specific ratios listed above, a secondary battery to which the anode material including the oxide mixture containing copper, manganese and silicon is applied has excellent capacity and improved capacity retention.
In the present embodiment, cuO and Cu can be selectively mixed in the mixing step 2 At least one of O, siO 2 At least one of SiO, mnO 2 、Mn 2 O 3 With Mn 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 element M. The atomic number ratio of M is from greater than 0 to less than or equal to 10atomic% relative to the total atomic number of elements other than oxygen in the oxide mixture containing copper, manganese and silicon. It is noted that the mixture of the oxides of copper, manganese and silicon mixed with the oxide containing M and having an atomic number ratio of M of more than 0 to 10atomic% has a conductivity increased by about 10% or more, compared with the mixture of the oxides of copper, manganese and silicon not mixed with the oxide containing M. It should be noted that in this embodiment, the elements in the oxide mixture containing copper, manganese and siliconThe numerical value of the atomic ratio of the element may have an error range of + -10% due to formation or diffusion unevenness of oxygen vacancies.
In the present embodiment, the copper, manganese and silicon containing oxide mixture obtained by the mixing step of the copper, manganese and silicon oxides has a synergistic effect due to the interaction between the various oxides, so that the capacity of the secondary battery using the anode material including the copper, manganese and silicon containing oxide mixture can be remarkably increased. In addition, in the present embodiment, by manufacturing the anode using an anode material including an oxide mixture containing copper, manganese, and silicon, whereby lithium ions can migrate in and out therein via different paths, polarization effects can be slowed down, and charge-discharge cycle life can be improved. In addition, copper oxide can achieve a good cycle life as a negative electrode material, manganese oxide can achieve a low overpotential as a negative electrode material, and silicon oxide can achieve a good lithium ion conductivity as a negative electrode material, so a secondary battery using a negative electrode material including an oxide mixture obtained by mixing copper oxide, manganese oxide, and silicon oxide can have excellent performance and safety.
Oxide mixtures containing tin, manganese and nickel
In the present embodiment, the oxide mixture containing tin, manganese and nickel may be made of SnO and SnO 2 At least one of them, mnO 2 、Mn 2 O 3 With Mn 3 O 4 At least one of NiO and Ni 2 O 3 At least one of them is subjected to a mixing step. That is, the mixture of oxides containing tin, manganese and nickel may be obtained by performing a mixing step of the oxides of tin, manganese and nickel. In addition, in the present embodiment, the atomic number 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 is in accordance with the specific ratios listed above, a secondary battery employing a negative electrode material including the oxide mixture containing tin, manganese and nickel has excellent capacityAn improved capacitance retention.
In the present embodiment, when the mixing step is performed, snO and SnO can be selectively mixed 2 At least one of them, mnO 2 、Mn 2 O 3 With Mn 3 O 4 At least one of NiO and 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 element M. The atomic number ratio of M is from more than 0 to 10atomic% or less relative to the total atomic number of the metal elements in the oxide mixture containing tin, manganese and nickel. It is worth mentioning that the mixture of tin, manganese and nickel oxides mixed with the M-containing oxide and having an atomic number ratio of M of greater than 0 to less than or equal to 10atomic% has an increased conductivity of about 10% or more, as compared with the mixture of tin, manganese and nickel oxides not mixed with the M-containing oxide. It should be noted that in the present embodiment, the numerical value of the atomic ratio of the elements in the oxide mixture containing tin, manganese and nickel may have an error range of ±10% due to formation or non-uniformity of diffusion of oxygen vacancies.
In the present embodiment, the synergistic effect of the tin, manganese and nickel-containing oxide mixture obtained by the mixing step of the tin oxide, manganese oxide and nickel oxide due to the interaction between the plurality of oxides allows the capacity of the secondary battery to be significantly increased using the anode material including the tin, manganese and nickel-containing oxide mixture. In addition, in the present embodiment, by manufacturing the anode using an anode material including a mixture of oxides containing tin, manganese, and nickel, whereby lithium ions can migrate in and out therein via different paths, polarization effects can be slowed down, and charge-discharge cycle life can be improved. In addition, tin oxide can achieve high capacity performance as a negative electrode material, manganese oxide can achieve low overpotential as a negative electrode material, and nickel oxide can achieve good lithium ion conductivity as a negative electrode material, so a secondary battery using a negative electrode material including an oxide mixture obtained by mixing tin oxide, manganese oxide, and nickel oxide can have excellent performance and safety.
Oxide mixtures containing manganese, copper and nickel
In the present embodiment, the oxide mixture containing manganese, copper and nickel may be composed of MnO, mnO 2 、Mn 2 O 3 With Mn 3 O 4 At least one of CuO and Cu 2 At least one of O, niO and Ni 2 O 3 At least one of them is subjected to a mixing step. That is, the manganese, copper and nickel containing oxide mixture may be obtained by performing a mixing step of manganese oxide, copper oxide, and nickel oxide. In the present 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 is in accordance with the specific ratios listed above, a secondary battery to which the anode material including the manganese, copper and nickel-containing oxide mixture is applied has excellent capacity and improved capacity retention.
