CN113130889B - 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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CN113130889B
CN113130889B CN202010057891.XA CN202010057891A CN113130889B CN 113130889 B CN113130889 B CN 113130889B CN 202010057891 A CN202010057891 A CN 202010057891A CN 113130889 B CN113130889 B CN 113130889B
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oxide
copper
formula
secondary battery
tin
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CN113130889A (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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Priority to CN202210497290.XA priority patent/CN114725368B/en
Priority to CN202010057891.XA priority patent/CN113130889B/en
Priority to CN202210497314.1A priority patent/CN114725359B/en
Priority to CN202210497339.1A priority patent/CN114725360B/en
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Priority to CN202210497310.3A priority patent/CN114725373B/en
Priority to CN202210497341.9A priority patent/CN114824248B/en
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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 includes 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 comprises 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 cathode material for the secondary battery ensures that the secondary battery has good electric capacity and stability.

Description

Negative electrode material for secondary battery, negative electrode, and secondary battery
Technical Field
The present invention relates to an electrode material, an electrode, and a battery, and particularly 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 for secondary lithium batteries that can be repeatedly charged and discharged and have the characteristics of light weight, high voltage value, high energy density, and the like has increased dramatically. Accordingly, the demand for properties such as light weight, durability, high voltage, high energy density, and high safety of the secondary lithium battery is also increasing nowadays. The secondary lithium battery has quite high application and expansion potential especially in light electric vehicles, electric vehicles and large-scale electricity storage industries. The most common commercial electrode material is graphite, but the capacity of graphite (372 mAh/g theoretical) is low, and the performance of the battery made therefrom is limited. Therefore, it is one of the objectives of those skilled in the art to find an electrode material for a secondary battery having high stability and high capacity.
Disclosure of Invention
In view of the above, the present invention provides a negative electrode material and a negative electrode for a secondary battery, which can provide the secondary battery with good capacity and stability.
An embodiment of the present invention provides a negative electrode material for a secondary battery, including a cobalt copper tin oxide represented by one of the following formulas (1) to (3):
Co5Cu1Sn3MOx1the compound of the formula (1),
Co2Cu1Sn1MOx2the compound of the formula (2),
Co1Cu1Sn1MOx3the compound of the formula (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 the group consisting of Ni, Cr, Mn, Zn, Al, Ti, In, Mo and W, and the atomic number ratio of M is 10 atomic% or less with respect to the total number of atoms of the metal elements In the cobalt-copper-tin oxide represented by formula (1), formula (2) or formula (3).
Another embodiment of the present invention provides an anode material for a secondary battery comprising Co3O4、Co2O3And at least one of CoO, CuO and Cu2At least one of O, SnO and SnO2At least one of the above-mentioned oxides, wherein the atomic ratio of cobalt, copper and tin in the oxide mixture is 5: 1: 3. 2: 1: 1 or 1: 1: 1.
another embodiment of the present invention provides an anode material for a secondary battery, including a silicon tin iron oxide represented by one of the following formulas (4) to (6):
Si4Sn1Fe16MOx4the compound of the formula (4),
Si1Sn1Fe1MOx5the compound of the formula (5),
Si4Sn1Fe1MOx6the compound of the formula (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 the group consisting of Cr, Mn, Zn, Al, Ti, In, Mo and W, and the atomic number ratio of M is 10 atomic% or less with respect 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 SiO2And at least one of SiO, SnO and SnO2At least one of them, and Fe2O3、Fe3O4An oxide mixture resulting from a mixing step with at least one of FeO, wherein the atomic ratio of silicon, tin and iron in the oxide mixture is 4: 1: 16. 1: 1: 1 or 4: 1: 1.
another embodiment of the present invention provides an anode material for a secondary battery including a copper-manganese-silicon oxide represented by the following formula (7):
Cux7Mn7-x7SiMO12the compound of the formula (7),
wherein x7 is 0 to 1 inclusive, 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 10 atomic% 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 CuO and Cu2At least one of O, SiO2At least one of SiO, MnO and MnO2、Mn2O3With Mn3O4At least one of copper, manganese and silicon in the oxide mixtureThe atomic ratio of (A) to (B) is 1: 1: 1. 1: 4: 1. 4: 1: 1 or 1: 1: 4.
another embodiment of the present invention provides an anode material for a secondary battery including a tin-manganese-nickel oxide represented by one of the following formulas (8) to (11):
Sn1Mn2Ni1MOx8the compound of the formula (8),
Sn1Mn1Ni2MOx9the compound of the formula (9),
Sn2Mn1Ni1MOx10the compound of the formula (10),
Sn1Mn1Ni1MOx11in the formula (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 the group consisting of Cr, Mn, Zn, Al, Ti, In, Mo and W, and the atomic number ratio of M is 10 atomic% or less with respect to the total number of atoms of the metal elements In the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10) or formula (11).
In another embodiment of the present invention, a negative electrode material for a secondary battery comprises SnO and SnO2At least one of, MnO and MnO2、Mn2O3With Mn3O4At least one of the above, NiO and Ni2O3At least one of the above-mentioned oxides, wherein the atomic ratio of tin, manganese and nickel in the oxide mixture is 1: 2: 1. 1: 1: 1. 1: 1: 2 or 2: 1: 1.
another embodiment of the present invention provides an anode material for a secondary battery including a manganese copper nickel oxide represented by one of the following formulas (12) to (14):
Mn3Cu2Ni1MO8in the formula (12),
Mn2Cu1Ni1MO4a compound of the formula (13),
Mn1Cu1Ni1MO4in the formula (14),
wherein M is at least one element selected from the group consisting of Fe, Cr, Zn, Al, Ti, In, Mo, W and Si, and the atomic number ratio of M is 10 atom% or less with respect to the total number of atoms of the metal elements In the manganin nickel oxide represented by formula (12), formula (13) or formula (14).
Another embodiment of the present invention provides a negative electrode material for a secondary battery comprising MnO and MnO2、Mn2O3With Mn3O4At least one of CuO and Cu2At least one of O, NiO and Ni2O3At least one of the above-mentioned oxides, wherein the atomic ratio of manganese, copper and nickel in the oxide mixture is 3: 2: 1. 2: 1: 1 or 1: 1: 1.
another embodiment of the present invention provides an anode material for a secondary battery including a nickel copper tin oxide represented by one of the following formulas (15) to (17):
NiCuSn2MOx15a compound of the formula (15),
Ni2CuSn3MOx16a compound of the formula (16),
NiCu2Sn3MOx17a compound of the formula (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 the group consisting of Cr, Mn, Zn, Al, Ti, In, Mo, W and Co, and the atomic number ratio of M is 10 atomic% or less with respect 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 Ni2O3At least one of NiO and CuO, and Cu2At least one of O, SnO and SnO2At least one of the above-mentioned oxides, wherein the atomic ratio of cobalt, copper and tin in the oxide mixture is 1: 1: 2. 2: 1: 3 or 1: 2: 3.
an anode for a secondary battery according to an embodiment of the present invention includes a current collector and an anode material layer. The anode material layer is disposed on the current collector, and includes any one of the anode materials for secondary batteries described above.
One 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 the 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.
In view of the above, the negative electrode material for a secondary battery of the present invention can be applied to a secondary battery by including the metal oxide represented by one of formulas (1) to (17), or including 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 which the atomic numbers of the elements have a specific ratio, and can provide a secondary battery having good capacity, stability, and charge-discharge cycle life.
In order to make the aforementioned and other features and advantages of the 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 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 graph showing cycle life curves of the secondary batteries of example 4 and comparative examples 2 to 4;
FIG. 6 is a graph showing cycle life curves of the secondary batteries of example 5 and comparative examples 4 to 6;
FIG. 7 is a graph showing cycle life curves 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 graph showing cycle life curves of the secondary batteries of example 9 and comparative examples 4 and 8 to 9;
FIG. 11 is a graph showing cycle life curves of the secondary batteries of example 10 and comparative examples 4 and 8 to 9;
fig. 12 is a cycle life graph of the secondary battery of example 11;
FIG. 13 is a graph showing cycle life curves of the secondary batteries of example 12 and comparative examples 3, 8 to 9;
FIG. 14 is a graph showing cycle life curves of the secondary batteries of example 13 and comparative examples 3 to 4 and 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, 104 a: a current collector;
102 b: a negative electrode material layer;
104: a positive electrode;
104 b: a positive electrode material layer;
106: an isolation film;
108: an electrolyte;
110: an accommodating area;
112: and (7) packaging the structure.
Detailed Description
In this context, a range denoted by "a numerical value to another numerical value" is a general expression avoiding reciting all numerical values in the range in the specification. Thus, recitation of a range of values herein is intended to encompass any value within the range and any smaller range defined by any value within the range, as if the range and smaller range were explicitly recited in the specification.