In the present embodiment, mnO and MnO can be selectively added in the mixing step 2 、Mn 2 O 3 With Mn 3 O 4 At least one of CuO and Cu 2 At least one of O, niO and Ni 2 O 3 Is mixed with an oxide containing M, wherein M is selected from at least one element of Fe, cr, zn, al, ti, in, mo, W and Si. That is, the manganese, copper and nickel containing oxide mixture may optionally include element M. The atomic number ratio of M is from more than 0 to 10atomic% or less relative to the total atomic number of the metal elements in the oxide mixture containing manganese, copper and tin. It is noted that the mixture of oxides containing manganese, copper and nickel, in which the oxides containing M are mixed and the atomic number ratio of M is from more than 0 to 10atomic%, has an increased conductivity of about 5% or more, compared with the mixture of oxides containing manganese, copper and nickel, in which the oxides containing M are not mixed. Note that in this embodiment, the alloy contains manganese and copper The numerical value of the atomic ratio of the element in the oxide mixture with nickel may have an error range of + -10% due to formation or diffusion unevenness of oxygen vacancies.
In the present embodiment, by manufacturing the anode using an anode material including a mixture of oxides including manganese, copper, and nickel, lithium ions can migrate in and out therein via different paths, so that polarization effects can be slowed down and charge-discharge cycle life can be improved. In addition, since manganese oxide can achieve a low overpotential as a negative electrode material, copper oxide can achieve a good cycle life as a negative electrode material, and nickel oxide can achieve a high capacity performance as a negative electrode material, a secondary battery using a negative electrode material including an oxide mixture obtained by mixing manganese oxide, copper oxide, and nickel oxide can have excellent performance and safety.
Nickel, copper and tin containing oxide mixtures
In the present embodiment, the oxide mixture containing nickel, copper and tin may be formed of Ni 2 O 3 At least one of NiO, cuO and Cu 2 At least one of O, and SnO 2 At least one of them is subjected to a mixing step. That is, the nickel, copper and tin containing oxide mixture may be obtained by mixing nickel oxide, copper oxide, and tin oxide. In addition, in the present 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 is in accordance with the specific ratios listed above, a secondary battery to which the anode material including the nickel, copper and tin-containing oxide mixture is applied has excellent capacity and improved capacity retention.
In the present embodiment, ni can be selectively added at the time of the mixing step 2 O 3 At least one of NiO, cuO and Cu 2 At least one of O and SnO 2 Is mixed with an oxide containing M, wherein M is at least one element selected from Cr, mn, zn, al, ti, in, mo, W and Co. That is to say that the first and second,the nickel, copper and tin containing oxide mixture may optionally include element M. The atomic number ratio of M is from more than 0 to 10atomic% relative to the total atomic number of the metallic elements in the oxide mixture containing nickel, copper and tin. It is worth mentioning that the mixture of nickel-containing, copper-tin oxides mixed with the M-containing oxide and having an atomic number ratio of M of greater than 0 to less than or equal to 10atomic% has an increased conductivity of about 8% or more, as compared to the mixture of nickel-containing, copper-tin oxides not mixed with the M-containing oxide. Note that in this embodiment, the numerical value of the atomic ratio of the elements in the oxide mixture containing nickel, copper, and tin may have an error range of ±10% due to formation or non-uniformity of diffusion of oxygen vacancies.
In the present embodiment, by manufacturing the anode using an anode material including an oxide mixture containing nickel, copper, and tin, whereby lithium ions can migrate in and out therein via different paths, polarization effects can be slowed down, and charge-discharge cycle life can be improved. In this way, the capacity of a secondary battery using the anode material including the oxide mixture containing nickel, copper and tin can be remarkably increased. In addition, tin oxide can achieve high capacity performance as a negative electrode material, copper oxide can achieve good cycle life as a negative electrode material, and nickel oxide can achieve good lithium ion conductivity as a negative electrode material, so a secondary battery using a negative electrode material including an oxide mixture obtained by mixing nickel oxide, copper oxide, and tin oxide can have excellent performance and be safe.
Another embodiment of the present invention also proposes a secondary battery to which any one of the anode materials proposed in the foregoing embodiments is applied.
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 a package structure 112. In the present embodiment, the secondary battery 100 may further include a separation film 106. In the present embodiment, the secondary battery 100 may be a lithium ion battery.
In this embodiment, the anode 102 may include a current collector 102a and an anode material layer 102b disposed on the current collector 102 a. In this embodiment, the current collector 102a may be a metal foil, such as a copper foil, a nickel foil, or a 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 anode material layer 102b includes any of the anode materials set forth in the foregoing embodiments. In this embodiment, the negative electrode material may 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 the present embodiment, the anode material layer 102b may further include a conductive aid and a binder. In this embodiment, the conductive agent may be natural graphite, artificial graphite, carbon black (carbon black), conductive carbon (e.g., VGCF, super P, KS4, KS6, or ECP), acetylene black (acetylene black), ketjen black (Ketjen black), carbon whiskers (carbon whiskers), carbon fibers, metal powders, metal fibers, or conductive ceramic (ceramics) materials. In detail, the conductive agent is used to improve the electrical contact between the negative electrode materials. In this embodiment, the adhesive may be a Polydifluoroethylene (PVDF), a Styrene Butadiene Rubber (SBR), a polyamide, a melamine resin, or a combination thereof. In detail, the anode material may be adhered to the current collector 102a by an adhesive.
In the present embodiment, the positive electrode 104 and the negative electrode 102 are arranged separately. In the present embodiment, the positive electrode 104 includes a current collector 104a and a positive electrode material layer 104b disposed on the current collector 104 a. In this embodiment, the current collector 104a may be a metal foil, such as a copper foil, a nickel foil, an aluminum foil, or a 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 the present embodiment, the positive electrode material may include lithium cobalt oxide (LiCoO) 2 ) Lithium manganate (LiMn) 2 O 4 ) Lithium nickelate (LiNiO) 2 ) Lithium iron phosphate (LiFePO) 4 ) Or a combination thereof. In the present embodiment, the positive electrode materialThe material may be disposed on the current collector 104a by, for example, coating, sputtering, hot pressing, sintering, physical vapor deposition, or chemical vapor deposition. In addition, in the present embodiment, the positive electrode material layer 104b may further include an adhesive. In this embodiment, the adhesive may be a Polydifluoroethylene (PVDF), a Styrene Butadiene Rubber (SBR), a polyamide, a melamine resin, or a combination thereof. In detail, the positive electrode material may be adhered to the current collector 104a by an adhesive.
In the present embodiment, the electrolyte 108 is provided between the negative electrode 102 and the positive electrode 104. Electrolyte 108 may include a liquid electrolyte, a colloidal electrolyte, a molten salt electrolyte, or a solid electrolyte.
In the present embodiment, the separator 106 is disposed between the anode 102 and the cathode 104, the separator 106, the anode 102 and the cathode 104 define a receiving area 110, and the electrolyte 108 is disposed in the receiving area 110. In the present embodiment, the material of the isolation film 106 may be an insulating material, such as Polyethylene (PE), polypropylene (PP), or a composite structure (e.g., PE/PP/PE) formed by the above materials.
In the present embodiment, the secondary battery 100 includes the separation film 106 to separate the anode 102 from the cathode 104 and allow penetration of ions, but the present invention is not limited thereto. In other embodiments, where the electrolyte 108 is a solid state electrolyte, the secondary battery 100 does not include a separator.
In this embodiment, the encapsulation structure 112 encapsulates the negative electrode 102, the positive electrode 104, and the electrolyte 108. In the present embodiment, the material of the package structure 112 is, for example, aluminum foil or stainless steel.
In the present 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 wound structure in which a negative electrode, a positive electrode, and a separator film, if necessary, are wound, or a laminated structure in which a flat plate is laminated. In the present embodiment, the secondary battery 100 is, for example, a paper (paper) type battery, a button type battery, a coin (coin) type battery, a laminate type battery, a cylindrical type battery, or a square type battery.
In particular, since the negative electrode 102 of the secondary battery 100 uses any of the negative electrode materials according to the foregoing embodiments, the secondary battery 100 can have good capacity, stability, and charge-discharge cycle life as described above.
Hereinafter, the features of the present invention will be described more specifically with reference to examples 1 to 14 and comparative examples 1 to 9. Although the following examples 1 to 14 are described, the materials used, the amounts and ratios thereof, the details of the treatment, the flow of the treatment, and the like may be appropriately changed without departing from the scope of the present invention. Accordingly, the present invention should not be construed restrictively by examples described below.
Example 1
Preparation of negative electrode material
CoO powder (cobalt-containing precursor), cuO powder (copper-containing precursor), snO powder (tin-containing precursor) and W oxide powder (elemental M-containing precursor) were each milled at room temperature by a ball mill, and then mixed and pressed into Green pellets (about 1 cm in diameter). The green body was placed in a high temperature furnace to obtain a cobalt copper tin oxide block represented by the aforementioned formula (1) (i.e., the anode material of example 1), wherein x1 is 8, element M is W, the atomic number ratio of element M is about 1 to 10atomic%, and the average particle diameter of cobalt copper tin oxide is between about 0.1 μm and about 10 μm.
Preparation of secondary battery
The crushed and ground anode material of example 1, super P conductive carbon and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water were slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to the slurry and the slurry was slurried for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and after the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, the dried copper foil was cut into an anode of example 1 having a diameter of about 12.8mm by a cutter.
Button cell (model: CR 2032) was assembled using the anode of example 1 as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 1 was produced.
Example 2
Preparation of negative electrode material
CoO powder (cobalt-containing precursor), cuO powder (copper-containing precursor), snO powder (tin-containing precursor) and W oxide powder (elemental M-containing precursor) were each milled at room temperature by a ball mill, and then mixed and pressed into Green pellets (about 1 cm in diameter). The green body was placed in a high temperature furnace to obtain a cobalt copper tin oxide block represented by the aforementioned formula (2) (i.e., the anode material of example 2), wherein x2 is 4, element M is W, the atomic number ratio of element M is about 1 to 10atomic%, and the average particle diameter of cobalt copper tin oxide is between about 0.1 μm and about 10 μm.