As used herein, "about", "approximately", "essentially", or "substantially" includes the stated value and the average value within an acceptable range of deviation of the specified value as determined by one of ordinary skill in the art, taking into account the measurement in question and the specified amount of error associated with the measurement (i.e., the limitations of the measurement system). For example, "about" can mean within one or more standard deviations of the stated value, or within, for example, ± 30%, ± 20%, ± 15%, ± 10%, ± 5%. Further, as used herein, "about," "approximately," "essentially," or "substantially" may be selected based on the measured property or other property to select a more acceptable range of deviation or standard deviation, and not all properties may be accommodated with one standard deviation.
In order to prepare a negative electrode material which can be applied to a negative electrode of a secondary battery and enables the secondary battery to have good stability and electric capacity, the invention provides a negative electrode material which can achieve the advantages. Hereinafter, the present invention will be described with reference to specific embodiments.
One embodiment of the present invention provides an anode 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.
In this embodiment, the method for producing the 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 metal oxide containing four or more elements is prepared using a hydrothermal process, the temperature may be about 200 ℃ or more, the holding time may be about 5 hours or more, and the ambient pressure may be about 10-2Torr is higher than. In the embodiment of preparing the metal oxide containing four or more elements using the coprecipitation method, coprecipitation is first performed, the reaction temperature 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 finished, the reaction product is calcined, wherein the calcination temperature can be more than about 300 ℃, and the holding time can be aboutFor more than 1 hour. In embodiments where the metal oxide containing four or more elements is prepared using a sol-gel process, the temperature may be about 100 ℃ or more, the solution pH may be about 2 to about 12, and the holding time may be about 5 hours or more. In addition, in an embodiment in which the metal oxide containing four or more elements is prepared using a solid state method, the temperature may be about 100 ℃ or more, and the holding time may be about 8 hours or more. In embodiments where the metal oxide containing four or more elements is prepared using an evaporation method, the temperature may be about 25 ℃ or more, the evaporation time may be about 1 hour or more, and the ambient pressure may be about 10-3Torr is higher than. In embodiments where the metal oxide containing four or more elements is prepared using a sputtering process, the temperature may be about 25 ℃ or more, the sputtering time may be about 0.5 hours or more, and the ambient pressure may be about 10-3Torr is higher than. In embodiments where the metal oxide containing four or more elements is prepared using a vapor deposition process, the temperature may be about 25 ℃ or more, the deposition time may be about 1 hour or more, and the ambient pressure may be about 10-3Torr is higher than.
In the present 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-mentioned various oxides will be described in detail.
Cobalt copper tin oxide
In the present embodiment, the cobalt copper tin oxide may be represented by one of the following formulas (1) to (3):
Co5Cu1Sn3MOx1the compound of the formula (1),
Co2Cu1Sn1MOx2the compound of the formula (2),
Co1Cu1Sn1MOx3and (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 each satisfy the specific values listed above, the secondary battery using the negative electrode material including the cobalt-copper-tin oxide has excellent capacity, improved capacity retention rate, and excellent cycle life.
In each of formula (1), formula (2), and formula (3), M may be at least one element selected from Ni, Cr, Mn, Zn, Al, Ti, In, Mo, and W. The atomic number ratio of M is 10 atomic% or less relative to the total number of atoms of the metal elements in the cobalt-copper-tin oxide represented by formula (1), formula (2), or formula (3). 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 worth mentioning that cobalt copper tin oxide containing M with atomic number ratio of more than 0 and 10 atomic% or less has conductivity increased by about 10% or more compared to cobalt copper tin oxide not containing the element M. In the present embodiment, in the case of a cobalt copper tin oxide containing the element M, M may be substituted for a part of cobalt, copper and/or tin. For example, in one embodiment, M may replace a portion of the 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 numerical value of the number of atoms in the cobalt copper tin oxide represented by formula (1), formula (2), or formula (3) has an error range of ± 10% due to the formation of oxygen vacancies or uneven diffusion.
In the present 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 (chalcopyrate 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 structure, whereby lithium ions can be easily and rapidly introduced and removed in a secondary battery using the negative electrode material including the cobalt copper tin oxide, thereby effectively improving the diffusion rate of lithium ions and the ionic conductivity. In addition, the cobalt copper tin oxide represented by formula (1), formula (2), or formula (3) is less likely to collapse during charge and discharge by having the above structure, whereby a secondary battery using the negative electrode material including the cobalt copper tin oxide can maintain a good charge and discharge cycle life.
In the present embodiment, the average particle size of the cobalt-copper-tin oxide is, for example, between about 10nm and about 1 mm. If the average particle diameter of the cobalt copper tin oxide falls within the above range, a negative electrode having good characteristics can be advantageously formed. In the embodiment of manufacturing cobalt copper tin oxide by the solid state method, in order to obtain cobalt copper tin oxide having the above-mentioned specific average particle diameter range, grinding may be performed using a mortar, a ball mill (ball mill), a sand mill, a vibration ball mill, or a planetary ball mill (planet ball mill), 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):
Si4Sn1Fe16MOx4in the formula (4),
Si1Sn1Fe1MOx5the compound of the formula (5),
Si4Sn1Fe1MOx6formula (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 within the above ranges, respectively, the secondary battery using the negative electrode material including the silicon tin iron oxide has excellent capacity and improved capacity retention ratio.
In each of formula (4), formula (5), and formula (6), M may be at least one element selected from Cr, Mn, Zn, Al, Ti, In, Mo, and W. The atomic number ratio of M is 10 atomic% or less with respect to the total number of atoms of elements other than oxygen in the silicon-tin-iron oxide represented by formula (4), formula (5), or formula (6). 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 worth mentioning that the ferrosilicon-tin oxide containing M with an atomic number ratio of more than 0 and 10 atomic% or less has an increased conductivity by about 10% or more as compared with the ferrosilicon-tin oxide not containing the element M. In the present embodiment, in the case of a silicon tin iron oxide containing the element M, M may be substituted for 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, although the invention is not limited thereto. Note that in this embodiment, the numerical value of the number of atoms in the silicon tin iron oxide represented by formula (4), formula (5), or formula (6) has an error range of ± 10% due to the formation of oxygen vacancies or uneven diffusion.
In this embodiment, the silicon tin iron oxide represented by formula (4), formula (5), or formula (6) may have an Orthorhombic structure (Rhombohedral structure), a Cubic Bixbyite structure (Cubic Bixbyite structure), a Spinel structure (Spinel structure), or an Orthorhombic structure (Orthorhombic structure). It is worth mentioning that the ferrosilicon-tin oxide represented by formula (4), formula (5) or formula (6) allows more oxygen vacancies by having the above structure, whereby lithium ions can be easily and rapidly introduced and discharged in a secondary battery using the negative electrode material including the ferrosilicon-tin oxide, thereby effectively improving the diffusion rate of lithium ions and the ionic conductivity. In addition, the ferrosilicon-tin oxide represented by formula (4), formula (5), or formula (6) is less likely to collapse during charge and discharge by having the above structure, whereby a secondary battery using a negative electrode material including the ferrosilicon-tin oxide can maintain a good charge and discharge cycle life.
In the present 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 ferrosilicon tin oxide falls within the above range, a negative electrode having good characteristics can be advantageously formed. In the embodiment of producing the ferrosilicon tin oxide by the solid state method, in order to obtain the above ferrosilicon tin oxide having a specific average particle diameter range, the milling may be performed using a mortar, a ball mill (ball mill), a sand mill, a vibration ball mill, or a planetary ball mill (planet ball mill), but the present invention is not limited thereto.
Copper manganese silicon oxide
In the present embodiment, the copper-manganese-silicon oxide can be represented by the following formula (7): cux7Mn7-x7SiMO12Formula (7). In formula (7), x7 is greater than 0 to 1 or less. If x7 is within the above range, a secondary battery using the negative electrode material comprising the copper manganese silicon oxide 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 10 atomic% or less with respect 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 only include four elements, i.e., copper, manganese, silicon, and oxygen. It is worth mentioning that the copper manganese silicon oxide containing M with an atomic number ratio of more than 0 and 10 atomic% or less has an increased conductivity by about 10% or more compared to the copper manganese silicon oxide containing no element M. In addition, in the present embodiment, in the case of a 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 limited thereto. Note that, in this embodiment, the numerical value of the atomic number of copper and manganese in the copper-manganese-silicon oxide represented by formula (7) has an error range of ± 10% due to the diffusion unevenness or the formation of oxygen vacancies, whereby a non-integer ratio compound is formed.
In the present embodiment, the copper-manganese-silicon oxide represented by formula (7) may have an absurmbackite structure, a pyroxene structure, or a pyrolusite structure. It is worth mentioning that the copper manganese silicon oxide represented by formula (7) has the above structure, whereby in a secondary battery to which a negative electrode material including the copper manganese silicon oxide is applied, energy loss due to an overvoltage (overpotential) can be reduced, a lithium ion diffusion rate and an ion conductivity can be improved, and a charge-discharge cycle life can be improved.
In the present embodiment, the average particle size of the copper-manganese-silicon oxide is, for example, between about 10nm and about 1 mm. If the average particle diameter of the copper-manganese-silicon oxide falls within the above range, a negative electrode having good characteristics can be favorably formed. In the embodiment of manufacturing the copper-manganese-silicon oxide by the solid-state method, in order to obtain the copper-manganese-silicon oxide having the specific average particle diameter range, the polishing may be performed using a mortar, a ball mill (ball mill), a sand mill, a vibration ball mill, or a planetary ball mill (planet ball mill), 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):
Sn1Mn2Ni1MOx8the compound of the formula (8),
Sn1Mn1Ni2MOx9the compound of the formula (9),
Sn2Mn1Ni1MOx10in the formula (10),
Sn1Mn1Ni1MOx11formula (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 within the above ranges, respectively, the secondary battery to which the negative electrode material including the tin-manganese-nickel oxide is applied has excellent capacity and improved capacity retention rate.
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 10 atomic% or less with respect to the total number of atoms of the metal elements in the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10), or formula (11). In other words, the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10), or formula (11) may not contain the element M, but include only four elements, i.e., tin, manganese, nickel, and oxygen. It is worth mentioning that tin manganese nickel oxide containing M with atomic number ratio of more than 0 and 10 atomic% or less has conductivity increased by about 10% or more as compared with tin manganese nickel oxide not containing the element M. In the present embodiment, in the case of a tin-manganese-nickel oxide containing the element M, M may be substituted for 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 numerical value of the number of atoms in the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10), or formula (11) has an error range of ± 10% due to the formation of oxygen vacancies or uneven diffusion.
In the present embodiment, the tin manganese nickel oxide represented by formula (8), formula (9), formula (10), or formula (11) may have a Spinel structure (Spinel structure), a Rutile structure (ruthenium 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 structure, whereby lithium ions can be easily and rapidly introduced and discharged in a secondary battery using the negative electrode material including the tin-manganese-nickel oxide, thereby effectively improving the diffusion rate of lithium ions and the ionic conductivity. In addition, the tin-manganese-nickel oxide represented by formula (8), formula (9), formula (10), or formula (11) is less likely to collapse during charge and discharge due to the above-described structure, and thus a secondary battery using a negative electrode material including the tin-manganese-nickel oxide can maintain a good charge and discharge cycle life.
In the present embodiment, the average particle size of the tin-manganese-nickel oxide is, for example, between about 10nm and about 1 mm. If the average particle diameter of the tin-manganese-nickel oxide falls within the above range, a negative electrode having good characteristics can be advantageously formed. In the embodiment of producing tin-manganese-nickel oxide by the solid state method, in order to obtain tin-manganese-nickel oxide having the above-described specific average particle size range, the tin-manganese-nickel oxide may be ground using a mortar, a ball mill (ball mill), a sand mill, a vibration ball mill, or a planetary ball mill (planet ball mill), but the present invention is not limited thereto.
Manganese copper nickel oxide
In the present embodiment, the manganin nickel oxide may be represented by one of the following formulas (12) to (14):
Mn3Cu2Ni1MO8in the formula (12),
Mn2Cu1Ni1MO4a compound of the formula (13),
Mn1Cu1Ni1MO4formula (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 using the negative electrode material including the manganin nickel oxide has excellent capacity and improved capacity retention ratio, as represented by one of formulas (12) to (14) by the manganin nickel oxide.
In each of formula (12), formula (13), and formula (14), M may be at least one element selected from Fe, Cr, Zn, Al, Ti, In, Mo, W, and Si. The atomic number ratio of M is 10 atomic% or less relative to the total number of atoms of the metal elements in the manganese-copper-nickel oxide represented by formula (12), formula (13), or formula (14). In other words, the manganin nickel oxide represented by formula (12), formula (13) or formula (14) may not contain the element M, but only include four elements, i.e., manganese, copper, nickel and oxygen. It is worth mentioning that the manganin nickel oxide containing M with atomic number ratio of more than 0 and 10 atomic% or less has conductivity increased by about 10% or more compared to the manganin nickel oxide not containing the element M. In the present embodiment, in the case of a manganese copper nickel oxide containing the 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 manganese and a portion of 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 limited thereto. Note that in this embodiment, the numerical value of the number of atoms in the manganin nickel oxide represented by formula (12), formula (13), or formula (14) has an error range of ± 10% due to the formation of oxygen vacancies or uneven diffusion.
In the present embodiment, the manganin nickel oxide represented by formula (12), formula (13), or formula (14) may have a Tetragonal 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 manganin nickel oxide represented by formula (12), formula (13) or formula (14) allows more oxygen vacancies by having the above structure, whereby lithium ions can be easily and rapidly introduced and discharged in a secondary battery using the negative electrode material including the manganin nickel oxide, thereby effectively improving the diffusion rate of lithium ions and the ionic conductivity. In addition, since the manganin nickel oxide represented by formula (12), formula (13), or formula (14) has the above structure, it is not easily collapsed during charge and discharge, and thus a secondary battery using a negative electrode material including the manganin nickel oxide can maintain a good charge and discharge cycle life.
In the present embodiment, the average particle size of the manganin nickel oxide is, for example, between about 10nm to about 1 mm. If the average particle diameter of the manganin nickel oxide falls within the above range, a negative electrode having good characteristics can be advantageously formed. In the embodiment of producing the manganin nickel oxide by the solid state method, in order to obtain the above manganin nickel oxide having a specific average particle diameter range, the milling may be performed using a mortar, a ball mill (ball mill), a sand mill, a vibration ball mill, or a planetary ball mill (planet ball mill), 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):
NiCuSn2MOx15a compound of the formula (15),
Ni2CuSn3MOx16a compound of the formula (16),
NiCu2Sn3MOx17formula (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 each satisfy the specific values listed above, the secondary battery using the negative electrode material including the nickel-copper-tin oxide 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 10 atomic% or less relative to the total number of atoms of the metal elements in the nickel-copper-tin oxide represented by formula (15), formula (16), or formula (17). 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 worth mentioning that the nickel copper tin oxide containing M with the atomic number ratio of more than 0 and 10 atomic% or less has the conductivity increased by about 15% or more, as compared with the nickel copper tin oxide not containing the element M. In the present embodiment, in the case of a nickel copper tin oxide containing the element M, M may be substituted for 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 nickel and a portion of 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 numerical value of the number of atoms in the nickel-copper-tin oxide represented by formula (15), formula (16), or formula (17) has an error range of ± 10% due to the formation of oxygen vacancies or uneven diffusion.
In the present 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 (chalcopyrate 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 structure, whereby lithium ions can be easily and rapidly introduced and removed in a secondary battery using the negative electrode material including the nickel copper tin oxide, thereby effectively improving the diffusion rate of lithium ions and the ionic conductivity. In addition, the nickel copper tin oxide represented by formula (15), formula (16), or formula (17) is less likely to collapse during charge and discharge by having the above structure, and thus a secondary battery using the negative electrode material including the nickel copper tin oxide can maintain a good charge and discharge cycle life.
In the present embodiment, the average particle size of the nickel copper tin oxide is, for example, between about 10nm and about 1 mm. If the average particle diameter of the nickel copper tin oxide falls within the above range, a negative electrode having good characteristics can be advantageously formed. In the embodiment of producing nickel copper tin oxide by the solid state method, in order to obtain the above nickel copper tin oxide having the specific average particle diameter range, the milling may be performed using a mortar, a ball mill (ball mill), a sand mill, 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 the 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 a physical dry mixing process is used to prepare the oxide mixture containing four or more elements, the mixing temperature may be room temperature, for example, about 25 ℃ or more. In embodiments where a physical wet mixing method is used to prepare the oxide mixture containing four or more 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 mixture containing cobalt, copper and tin
In this embodiment, the oxide mixture containing cobalt, copper and tin may be formed from Co3O4、Co2O3And at least one of CoO, CuO and Cu2At least one of O, SnO and SnO2At least one of the above-mentioned components is mixed. That is, the oxide mixture containing cobalt, copper and tin can be obtained by performing a mixing step of cobalt oxide, copper oxide and tin oxide. In addition, in 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 ratio of cobalt, copper and tin is in accordance with the specific ratio as listed above, the secondary battery using the negative electrode material including the oxide mixture containing cobalt, copper and tin has excellent capacity and improved capacity retention.
In the present embodiment, Co may be selectively added in the mixing step3O4、Co2O3And at least one of CoO, CuO and Cu2At least one of O and SnO2Is mixed together with an oxide containing M, wherein M is at least one element selected from the group consisting of Ni, Cr, Mn, Zn, Al, Ti, In, Mo and W. That is, the cobalt, copper and tin containing oxide mixture may optionally include the element M. The atomic number ratio of M is more than 0 and 10 atomic% or less relative to the total atomic number of the metal elements in the oxide mixture containing cobalt, copper and tin. It is worth mentioning that the cobalt, copper and tin oxide mixture mixed with the M-containing oxide and having an atomic number ratio of M of more than 0 to 10 atomic% has an increased conductivity of about 8% or more compared to the cobalt, copper and tin oxide mixture not mixed with the M-containing oxide. Note that, in the present embodiment, the numerical value of the atomic ratio of the elements in the oxide mixture containing cobalt, copper, and tin has an error range of ± 10% due to the formation of oxygen vacancies or the non-uniform diffusion.