Preparation of secondary battery
The crushed and ground anode material of example 2, super P conductive carbon, and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water were slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to mix for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and after the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, the dried copper foil was cut into an anode of example 2 having a diameter of about 12.8mm with a cutter.
Button cell (model: CR 2032) was assembled using the anode of example 2 as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 2 was produced.
Example 3
Preparation of negative electrode material
CoO powder (cobalt-containing precursor), cuO powder (copper-containing precursor), snO powder (tin-containing precursor) and W oxide powder (elemental M-containing precursor) were each milled at room temperature by a ball mill, and then mixed and pressed into Green pellets (about 1 cm in diameter). The green body was placed in a high temperature furnace to obtain a cobalt copper tin oxide block represented by the aforementioned formula (3) (i.e., the anode material of example 3), wherein x3 is 4, element M is W, the atomic number ratio of element M is about 1 to 10atomic%, and the average particle diameter of cobalt copper tin oxide is between about 0.1 μm and about 10 μm.
Preparation of secondary battery
The crushed and ground anode material of example 3, super P conductive carbon, and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water were slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to mix for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and after the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, the dried copper foil was cut into an anode of example 3 having a diameter of about 12.8mm with a cutter.
Button cell (model: CR 2032) was assembled using the anode of example 3 as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 3 was produced.
Example 4
Preparation of negative electrode material
CoO powder (cobalt oxide), cuO powder (copper oxide) and SnO powder are each prepared by ball milling at room temperature 2 After grinding and mixing the powder (tin oxide) and the W oxide powder (oxide containing element M) to obtain an oxide mixture containing cobalt, copper and tin (i.e. the anode material of example 4), wherein the raw materials of cobalt, copper and tinThe ratio of the sub-numbers is 1:1:1, wherein the element M is W, and the atomic number ratio of the element M is about 1-10 atomic%.
Preparation of secondary battery
The anode material of example 4, super P conductive carbon, and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water was slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to the slurry to mix for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, after which the dried copper foil was cut into an anode of example 4 having a diameter of about 12.8mm by a cutter.
Button cell (model: CR 2032) was assembled using the anode of example 4 as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 4 was produced.
Example 5
Preparation of negative electrode material
SiO was separated at room temperature by ball mill 2 Powder (silicon-containing precursor), snO 2 Powder (tin-containing precursor), fe 2 O 3 Powder (iron-containing precursor), tiO 2 After grinding the powders (precursor containing element M), the powders were mixed and pressed into Green billets (Green billets) having a diameter of about 1 cm. The green body was placed in a high temperature furnace to obtain a bulk silicon tin iron oxide (i.e., the anode material of example 4) represented by the aforementioned formula (4), wherein x4 is 21, element M is Ti, the atomic number ratio of element M is about 1 to 10atomic%, and the average particle diameter of silicon tin iron oxide is about 0.1 μm to about 10 μm.
Preparation of secondary battery
The crushed and ground anode material of example 5, super P conductive carbon and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water were slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to the slurry and the slurry was slurried for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and after the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, the dried copper foil was cut into an anode of example 5 having a diameter of about 12.8mm by a cutter.
Button cell (model: CR 2032) was assembled using the anode of example 5 as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 5 was produced.
Example 6
Preparation of negative electrode material
SiO was separated at room temperature by ball mill 2 Powder (silicon oxide), snO 2 Powder (tin oxide), fe 2 O 3 Powder (iron oxide), tiO 2 After the powder (oxide containing element M) was ground and mixed, an oxide mixture containing silicon, tin and iron (i.e., the anode material of example 6) was obtained, in which the atomic number ratio of silicon, tin and iron was 4:1:16, the element M is Ti, and the atomic number ratio of the element M is about 1 to 10atomic%.
Preparation of secondary battery
The anode material of example 6, super P conductive carbon, and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water was slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to the slurry to mix for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, after which the dried copper foil was cut into an anode of example 6 having a diameter of about 12.8mm in a cutter.
Button cells (model: CR 2032) were assembled,wherein the anode of example 6 was used as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 6 was produced.
Example 7
Preparation of negative electrode material
At room temperature, cuO powder (copper-containing precursor), mnO powder (manganese-containing precursor) and SiO were each prepared by ball milling 2 Powder (silicon-containing precursor), tiO 2 After grinding the powders (precursor containing element M), the powders were mixed and pressed into Green billets (Green billets) having a diameter of about 1 cm. The green body was placed in a high temperature furnace to obtain a copper-manganese-silicon oxide block represented by the aforementioned formula (7) (i.e., the anode material of example 7), wherein x7 is 1, element M is Ti, the atomic number ratio of element M is about 1 to 10atomic%, and the average particle diameter of copper-manganese-silicon oxide is about 0.1 μm to about 10 μm.