In this embodiment, by fabricating the negative electrode using the negative electrode material including the oxide mixture including cobalt, copper, and tin, lithium ions can migrate in and out through different paths therein, so that the polarization effect can be reduced and the charge-discharge cycle life can be improved. Thus, the capacity of a secondary battery using the negative electrode material comprising the oxide mixture of 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 that a secondary battery using a negative electrode material including an oxide mixture obtained by a mixing step of cobalt oxide, copper oxide, and tin oxide can have excellent performance and safety.
Oxide mixture containing silicon, tin and iron
In this embodiment, the oxide mixture containing silicon, tin and iron may be formed of SiO2And at least one of SiO, SnO and SnO2At least one of (1) and Fe2O3、Fe3O4And at least one of FeO and the mixture. That is, the oxide mixture containing silicon, tin and iron may be obtained by performing a mixing step of silicon oxide, tin oxide and iron oxide. In addition, in the present embodiment, the atomic ratio of silicon, tin, and iron in the oxide mixture containing silicon, tin, and iron may be 4: 1: 16. 1: 1: 1 or 4: 1: 1. if the atomic ratio of silicon, tin and iron satisfies the specific ratios listed above, the secondary battery using the anode material including the oxide mixture containing silicon, tin and iron has excellent capacity and improved capacity retention.
In the present embodiment, when the mixing step is performed, SiO may be selectively mixed2And at least one of SiO, SnO and SnO2At least one of (1) and Fe2O3、Fe3O4At least one of the FeO is mixed with an oxide containing M, wherein M is at least one element selected from Cr, Mn, Zn, Al, Ti, In, Mo and W. That is, the oxide mixture containing silicon, tin and iron may optionally include the element M. The atomic number ratio of M is more than 0 and less than or equal to the total atomic number of elements other than oxygen in the oxide mixture containing silicon, tin and ironAt 10 atomic%. It is worth mentioning that the oxide mixture containing silicon, tin and iron mixed with the oxide containing M with the atomic number ratio of M being more than 0 to 10 atomic% has an increased conductivity of about 10% or more compared to the oxide mixture containing silicon, tin and iron not mixed with the oxide containing M. Note that, in the present embodiment, the numerical value of the atomic ratio of the elements in the oxide mixture containing silicon, tin, and iron has an error range of ± 10% due to the formation of oxygen vacancies or the non-uniform diffusion.
In the present embodiment, by fabricating the negative electrode using the negative electrode material including the oxide mixture including silicon, tin, and iron, lithium ions may migrate in and out through different paths therein, so that the polarization effect may be reduced, and the charge-discharge cycle life may be improved. As a result, the capacity of a secondary battery using the anode material including the oxide mixture containing 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 that a secondary battery using a negative electrode material including an oxide mixture obtained by a mixing step of silicon oxide, tin oxide, and iron oxide can have excellent performance and safety.
Oxide mixture containing copper, manganese and silicon
In this embodiment, the oxide mixture containing Cu, Mn and Si may be formed from CuO and Cu2At least one of O, SiO2At least one of SiO, MnO and MnO2、Mn2O3With Mn3O4At least one of the above-mentioned components is mixed. That is, the oxide mixture containing copper, manganese and silicon may be obtained by performing a mixing step of copper oxide, manganese oxide and silicon oxide. In addition, in the present embodiment, the atomic ratio of copper, manganese, and silicon in the oxide mixture containing copper, manganese, and silicon may be 1: 1: 1. 1: 4: 1. 4: 1: 1 or 1: 1: 4. if the atomic ratio of copper, manganese and silicon is in accordance withIn the above-listed specific ratios, the secondary battery using the negative electrode material comprising the oxide mixture containing copper, manganese and silicon has excellent capacity and improved capacity retention.
In the present embodiment, CuO and Cu may be selectively mixed while the mixing step is performed2At least one of O, SiO2At least one of SiO, MnO and MnO2、Mn2O3With Mn3O4Is mixed together with an oxide containing M, wherein M is at least one element selected from the group consisting of Cr, W, Sn, Ni, Zn, Al, Ti, In and Mo. That is, the oxide mixture containing copper, manganese and silicon may optionally include the element M. The atomic number ratio of M is more than 0 and 10 atomic% or less with respect to the total atomic number of elements other than oxygen in the oxide mixture containing copper, manganese and silicon. It is worth mentioning that the mixture of oxides of copper, manganese and silicon mixed with an oxide containing M and having an atomic number ratio of M of greater than 0 to equal to or less than 10 atomic% has an increased conductivity of about 10% or more compared to the mixture of oxides of copper, manganese and silicon not mixed with an oxide containing M. It is to be noted that, in the present embodiment, the numerical value of the atomic ratio of the elements in the oxide mixture containing copper, manganese and silicon has an error range of ± 10% due to the formation of oxygen vacancies or the non-uniform diffusion.
In the present embodiment, the synergistic effect of the mixture of oxides of copper, manganese and silicon obtained by the mixing step of the oxide of copper, the oxide of manganese and the oxide of silicon due to the interaction between the plurality of oxides allows the capacity of the secondary battery to be remarkably increased in which the negative electrode material including the mixture of oxides of copper, manganese and silicon is applied. In addition, in the present embodiment, by manufacturing the negative electrode using the negative electrode material including the oxide mixture containing copper, manganese, and silicon, lithium ions can migrate in and out through different paths therein, so that the polarization effect can be reduced, and the charge-discharge cycle life can be improved. In addition, since the copper oxide can achieve a good cycle life as a negative electrode material, the manganese oxide can achieve a low overpotential as a negative electrode material, and the silicon oxide can achieve a good lithium ion conductivity as a negative electrode material, a secondary battery using a negative electrode material including an oxide mixture obtained by a mixing step of the copper oxide, the manganese oxide, and the silicon oxide can have excellent performance and safety.
Oxide mixture containing tin, manganese and nickel
In this embodiment, the oxide mixture containing tin, manganese and nickel can be made of SnO and SnO2At least one of, MnO and MnO2、Mn2O3With Mn3O4At least one of NiO and Ni2O3At least one of the above-mentioned components is mixed. That is, the oxide mixture containing tin, manganese and nickel may be obtained by performing a mixing step of tin oxide, manganese oxide and nickel oxide. In addition, in the present embodiment, the atomic ratio of tin, manganese, and nickel in the oxide mixture containing tin, manganese, and nickel may be 1: 2: 1. 1: 1: 1. 1: 1: 2 or 2: 1: 1. if the atomic ratio of tin, manganese and nickel is in accordance with the specific ratio as listed above, the secondary battery using the negative electrode material including the oxide mixture containing tin, manganese and nickel has excellent capacity and improved capacity retention.
In this embodiment, when the mixing step is performed, SnO and SnO may be selectively mixed2At least one of, MnO and MnO2、Mn2O3With Mn3O4At least one of NiO and Ni2O3Is mixed together with an oxide containing M, wherein M is at least one element selected from the group consisting of Cr, W, Si, Cu, Zn, Al, Ti, In and Mo. That is, the oxide mixture containing tin, manganese and nickel may optionally include the element M. The atomic number ratio of M is more than 0 to 10 atomic% or less with respect to the total atomic number of the metal elements in the oxide mixture containing tin, manganese and nickel. It is worth mentioning that the M-containing oxide is mixed in such a manner that the atomic number ratio of M is intermediate to that of the M-containing oxide in comparison with the oxide mixture containing tin, manganese and nickel in which the M-containing oxide is not mixedThe conductivity of the oxide mixture containing tin, manganese and nickel is increased by more than about 10% when the concentration is more than 0 and less than or equal to 10 atomic%. Note that, in the present embodiment, the numerical value of the atomic ratio of the elements in the oxide mixture containing tin, manganese, and nickel has an error range of ± 10% due to the formation of oxygen vacancies or the non-uniform diffusion.
In the present embodiment, the synergistic effect of the oxide mixture containing tin, manganese and nickel obtained by the mixing step of the oxide of tin, the oxide of manganese and the oxide of nickel due to the interaction between the plurality of oxides allows the capacity of the secondary battery to be remarkably increased in which the negative electrode material including the oxide mixture containing tin, manganese and nickel is applied. In addition, in the present embodiment, by fabricating the negative electrode using the negative electrode material including the oxide mixture including tin, manganese, and nickel, lithium ions can migrate in and out through different paths therein, so that the polarization effect can be reduced, and the charge-discharge cycle life can be improved. In addition, since a high capacity performance can be achieved by using tin oxide as a negative electrode material, a low overpotential can be achieved by using manganese oxide as a negative electrode material, and a good lithium ion conductivity can be achieved by using nickel oxide as a negative electrode material, 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 mixture containing manganese, copper and nickel
In this embodiment, the oxide mixture containing manganese, copper and nickel may be composed of MnO and MnO2、Mn2O3With Mn3O4At least one of CuO and Cu2At least one of O, NiO and Ni2O3At least one of the above-mentioned components is mixed. That is, the oxide mixture containing manganese, copper and nickel may be obtained by performing a mixing step of manganese oxide, copper oxide and nickel oxide. In addition, 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 ratio of the atomic numbers of manganese, copper and nickel is in accordance with the specific ratios listed above, the secondary battery using the negative electrode material including the oxide mixture containing manganese, copper and nickel has excellent capacity and improved capacity retention.