Preparation of secondary battery
The crushed and ground anode material of example 7, super P conductive carbon, and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water were slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to mix for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and after the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, the dried copper foil was cut into an anode of example 7 having a diameter of about 12.8mm with a cutter.
Button cell (model: CR 2032) was assembled using the anode of example 7 as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 7 was produced.
Example 8
Preparation of negative electrode material
CuO powder (copper oxide), mnO powder (manganese oxide) and SiO powder were each prepared at room temperature by a ball mill 2 Powder (silicon oxide), tiO 2 After the powder (oxide containing element M) was ground and mixed, an oxide mixture containing copper, manganese and silicon (i.e., anode material of example 8) was obtained, in which the atomic number ratio of copper, manganese and silicon was 1:4:1, the element M is Ti, and the atomic number ratio of the element M is about 1 to 10atomic%.
Preparation of secondary battery
The anode material of example 8, super P conductive carbon and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water was slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to the slurry and the slurry was slurried for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, after which the dried copper foil was cut into an anode of example 8 having a diameter of about 12.8mm in a cutter.
Button cell (model: CR 2032) was assembled using the anode of example 8 as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 8 was produced.
Example 9
Preparation of negative electrode material
SnO was separated at room temperature by ball mill 2 Powder (tin-containing precursor), mnO 2 After grinding the powder (manganese-containing precursor), niO powder (nickel-containing precursor), mo oxide powder (elemental M-containing precursor), the powders were mixed and pressed into Green pellets (Green pellet) having a diameter of about 1 cm. Placing the green body in a high temperature furnace to obtain tin represented by the formula (8)The manganese nickel oxide block (i.e., the anode material of example 9) in which x8 is 7, element M is Mo, the atomic number ratio of element M is about 1 to 10atomic, and the average particle diameter of tin manganese nickel oxide is about 0.1 μm to about 10 μm.
Preparation of secondary battery
The crushed and ground anode material of example 9, super P conductive carbon, and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water were slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to mix for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and after the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, the dried copper foil was cut into an anode of example 9 having a diameter of about 12.8mm with a cutter.
Button cell (model: CR 2032) was assembled using the anode of example 9 as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 9 was produced.
Example 10
Preparation of negative electrode material
SnO was separated at room temperature by ball mill 2 Powder (tin oxide), mnO 2 After grinding and mixing the powder (manganese oxide), niO powder (nickel oxide) and Mo oxide powder (oxide containing element M) to obtain an oxide mixture containing tin, manganese and nickel (i.e., the anode material of example 10), wherein the atomic number ratio of tin, manganese and nickel is 1:2:1, the element M is Mo, and the atomic number ratio of the element M is about 1-10 atomic%.
Manufacture of secondary battery
The anode material of example 10, super P conductive carbon, and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water was slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to the slurry to mix for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, after which the dried copper foil was cut into an anode of example 10 having a diameter of about 12.8mm in a cutter.
Button cell (model: CR 2032) was assembled using the anode of example 10 as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, the secondary battery of example 10 was produced.
Example 11
Preparation of negative electrode material
MnO was separated at room temperature by ball mill 2 After grinding the powder (manganese-containing precursor), cuO powder (copper-containing precursor), niO powder (nickel-containing precursor) and Mo oxide powder (elemental M-containing precursor), the powders were mixed and pressed into Green billets (Green billets) having a diameter of about 1 cm. The green body was placed in a high temperature furnace to obtain a bulk material of manganese copper nickel oxide represented by the aforementioned formula (13) (i.e., the anode material of example 11), wherein the element M is Mo, the atomic number ratio of the element M is about 1 to 10atomic%, and the average particle diameter of the manganese copper tin oxide is about 0.1 μm to about 10 μm.
Preparation of secondary battery
The crushed and ground anode material of example 11, super P conductive carbon, and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water were slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to mix for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and after the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, the dried copper foil was cut into an anode of example 11 having a diameter of about 12.8mm with a cutter.
Button cell (model: CR 2032) was assembled using the anode of example 11 as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 11 was produced.
Example 12
Preparation of negative electrode material
At room temperature, respectively mixing MnO with ball mill 2 After grinding and mixing of the powder (manganese oxide), cuO powder (copper oxide), niO powder (nickel oxide), mo oxide powder (oxide containing element M) to obtain an oxide mixture containing manganese, copper and nickel (i.e., anode material of example 12), wherein the atomic number ratio of manganese, copper and nickel is 2:1:1, the element M is Mo, and the atomic number ratio of the element M is about 1-10 atomic%.
Preparation of secondary battery
The anode material of example 12, super P conductive carbon, and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water was slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to the slurry to mix for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, after which the dried copper foil was cut into an anode of example 12 having a diameter of about 12.8mm in a cutter.
Button cell (model: CR 2032) was assembled using the anode of example 12 as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 12 was produced.
Example 13
Preparation of negative electrode material
NiO powder (nickel oxide), cuO powder (copper oxide) and SnO are respectively mixed with a ball mill at room temperature 2 After the powder (tin oxide) and the W oxide powder (oxide containing element M) were ground and mixed, an oxide mixture containing nickel, copper and tin (i.e., anode material of example 13) was obtained, in which the atomic number ratio of nickel, copper and tin was 1:1:2, the element M is W, and the atomic number ratio of the element M is about 1 to 10atomic%.
Preparation of secondary battery
The crushed and ground anode material of example 13, super P conductive carbon, and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water were slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to the slurry and the slurry was slurried for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and after the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, the dried copper foil was cut into an anode of example 13 having a diameter of about 12.8mm in a cutter.
Button cell (model: CR 2032) was assembled using the anode of example 13 as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 13 was produced.
Example 14
Preparation of negative electrode material
NiO powder (precursor containing nickel), cuO powder (precursor containing copper) and SnO are respectively mixed with a ball mill at room temperature 2 After grinding the powder (tin-containing precursor) and the W-oxide powder (elemental M-containing precursor), the powders were mixed and pressed into Green billets (Green billets) having a diameter of about 1 cm. Placing the green body in a high temperature furnace to obtain a nickel copper tin oxide block represented by the above formula (15) (i.e., the anode material of example 14), wherein x15 is 6, M is W, M is a raw material of the elementThe ratio of the number of the sub-numbers is about 1 to 10atomic, and the average particle diameter of the manganese copper tin oxide is about 0.1 μm to about 10 μm.
Preparation of secondary battery
The crushed and ground anode material of example 14, super P conductive carbon, and a binder (i.e., sodium carboxymethylcellulose (CMC) dissolved in water were slurried at a weight ratio of 7:2:1, then zirconium dioxide pellets were added to mix for about 30 minutes to form an anode slurry, and then the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and uniformly scraped, and after the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, the dried copper foil was cut into an anode of example 14 having a diameter of about 12.8mm with a cutter.
Button cell (model: CR 2032) was assembled using the anode of example 14 as the working electrode, lithium metal as the counter electrode, 1M LiPF 6 Added to an organic solvent as an electrolyte, a polypropylene film (trade name: celgard #2400, manufactured by Celgard) as a separator, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 14 was produced.
Comparative example 1
Preparation of secondary battery
A secondary battery of comparative example 1 was produced according to the same manufacturing procedure as in example 1, except that: in the secondary battery of example 1, the working electrode was the negative electrode using example 1; in the secondary battery of comparative example 1, the material of the working electrode was Co 2 SnO 4 。
Comparative example 2
Preparation of secondary battery
A secondary battery of comparative example 2 was produced in accordance with the same manufacturing procedure as in example 1, except that: in the secondary battery of example 1, the working electrode was the negative electrode using example 1; in the secondary battery of comparative example 2, however, the material of the working electrode was CoO.
Comparative example 3
Preparation of secondary battery
A secondary battery of comparative example 3 was produced in accordance with the same manufacturing procedure as in example 1, except that: in the secondary battery of example 1, the working electrode was the negative electrode using example 1; in the secondary battery of comparative example 3, the material of the working electrode was CuO.
Comparative example 4
Preparation of secondary battery
A secondary battery of comparative example 4 was produced in accordance with the same manufacturing procedure as in example 1, except that: in the secondary battery of example 1, the working electrode was the negative electrode using example 1; in the secondary battery of comparative example 4, the material of the working electrode was SnO 2 。
Comparative example 5
Preparation of secondary battery
A secondary battery of comparative example 5 was produced in accordance with the same manufacturing procedure as in example 1, except that: in the secondary battery of example 1, the working electrode was the negative electrode using example 1; in the secondary battery of comparative example 5, the material of the working electrode was SiO 2 。
Comparative example 6
Preparation of secondary battery
A secondary battery of comparative example 6 was produced in accordance with the same manufacturing procedure as in example 1, except that: in the secondary battery of example 1, the working electrode was the negative electrode using example 1; in the secondary battery of comparative example 6, the material of the working electrode was Fe 2 O 3 。
Comparative example 7
Preparation of secondary battery
A secondary battery of comparative example 7 was produced in accordance with the same manufacturing procedure as in example 1, except that: in the secondary battery of example 1, the working electrode was the negative electrode using example 1; in the secondary battery of comparative example 7, however, the material of the working electrode was MnO.
Comparative example 8
Preparation of secondary battery
Comparison was made according to the same manufacturing procedure as in example 1The secondary battery of example 8 is different in that: in the secondary battery of example 1, the working electrode was the negative electrode using example 1; in the secondary battery of comparative example 8, the material of the working electrode was MnO 2 。
Comparative example 9
Preparation of secondary battery
A secondary battery of comparative example 9 was produced in accordance with the same manufacturing procedure as in example 1, except that: in the secondary battery of example 1, the working electrode was the negative electrode using example 1; in the secondary battery of comparative example 9, the material of the working electrode was NiO.
After the secondary batteries of examples 1 to 14 and the secondary batteries of comparative examples 1 to 9 were produced, charge and discharge cycle tests were performed on the secondary batteries of examples 1 to 14 and the secondary batteries of comparative examples 1 to 9, respectively.