In the present embodiment, MnO and MnO may be selectively used in the mixing step2、Mn2O3With Mn3O4At least one of CuO and Cu2At least one of O, NiO and Ni2O3Is mixed together with an oxide containing M, wherein M is at least one element selected from the group consisting of Fe, Cr, Zn, Al, Ti, In, Mo, W and Si. That is, the oxide mixture containing manganese, copper and nickel may optionally include the element M. The atomic number ratio of M is more than 0 to 10 atomic% or less relative to the total atomic number of the metal elements in the oxide mixture containing manganese, copper, and tin. It is worth mentioning that the oxide mixture containing manganese, copper and nickel mixed with the oxide containing M and having the atomic number ratio of M of more than 0 to 10 atomic% has an increased conductivity of about 5% or more, as compared to the oxide mixture containing manganese, copper and nickel not mixed with the oxide containing M. Note that, in the present embodiment, the numerical value of the atomic ratio of the elements in the oxide mixture containing manganese, copper, and nickel has an error range of ± 10% due to the formation of oxygen vacancies or the non-uniform diffusion.
In this embodiment, by fabricating the negative electrode using the negative electrode material including the oxide mixture including manganese, copper, and nickel, lithium ions can migrate in and out through different paths therein, so that the polarization effect can be reduced, and the 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 a mixing step of manganese oxide, copper oxide, and nickel oxide can have excellent performance and safety.
Oxide mixture containing nickel, copper and tin
In this embodiment, the oxide mixture containing nickel, copper and tin may be formed from Ni2O3At least one of NiO and CuO, and Cu2At least one of O, SnO and SnO2At least one of the above-mentioned components is mixed. That is, the mixture of oxides containing nickel, copper and tin may be obtained by performing a mixing step of oxides of nickel, copper and tin. 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 ratio of nickel, copper and tin is in accordance with the specific ratio as listed above, a secondary battery using the negative electrode material including the oxide mixture containing nickel, copper and tin has excellent capacity and improved capacity retention.
In the present embodiment, Ni may be selectively added when the mixing step is performed2O3At least one of NiO and CuO, and Cu2At least one of O and SnO2Is mixed together with an oxide containing M, wherein M is at least one element selected from the group consisting of Cr, Mn, Zn, Al, Ti, In, Mo, W and Co. That is, the oxide mixture containing nickel, copper and tin may optionally include the element M. The atomic number ratio of M is more than 0 and 10 atomic% or less relative to the total atomic number of the metal elements in the oxide mixture containing nickel, copper and tin. It is worth mentioning that the mixture of oxides containing nickel, copper and tin mixed with the oxide containing M with the atomic number ratio of M being more than 0 to 10 atomic% has an increased conductivity of about 8% or more compared to the mixture of oxides containing nickel, copper and tin not mixed with the oxide containing M. Note that, in the present embodiment, the numerical value of the atomic ratio of the elements in the oxide mixture containing nickel, copper, and tin has an error range of ± 10% due to the formation of oxygen vacancies or the non-uniform diffusion.
In the present embodiment, the negative electrode is made of a negative electrode material including an oxide mixture including nickel, copper, and tin, whereby lithium ions can migrate in and out through different paths therein, so that the polarization effect can be reduced, and the charge-discharge cycle life can be improved. As a result, the capacity of a secondary battery using the negative electrode material comprising the mixture of oxides of 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 that a secondary battery using a negative electrode material including an oxide mixture obtained by a mixing step of nickel oxide, copper oxide, and tin oxide can have excellent performance and safety.
Another embodiment of the present invention also provides a secondary battery to which any one of the anode materials proposed in the foregoing embodiments is applied.
Fig. 1 is a schematic 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 cathode 102, an anode 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 addition, in the present embodiment, the secondary battery 100 may be a lithium ion battery.
In the present embodiment, the anode 102 may include a current collector 102a and an anode material layer 102b disposed on the current collector 102 a. In the present embodiment, the current collector 102a may be a metal foil, such as a copper foil, a nickel foil, or a highly conductive stainless steel foil. In the present embodiment, the thickness of the current collector 102a may be between about 5 μm to about 300 μm.
In the present embodiment, the anode material layer 102b includes any one of the anode materials proposed in the foregoing embodiments. In the present embodiment, the anode 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 this embodiment, the negative electrode material layer 102b may further include a conductive agent and a binder. In the present embodiment, the conductive aid 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 whisker (carbon whisker), carbon fiber, metal powder, metal fiber, or conductive ceramic (ceramics) material. In detail, the conductive agent is used to improve the electrical contact between the negative electrode materials. In the present embodiment, the adhesive may be polyvinylidene fluoride (PVDF), Styrene Butadiene Rubber (SBR), polyamide, melamine resin, or a combination thereof. In detail, the anode material may be adhered to the collector 102a by an adhesive.
In the present embodiment, the positive electrode 104 and the negative electrode 102 are disposed separately. In this embodiment, the positive electrode 104 includes a current collector 104a and a positive electrode material layer 104b disposed on the current collector 104 a. In the present embodiment, the current collector 104a may be a metal foil, such as a copper foil, a nickel foil, an aluminum foil, or a highly conductive stainless steel foil. In the present embodiment, the thickness of the current collector 104a may be between about 5 μm to about 300 μm.
In this embodiment, the positive electrode material layer 104b includes a positive electrode material. In the present embodiment, the cathode material may include lithium cobalt oxide (LiCoO)2) Lithium manganate (LiMn)2O4) Lithium nickelate (LiNiO)2) Lithium iron phosphate (LiFePO)4) Or a combination thereof. In the present embodiment, the cathode material may be disposed on the current collector 104a by coating, sputtering, hot pressing, sintering, physical vapor deposition, or chemical vapor deposition, for example. In addition, in this embodiment, the positive electrode material layer 104b may further include a binder. In the present embodiment, the adhesive may be polyvinylidene fluoride (PVDF), Styrene Butadiene Rubber (SBR), polyamide, melamine resin, or a combination thereof. In detail, the positive electrode material may be adhered to the current collector 104a by an adhesive.
In the present embodiment, the electrolyte 108 is provided between the anode 102 and the cathode 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 negative electrode 102 and the positive electrode 104, the separator 106, the negative electrode 102 and the positive electrode 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) composed of the above materials.
In the present embodiment, the secondary battery 100 includes a separator 106 to separate the anode 102 and the cathode 104 and allow ions to penetrate therethrough, but the present invention is not limited thereto. In other embodiments, electrolyte 108 is a solid electrolyte, and secondary battery 100 does not include a separator.
In this embodiment, the encapsulation structure 112 covers 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 the negative electrode, the positive electrode, and an optional separator are wound, or a laminated structure in which flat plates are 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 proposed in the foregoing embodiments, the secondary battery 100 can have good capacity, stability, and charge/discharge cycle life as described above.
The features of the present invention will be described more specifically below with reference to examples 1 to 14 and comparative examples 1 to 9. Although the following examples 1 to 14 are described, the materials used, 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. Therefore, the present invention should not be construed restrictively by the examples described below.
Example 1
Preparation of negative electrode material
After respectively grinding CoO powder (a precursor containing cobalt), CuO powder (a precursor containing copper), SnO powder (a precursor containing tin), and W oxide powder (a precursor containing element M) at room temperature by a ball mill, these powders were mixed and pressed into Green pellets (Green pellets) having a diameter of about 1 cm. The green body was placed in a high temperature furnace to obtain a bulk cobalt copper tin oxide (i.e., the negative electrode material of example 1) represented by the formula (1) above, wherein x1 was 8, the element M was W, the atomic number ratio of the element M was about 1 to 10 atomic%, and the average particle size of the cobalt copper tin oxide was about 0.1 μ M to about 10 μ M.
Preparation of secondary battery
The anode material of example 1, which was crushed and ground, Super P conductive carbon, and a binder, i.e., sodium carboxymethyl cellulose (CMC) dissolved in water, were mixed in a weight ratio of 7:2:1, then, zirconia balls were added to the mixture to form anode slurry, and then, the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and was uniformly scraped, and after which the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, and after that, the dried copper foil was cut into anodes of example 1 having a diameter of about 12.8mm by a slitter.
A button cell (model: CR2032) was assembled using the negative electrode of example 1 as the working electrode, lithium metal as the opposite electrode, and 1M LiPF6Added to an organic solvent to serve as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by the company cargard) as an isolation film, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 1 was prepared.