Charge-discharge cycle test
The secondary batteries of examples 1 to 14 and the secondary batteries of comparative examples 1 to 9 were each subjected to a capacity test of battery cycle life (cycle life) at a voltage of 0.01V to 3V in an environment of about 15 ℃ to about 30 ℃. The measurement results are shown in fig. 2 to 15.
As can be seen from fig. 2 to 4, the secondary batteries of examples 1 to 3 all have better capacity and capacity maintenance rate after a high cycle number (> 250 times) compared to the secondary battery of comparative example 1.
Although the foregoing test was not performed on the secondary battery including the cobalt copper tin oxide represented by formula (1) in which x1 is 9 or 14, it will be understood by those skilled in the art from the foregoing description of the cobalt copper tin oxide and the test results of example 1 that the secondary battery including the cobalt copper tin oxide represented by formula (1) in which x1 is 9 or 14 will have good capacity and capacity maintenance rate.
Although the foregoing test was not performed on the secondary battery including the cobalt copper tin oxide represented by formula (2) having x2 of 6 or 8, it will be understood by those skilled in the art from the foregoing description and the test results of example 2 that the secondary battery including the cobalt copper tin oxide represented by formula (2) having x2 of 6 or 8 may have good capacity and capacity maintenance rate.
Although the foregoing test was not performed on the secondary battery including the cobalt copper tin oxide represented by formula (3) in which x3 is 3 or 5, it will be understood by those skilled in the art from the foregoing description and the test results of example 1 that the secondary battery including the cobalt copper tin oxide represented by formula (3) in which x3 is 3 or 5 may have good capacity and capacity maintenance rate.
As can be seen from fig. 5, the secondary battery of example 4 has a better capacity and capacity maintenance rate after a high cycle number (> 250 times) compared to the secondary batteries of comparative examples 2 to 4.
Although the atomic number ratio including cobalt, copper and tin is not 5:1:3 or 2:1:1, but from the foregoing description and the test results of example 4, those skilled in the art will understand that the number ratio of cobalt, copper, and tin, including the cobalt, copper, and tin, is 5:1:3 or 2:1:1, the secondary battery containing a mixture of oxides of cobalt, copper and tin has good capacity and capacity retention.
As can be seen from fig. 6 and 7, the secondary batteries of examples 5 and 6 have better capacity and capacity maintenance rate after a high cycle number (> 250 times) compared to the secondary batteries of comparative examples 4 to 6.
Although the foregoing test was not performed on the secondary battery including the silicon tin iron oxide represented by formula (4) in which x4 is greater than 21 to 34, it will be understood by those skilled in the art from the foregoing description and the test results of example 5 that the secondary battery including the silicon tin iron oxide represented by formula (4) in which x4 is greater than 21 to 34 may have good capacity and capacity maintenance rate.
Although the foregoing test was not performed on the secondary battery including the silicon tin iron oxide represented by formula (5) or formula (6), it will be understood by those skilled in the art from the foregoing description and the test results of example 5 that the secondary battery including the silicon tin iron oxide represented by formula (5) or formula (6) will have good capacity and capacity maintenance rate.
Although the atomic number ratio of silicon, tin to iron is not 1:1:1 or 4:1:1, but from the foregoing description and the test results of example 6, those skilled in the art will understand that the number ratio of silicon, tin to iron comprising 1:1:1 or 4:1:1, the secondary battery containing a mixture of oxides of silicon, tin and iron will have good capacity and capacity retention.
As can be seen from fig. 8, the secondary battery of example 7 has good capacity and capacity maintenance rate after a high cycle number (> 250 times).
Although the foregoing test was not performed on the secondary battery including the copper manganese silicon oxide represented by formula (7) in which x7 is greater than 0 to less than 1, it will be understood by those skilled in the art from the foregoing description and the test results of example 7 that the secondary battery including the copper manganese silicon oxide represented by formula (7) in which x7 is greater than 0 to less than 1 may have good capacity and capacity maintenance rate.
As can be seen from fig. 9, the secondary battery of example 8 has a better capacity and capacity retention rate after a high cycle number (> 250 times) compared to the secondary batteries of comparative examples 3, 5 and 7.
Although the atomic number ratio of copper, manganese to silicon is not 1:1: 1. 4:1:1 or 1:1:4, but from the foregoing description and the test results of example 8, those skilled in the art will understand that the number ratio of copper, manganese to silicon is 1:1: 1. 4:1:1 or 1:1:4, the secondary battery containing the oxide mixture of copper, manganese and silicon will have good capacity and capacity retention.
As can be seen from fig. 10 and 11, the secondary batteries of examples 9 and 10 have better capacity and capacity maintenance rate after a high cycle number (> 250 times) compared to the secondary batteries of comparative examples 4, 8 and 9.
Although the foregoing test was not performed on the secondary battery including the tin-manganese-nickel oxide represented by formula (8) having x8 of 4 to less than 7, it will be understood by those skilled in the art from the foregoing description and the test results of example 9 that the secondary battery including the tin-manganese-nickel oxide represented by formula (8) having x8 of 4 to less than 7 may have good capacity and capacity maintenance rate.
Although the foregoing test was not performed on the secondary battery including the tin-manganese-nickel oxide represented by formula (9), formula (10) or formula (11), it will be understood by those skilled in the art from the foregoing description and the test results of example 9 that the secondary battery including the tin-manganese-nickel oxide represented by formula (9), formula (10) or formula (11) has good capacity and capacity maintenance rate.
Although the atomic number ratio including tin, manganese, and nickel is not 1:1: 1. 1:1:2 or 2:1:1, but from the foregoing description and the test results of example 10, those skilled in the art will understand that the number ratio of atoms including tin, manganese, and nickel is 1:1: 1. 1:1:2 or 2:1:1, the secondary battery containing a mixture of oxides of tin, manganese and nickel will have good capacity and capacity retention.
As can be seen from fig. 12, the secondary battery of example 11 has good capacity and capacity retention after a high cycle number (> 250 times).
Although the foregoing test was not performed on the secondary battery including the manganese copper nickel oxide represented by formula (12) or formula (14), it will be understood by those skilled in the art from the foregoing description and the test results of example 11 that the secondary battery including the manganese copper nickel oxide represented by formula (12) or formula (14) may have good capacity and capacity maintenance rate.
As can be seen from fig. 13, the secondary battery of example 12 has a better capacity and capacity retention rate after a high cycle number (> 250 times) compared to the secondary batteries of comparative examples 3, 8 and 9.
Although the atomic number ratio of manganese, copper and nickel is not 3:2:1 or 1:1:1, but from the foregoing description and the test results of example 12, those skilled in the art will understand that the number ratio of manganese, copper and nickel comprising an oxide mixture of manganese, copper and nickel is 3:2:1 or 1:1:1, the secondary battery containing a mixture of oxides of manganese, copper and nickel will have good capacity and capacity retention.
As can be seen from fig. 14, the secondary battery of example 13 has a better capacity and capacity retention rate after a high cycle number (> 250 times) compared to the secondary batteries of comparative examples 3, 4 and 9.
Although the atomic number ratio of nickel, copper and tin is not 2:1:3 or 1:2:3, but from the foregoing description and the test results of example 13, those skilled in the art will understand that the number ratio of nickel, copper to tin included is 2:1:3 or 1:2:3, the secondary battery containing the oxide mixture of nickel, copper and tin will have good capacity and capacity maintenance.
As can be seen from fig. 15, the secondary battery of example 14 had good capacity and capacity retention after a high cycle number (> 250 times).
Although the foregoing test was not performed on the secondary battery including the nickel copper tin oxide represented by formula (15) in which x15 is 3 or 9, it will be understood by those skilled in the art from the foregoing description and the test results of example 14 that the secondary battery including the nickel copper tin oxide represented by formula (15) in which x15 is 3 or 9 may have good capacity and capacity maintenance rate.
Although the foregoing test was not performed on the secondary battery including the nickel copper tin oxide represented by formula (16) or formula (17), it will be understood by those skilled in the art from the foregoing description and the test results of example 14 that the secondary battery including the nickel copper tin oxide represented by formula (16) or formula (17) will have good capacity and capacity maintenance rate.
Based on the foregoing test results, it was confirmed that by preparing a negative electrode using the negative electrode material for a secondary battery of the present invention, a secondary battery to which the negative electrode is applied can have good capacity, stability, and charge-discharge cycle life.
In addition, the secondary battery using the negative electrode material for a secondary battery of the present invention has a higher capacity than commercially available graphite (theoretical capacity value of 372 mAh/g), and thus it is shown that the negative electrode material for a secondary battery of the present invention can effectively improve battery performance.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (5)

1. A negative electrode material for a secondary battery, comprising:
oxide mixture of CuO and Cu 2 At least one of O, siO 2 At least one of SiO, mnO 2 、Mn 2 O 3 With Mn 3 O 4 Wherein the atomic number ratio of copper, manganese to silicon in the oxide mixture is 1:1: 1. 1:4: 1. 4:1:1 or 1:1:4.
2. the anode material for a secondary battery according to claim 1, wherein the mixing step further comprises mixing an oxide containing M, wherein M is at least one element selected from Cr, W, sn, ni, zn, al, ti, in and Mo, and an atomic number ratio of M is from 0 to 10atomic% or more with respect to a total atomic number of elements other than an oxygen element in the oxide mixture.
3. A negative electrode for a secondary battery, comprising:
a current collector; and
a negative electrode material layer disposed on the current collector and including the negative electrode material for a secondary battery according to any one of claims 1 to 2.
4. A secondary battery, characterized by comprising:
a positive electrode;
a negative electrode disposed separately from the positive electrode, wherein the negative electrode is the negative electrode for a secondary battery according to claim 3;
an electrolyte disposed between the positive electrode and the negative electrode; and
and the packaging structure is used for coating the anode, the cathode and the electrolyte.
5. The secondary battery according to claim 4, further comprising a separator disposed between the positive electrode and the negative electrode, wherein the separator, the positive electrode, and the negative electrode define a receiving region, and wherein the electrolyte is disposed in the receiving region.
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