Example 2
Preparation of negative electrode material
After respectively grinding CoO powder (a precursor containing cobalt), CuO powder (a precursor containing copper), SnO powder (a precursor containing tin), and W oxide powder (a precursor containing element M) at room temperature by a ball mill, these powders were mixed and pressed into Green pellets (Green pellets) having a diameter of about 1 cm. The green body was placed in a high temperature furnace to obtain a bulk cobalt copper tin oxide (i.e., the negative electrode material of example 2) represented by the formula (2) above, wherein x2 was 4, the element M was W, the atomic number ratio of the element M was about 1 to 10 atomic%, and the average particle size of the cobalt copper tin oxide was about 0.1 μ M to about 10 μ M.
Preparation of secondary battery
The crushed and ground negative electrode material of example 2, Super P conductive carbon, and binder (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1, then, zirconia balls were added to the mixture to mix for about 30 minutes to form a negative electrode slurry, and then, the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and was uniformly scraped, and after that, 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 a negative electrode of example 2 having a diameter of about 12.8mm by a sheet cutter.
A button cell (model: CR2032) was assembled using the negative electrode of example 2 as the working electrode, lithium metal as the opposite electrode, and 1M LiPF6Added to an organic solvent to serve as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by the company cargard) as an isolation film, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 2 was prepared.
Example 3
Preparation of negative electrode material
After respectively grinding CoO powder (a precursor containing cobalt), CuO powder (a precursor containing copper), SnO powder (a precursor containing tin), and W oxide powder (a precursor containing element M) at room temperature by a ball mill, these powders were mixed and pressed into Green pellets (Green pellets) having a diameter of about 1 cm. The green body was placed in a high temperature furnace to obtain a bulk cobalt copper tin oxide represented by the aforementioned formula (3) (i.e., the negative electrode material of example 3), wherein x3 was 4, the element M was W, the atomic number ratio of the element M was about 1 to 10 atomic%, and the average particle size of the cobalt copper tin oxide was between about 0.1 μ M and about 10 μ M.
Preparation of secondary battery
The crushed and ground negative electrode material of example 3, Super P conductive carbon and binder (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1, then, zirconia balls were added to the mixture to mix for about 30 minutes to form a negative electrode slurry, and then, the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and was uniformly scraped, and after that, 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 a negative electrode of example 3 having a diameter of about 12.8mm by a sheet cutter.
A button cell (model: CR2032) was assembled using the negative electrode of example 3 as the working electrode, lithium metal as the opposite electrode, and 1M LiPF6Added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by the company cargard) as a separation film, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 3 was prepared.
Example 4
Preparation of negative electrode material
CoO powder (cobalt oxide), CuO powder (copper oxide), and SnO were each pulverized at room temperature by means of a ball mill2Powder (oxide of tin), W oxide powder (oxide containing element M) were mixed by grinding to obtain an oxide mixture containing cobalt, copper and tin (i.e., negative electrode material of example 4) in which the atomic ratio of cobalt, copper and tin was 1: 1: 1, the element M is W, and the atomic number ratio of the element M is about 1 to 10 atomic%.
Preparation of secondary battery
The negative electrode material of example 4, Super P conductive carbon, and binder (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water in a weight ratio of 7:2: 1) were mixed and then, zirconia balls were added to mix for about 30 minutes to form a negative electrode slurry, and then, the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and was uniformly scraped, and after which 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 a negative electrode of example 4 having a diameter of about 12.8mm by a slitter.
A button cell (model: CR2032) was assembled using the negative electrode of example 4 as the working electrode and lithium metal as the opposite electrode、1M LiPF6Added to an organic solvent to serve as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by the company cargard) as an isolation film, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 4 was manufactured.
Example 5
Preparation of negative electrode material
Respectively using a ball mill to prepare SiO at room temperature2Powder (silicon-containing precursor), SnO2Powder (precursor of tin), Fe2O3Powder (iron-containing precursor), TiO2After the powders (precursors containing element M) were ground, they were mixed and pressed into Green pellets (Green pellets) with a diameter of about 1 cm. The green body was placed in a high temperature furnace to obtain a bulk of ferrosilicon tin oxide represented by the aforementioned formula (4) (i.e., the negative electrode material of example 4), wherein x4 was 21, the element M was Ti, the atomic number ratio of the element M was about 1 to 10 atomic%, and the average particle size of the ferrosilicon tin oxide was about 0.1 μ M to about 10 μ M.
Preparation of secondary battery
The crushed and ground negative electrode material of example 5, Super P conductive carbon, and binder (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1, then, zirconia balls were added to the mixture to mix for about 30 minutes to form a negative electrode slurry, and then, the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and was uniformly scraped, and after that, 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 a negative electrode of example 5 having a diameter of about 12.8mm using a sheet cutter.
A button cell (model: CR2032) was assembled using the negative electrode of example 5 as the working electrode, lithium metal as the opposite electrode, and 1M LiPF6Added to an organic solvent as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by the company cargard) as a separation film, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 5 was manufactured.
Example 6
Preparation of negative electrode material
Respectively using a ball mill to prepare SiO at room temperature2Powder (oxide of silicon), SnO2Powder (tin oxide), Fe2O3Powder (iron oxide), TiO2After the powder (oxide containing element M) was mixed by grinding, an oxide mixture containing silicon, tin and iron (i.e., negative electrode material of example 6) in which the atomic 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 10 atomic%.
Preparation of secondary battery
The negative electrode material of example 6, Super P conductive carbon, and binder (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water in a weight ratio of 7:2: 1) were mixed and then, zirconia balls were added to mix for about 30 minutes to form a negative electrode slurry, and then, the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and was uniformly scraped, and after which 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 a negative electrode of example 6 having a diameter of about 12.8mm by a slitter.
A button cell (model: CR2032) was assembled using the negative electrode of example 6 as the working electrode, lithium metal as the opposite electrode, and 1M LiPF6Added to an organic solvent to serve as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by the company cargard) as an isolation film, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 6 was manufactured.
Example 7
Preparation of cathode material
At room temperature, CuO powder (copper-containing precursor), MnO powder (manganese-containing precursor), and SiO were each mixed by a ball mill2Powder (silicon containing precursor), TiO2After the powders (precursors containing element M) were ground, they were mixed and pressed into Green pellets (Green pellets) with a diameter of about 1 cm. The green body was placed in a high-temperature furnace to obtain a copper-manganese-silicon oxide represented by the aforementioned formula (7)The bulk material (i.e., the negative electrode material of example 7) wherein x7 is 1, the element M is Ti, the atomic number ratio of the element M is about 1 to 10 atomic%, and the average particle size of the copper manganese silicon oxide is about 0.1 μ M to about 10 μ M.
Preparation of secondary battery
The crushed and ground negative electrode material of example 7, Super P conductive carbon, and binder (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1, then, zirconia balls were added to mix for about 30 minutes to form a negative electrode 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 which 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 a negative electrode of example 7 having a diameter of about 12.8mm using a sheet cutter.
A button cell (model: CR2032) was assembled using the negative electrode of example 7 as the working electrode, lithium metal as the opposite electrode, and 1M LiPF6Added to an organic solvent to serve as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by the company cargard) as an isolation film, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 7 was prepared.
Example 8
Preparation of negative electrode material
CuO powder (copper oxide), MnO powder (manganese oxide), and SiO were each mixed at room temperature using a ball mill2Powder (silicon oxide), TiO2The powder (oxide containing element M) was mixed by grinding to obtain an oxide mixture containing copper, manganese and silicon (i.e., negative electrode material of example 8) in which the atomic 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 10 atomic%.
Preparation of secondary battery
The negative electrode material of example 8, Super P conductive carbon, and binder (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water in a weight ratio of 7:2: 1) were mixed and then, zirconia balls were added to mix for about 30 minutes to form a negative electrode slurry, and then, the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and was uniformly scraped, and after which 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 a negative electrode of example 8 having a diameter of about 12.8mm by a slitter.
A button cell (model: CR2032) was assembled using the negative electrode of example 8 as the working electrode, lithium metal as the opposite electrode, and 1M LiPF6Added to an organic solvent to serve as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by the company cargard) as an isolation film, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 8 was prepared.
Example 9
Preparation of cathode material
SnO is respectively treated by a ball mill at room temperature2Powder (precursor containing tin), MnO2After grinding powders (manganese containing precursor), NiO powder (nickel containing precursor), Mo oxide powder (element M containing precursor), these powders were mixed and pressed into Green pellets (Green pellet) with a diameter of about 1 cm. The green body was placed in a high temperature furnace to obtain a tin manganese nickel oxide bulk material (i.e., the negative electrode material of example 9) represented by the aforementioned formula (8), wherein x8 was 7, the element M was Mo, the atomic number ratio of the element M was about 1 to 10 atomic%, and the average particle diameter of the tin manganese nickel oxide was about 0.1 μ M to about 10 μ M.
Preparation of secondary battery
The crushed and ground negative electrode material of example 9, Super P conductive carbon, and binder (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1, then, zirconia balls were added to the mixture to mix for about 30 minutes to form a negative electrode slurry, and then, the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and was uniformly scraped, and after that, 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 a negative electrode of example 9 having a diameter of about 12.8mm using a sheet cutter.
A button cell (model: CR2032) was assembled using the negative electrode of example 9 as the working electrode, lithium metal as the opposite electrode, and 1M LiPF6Added to an organic solvent to serve as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by the company cargard) as an isolation film, 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 is respectively mixed by a ball mill at room temperature2Powder (oxide of tin), MnO2The powder (oxide of manganese), NiO powder (oxide of nickel), Mo oxide powder (oxide containing element M) were mixed by grinding to obtain an oxide mixture containing tin, manganese, and nickel (i.e., negative electrode material of example 10) in which the atomic ratio of tin, manganese, and nickel was 1: 2:1, the element M is Mo, and the atomic number ratio of the element M is about 1 to 10 atomic%.
Manufacture of secondary battery
The negative electrode material of example 10, Super P conductive carbon, and binder (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water in a weight ratio of 7:2: 1) were mixed and then, zirconia balls were added to mix for about 30 minutes to form a negative electrode slurry, and then, the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and was uniformly scraped, and after which 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 a negative electrode of example 10 having a diameter of about 12.8mm by a slitter.
A button cell (model: CR2032) was assembled using the negative electrode of example 10 as the working electrode, lithium metal as the opposite electrode, and 1M LiPF6Added to an organic solvent to serve as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by the company cargard) as an isolation film, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 10 was prepared.
Example 11
Preparation of negative electrode material
Respectively adding MnO at room temperature by using a ball mill2After grinding powders (manganese containing precursor), CuO powder (copper containing precursor), NiO powder (nickel containing precursor), Mo oxide powder (element M containing precursor), these powders were mixed and pressed into Green pellets (Green pellets) with a diameter of about 1 cm. The green body was placed in a high temperature furnace to obtain a manganese copper nickel oxide bulk material (i.e., the negative electrode material of example 11) represented by the aforementioned formula (13), wherein the element M was Mo, the atomic number ratio of the element M was about 1 to 10 atomic%, and the average particle diameter of the manganese copper tin oxide was about 0.1 μ M to about 10 μ M.
Preparation of secondary battery
The anode material of example 11, which was crushed and ground, Super P conductive carbon, and a binder, i.e., sodium carboxymethyl cellulose (CMC) dissolved in water, were mixed in a weight ratio of 7:2:1, then, zirconia balls were added to the mixture to form anode slurry, and then, the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and was uniformly scraped, and after which the copper foil coated with the slurry was dried in a vacuum oven at about 110 ℃ for about 12 hours, and after that, the dried copper foil was cut into anodes of example 11 having a diameter of about 12.8mm by a slitter.
A button cell (model: CR2032) was assembled using the negative electrode of example 11 as the working electrode, lithium metal as the opposite electrode, and 1M LiPF6Added to an organic solvent to serve as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by the company cargard) as an isolation film, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 11 was prepared.
Example 12
Preparation of negative electrode material
Respectively adding MnO by a ball mill at room temperature2Powders (oxides of manganese), CuO powders (oxides of copper), NiO powders (oxides of nickel), Mo oxide powders (oxides containing the element M) were mixed by grinding to obtain an oxide mixture containing manganese, copper and nickel (i.e., the anode material of example 12) in which manganese, copper and nickel were originally presentThe ratio of the sub-ratios is 2: 1: 1, the element M is Mo, and the atomic number ratio of the element M is about 1 to 10 atomic%.
Preparation of secondary battery
The negative electrode material of example 12, Super P conductive carbon, and binder (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water in a weight ratio of 7:2: 1) were mixed and then, zirconia balls were added to mix for about 30 minutes to form a negative electrode slurry, and then, the slurry was coated on a copper foil (the aforementioned current collector) using a doctor blade (100 μm) and was uniformly scraped, and after which 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 a negative electrode of example 12 having a diameter of about 12.8mm by a slitter.
A button cell (model: CR2032) was assembled using the negative electrode of example 12 as the working electrode, lithium metal as the opposite electrode, and 1M LiPF6Added to an organic solvent to serve as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by cargord (Celgard) corporation) to serve as a separator, and a stainless steel 304 or 316 cap to serve as a package structure. Thus, a secondary battery of example 12 was prepared.
Example 13
Preparation of negative electrode material
NiO powder (nickel oxide), CuO powder (copper oxide), and SnO were each pulverized at room temperature by means of a ball mill2Powder (oxide of tin), W oxide powder (oxide containing element M) were mixed by grinding to obtain an oxide mixture containing nickel, copper and tin (i.e., negative electrode material of example 13) in which the atomic 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 10 atomic%.
Preparation of secondary battery
The crushed and ground negative electrode material of example 13, Super P conductive carbon and binder (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1, then, zirconia balls were added to mix for about 30 minutes to form a negative electrode 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 which 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 a negative electrode of example 13 having a diameter of about 12.8mm by a sheet cutter.
A button cell (model: CR2032) was assembled using the negative electrode of example 13 as the working electrode, lithium metal as the opposite electrode, and 1M LiPF6Added to an organic solvent to serve as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by the company cargard) as an isolation film, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 13 was prepared.
Example 14
Preparation of negative electrode material
NiO powder (nickel-containing precursor), CuO powder (copper-containing precursor), and SnO were each mixed at room temperature using a ball mill2After grinding the powders (tin-containing precursor), W-oxide powder (element M-containing precursor), the powders were mixed and pressed into Green pellets (Green pellets) with a diameter of about 1 cm. The green body was placed in a high temperature furnace to obtain a nickel copper tin oxide bulk material represented by the aforementioned formula (15) (i.e., the negative electrode material of example 14) wherein x15 was 6, the element M was W, the atomic number ratio of the element M was about 1 to 10 atomic%, and the average particle diameter of manganese copper tin oxide was about 0.1 μ M to about 10 μ M.
Preparation of secondary battery
The crushed and ground negative electrode material of example 14, Super P conductive carbon, and binder (i.e., sodium carboxymethyl cellulose (CMC) dissolved in water) were mixed in a weight ratio of 7:2:1, then, zirconia balls were added to mix for about 30 minutes to form a negative electrode 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 which 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 a negative electrode of example 14 having a diameter of about 12.8mm using a sheet cutter.
Button cell batteries (model: CR2032) were assembled using the negative electrode of example 14 as the working electrodePolar, lithium metal as the opposite polar, 1M LiPF6Added to an organic solvent to serve as an electrolyte, a polypropylene film (trade name: Celgard #2400, manufactured by the company cargard) as an isolation film, and a stainless steel 304 or 316 cap as a package structure. Thus, a secondary battery of example 14 was prepared.
Comparative example 1
Preparation of secondary battery
A secondary battery of comparative example 1 was fabricated following the same fabrication procedure as in example 1, with the main differences being that: in the secondary battery of example 1, the working electrode was the negative electrode of example 1; in contrast, in the secondary battery of comparative example 1, the material of the working electrode was Co2SnO4。
Comparative example 2
Preparation of secondary battery
A secondary battery of comparative example 2 was fabricated following the same fabrication procedure as in example 1, with the main differences being that: in the secondary battery of example 1, the working electrode was the negative electrode of example 1; in contrast, in the secondary battery of comparative example 2, the material of the working electrode was CoO.
Comparative example 3
Preparation of secondary battery
A secondary battery of comparative example 3 was produced following the same production procedure as in example 1, with the main difference that: in the secondary battery of example 1, the working electrode was the negative electrode of example 1; in contrast, 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 fabricated following the same fabrication procedure as in example 1, with the main differences being that: in the secondary battery of example 1, the working electrode was the negative electrode of example 1; in contrast, in the secondary battery of comparative example 4, the material of the working electrode was SnO2。
Comparative example 5
Preparation of secondary battery
Prepared according to the same manufacturing procedure as in example 1The secondary battery of comparative example 5 is mainly different in that: in the secondary battery of example 1, the working electrode was the negative electrode of example 1; in contrast, in the secondary battery of comparative example 5, the material of the working electrode was SiO2。
Comparative example 6
Preparation of secondary battery
A secondary battery of comparative example 6 was produced following the same production procedure as in example 1, with the main difference that: in the secondary battery of example 1, the working electrode was the negative electrode of example 1; in contrast, in the secondary battery of comparative example 6, the material of the working electrode was Fe2O3。
Comparative example 7
Preparation of secondary battery
A secondary battery of comparative example 7 was produced following the same production procedure as in example 1, with the following main differences: in the secondary battery of example 1, the working electrode was the negative electrode of example 1; in contrast, in the secondary battery of comparative example 7, the material of the working electrode was MnO.
Comparative example 8
Preparation of secondary battery
A secondary battery of comparative example 8 was fabricated following the same fabrication procedure as in example 1, with the main differences being that: in the secondary battery of example 1, the working electrode was the negative electrode of example 1; in contrast, in the secondary battery of comparative example 8, the material of the working electrode was MnO2。
Comparative example 9
Preparation of secondary battery
A secondary battery of comparative example 9 was produced following the same production procedure as in example 1, with the following main differences: in the secondary battery of example 1, the working electrode was the negative electrode of example 1; in contrast, 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 prepared, the secondary batteries of examples 1 to 14 and the secondary batteries of comparative examples 1 to 9 were subjected to charge-discharge cycle tests, respectively.
Charge discharge cycle test
The secondary batteries of examples 1 to 14 and the secondary batteries of comparative examples 1 to 9 were subjected to a capacity test for a 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 had better electric capacity and electric capacity retention rate after a high number of cycles (>250 cycles) 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 would be understood by those skilled in the art that the secondary battery including the cobalt copper tin oxide represented by formula (1) in which x1 is 9 or 14 would have good capacity and capacity maintenance rate according to the foregoing description about the cobalt copper tin oxide and the test results of example 1.
Although the foregoing tests were not performed on the secondary battery including the cobalt copper tin oxide represented by formula (2) in which x2 was 6 or 8, it would be understood by those skilled in the art that the secondary battery including the cobalt copper tin oxide represented by formula (2) in which x2 was 6 or 8 would have good capacity and capacity maintenance rate according to the foregoing description and the test results of example 2.
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 would be understood by those skilled in the art that the secondary battery including the cobalt copper tin oxide represented by formula (3) in which x3 is 3 or 5 would have good capacity and capacity maintenance rate according to the foregoing description and the test results of example 1.
As can be seen from fig. 5, the secondary battery of example 4 has better electric capacity and electric capacity retention rate after a high number of cycles (>250 cycles) than the secondary batteries of comparative examples 2 to 4.
Although the atomic ratio of cobalt, copper and tin is not included in pairs of 5: 1: 3 or 2: 1: 1, a secondary battery containing an oxide mixture of cobalt, copper and tin, but according to the foregoing description and the test results of example 4, those skilled in the art will understand that the ratio of the number of atoms including cobalt, copper and tin is 5: 1: 3 or 2: 1: the secondary battery of 1 containing an oxide mixture of cobalt, copper and tin has good capacity and capacity maintenance rate.
As can be seen from fig. 6 and 7, the secondary batteries of examples 5 and 6 have better capacity and capacity retention rate after a high number of cycles (>250 cycles) than 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 would be understood by those skilled in the art that the secondary battery including the silicon tin iron oxide represented by formula (4) in which x4 is greater than 21 to 34 would have good capacity and capacity maintenance rate according to the foregoing description and the test results of example 5.
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 that the secondary battery including the silicon tin iron oxide represented by formula (5) or formula (6) has good capacity and capacity maintenance rate according to the foregoing description and the test results of example 5.
Although the atomic ratio of unpaired comprising silicon, tin and iron is 1: 1: 1 or 4: 1: 1 secondary battery containing a mixture of oxides of silicon, tin and iron the foregoing tests were carried out, but according to the foregoing description and the test results of example 6, it will be understood by those skilled in the art that the ratio of atoms including silicon, tin and iron is 1: 1: 1 or 4: 1: the secondary battery containing the oxide mixture of silicon, tin and iron of 1 has good capacity and capacity maintenance rate.
As can be seen from fig. 8, the secondary battery of example 7 had good capacity and capacity retention after a high number of cycles (>250 cycles).
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 would be understood by those skilled in the art 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 would have good capacity and capacity maintenance rate according to the foregoing description and the test results of example 7.
As can be seen from fig. 9, the secondary battery of example 8 has better electric capacity and electric capacity retention rate after a high number of cycles (>250 cycles) than the secondary batteries of comparative examples 3, 5 and 7.
Although the atomic ratio of copper, manganese and silicon included in the unpaired sample is 1: 1: 1. 4: 1: 1 or 1: 1: 4 secondary battery containing an oxide mixture of copper, manganese and silicon the foregoing tests were carried out, but according to the foregoing description and the test results of example 8, it will be understood by those skilled in the art that the ratio of atoms including copper, manganese and silicon is 1: 1: 1. 4: 1: 1 or 1: 1: the secondary battery of 4 containing the oxide mixture of copper, manganese and silicon has good capacity and capacity maintenance rate.
As can be seen from fig. 10 and 11, the secondary batteries of examples 9 and 10 had better capacity and capacity retention rate after a high number of cycles (>250 cycles) 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) in which x8 is 4 to less than 7, it would be understood by those skilled in the art that the secondary battery including the tin manganese nickel oxide represented by formula (8) in which x8 is 4 to less than 7 would have good capacity and capacity maintenance rate according to the foregoing description and the test results of example 9.
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 that the secondary battery including the tin manganese nickel oxide represented by formula (9), formula (10), or formula (11) has good electric capacity and electric capacity maintenance rate according to the foregoing description and the test results of example 9.
Although the atomic ratio of unpaired tin, manganese and nickel is 1: 1: 1. 1: 1: 2 or 2: 1: 1, the secondary battery containing an oxide mixture of tin, manganese and nickel was subjected to the foregoing test, but according to the foregoing description and the test results of example 10, it would be understood by those skilled in the art that the secondary battery containing an oxide mixture of tin, manganese and nickel in an atomic ratio of tin, manganese and nickel of 1: 1: 1. 1: 1: 2 or 2: 1: the secondary battery of 1 containing an oxide mixture of tin, manganese and nickel has good capacity and capacity maintenance rate.
As can be seen from fig. 12, the secondary battery of example 11 had good capacity and capacity retention after a high number of cycles (>250 cycles).
Although the foregoing tests were not performed on the secondary battery including the manganin nickel oxide represented by formula (12) or formula (14), it will be understood by those skilled in the art that the secondary battery including the manganin nickel oxide represented by formula (12) or formula (14) has good electric capacity and capacity maintenance rate according to the foregoing description and the test results of example 11.
As can be seen from fig. 13, the secondary battery of example 12 has better electric capacity and electric capacity retention rate after a high number of cycles (>250 cycles) than the secondary batteries of comparative examples 3, 8 and 9.
Although the atomic ratio of unpaired manganese, copper and nickel is 3: 2:1 or 1: 1: 1, the secondary battery containing an oxide mixture of manganese, copper and nickel was subjected to the foregoing test, but according to the foregoing description and the test results of example 12, it would be understood by those skilled in the art that the secondary battery containing an oxide mixture of manganese, copper and nickel in an atomic ratio of manganese, copper and nickel of 3: 2:1 or 1: 1: the secondary battery of 1 containing an oxide mixture of manganese, copper and nickel has good capacity and capacity maintenance rate.
As can be seen from fig. 14, the secondary battery of example 13 has better electric capacity and electric capacity retention rate after a high number of cycles (>250 cycles) than the secondary batteries of comparative examples 3, 4 and 9.
Although the atomic ratio of nickel, copper and tin is not specifically limited to 2: 1: 3 or 1: 2: 3, the secondary battery containing the oxide mixture of nickel, copper and tin was subjected to the foregoing test, but according to the foregoing description and the test results of example 13, it would be understood by those skilled in the art that the ratio of the number of atoms including nickel, copper and tin was 2: 1: 3 or 1: 2: the secondary battery of 3 containing an oxide mixture of nickel, copper and tin has good capacity and capacity maintenance rate.
As can be seen from fig. 15, the secondary battery of example 14 had good electric capacity and electric capacity retention rate after a high number of cycles (>250 cycles).
Although the foregoing test was not performed on the secondary battery including the nickel copper tin oxide represented by formula (15) in which x15 was 3 or 9, it would be understood by those skilled in the art that the secondary battery including the nickel copper tin oxide represented by formula (15) in which x15 was 3 or 9 would have good capacity and capacity maintenance rate according to the foregoing description and the test results of example 14.
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 would be understood by those skilled in the art that the secondary battery including the nickel copper tin oxide represented by formula (16) or formula (17) would have good electric capacity and capacity maintenance rate according to the foregoing description and the test results of example 14.
Based on the foregoing test results, it was confirmed that the secondary battery using the negative electrode material for a secondary battery according to the present invention can have good capacity, stability and charge-discharge cycle life by preparing the negative electrode.
In addition, compared with commercial graphite (the theoretical value of the capacitance is 372mAh/g), the secondary battery using the negative electrode material for the secondary battery has higher capacitance, so that the negative electrode material for the secondary battery can effectively improve the battery performance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (5)

1. A negative electrode material for a secondary battery, characterized by comprising a cobalt copper tin oxide represented by one of the following formulas (1) to (3):
Co5Cu1Sn3MOx1the compound of the formula (1),
Co2Cu1Sn1MOx2the compound of the formula (2),
Co1Cu1Sn1MOx3the compound of the formula (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 the group consisting of Ni, Cr, Mn, Zn, Al, Ti, In, Mo and W, and the atomic number ratio of M is 10 atomic% or less with respect to the total number of atoms of the metal elements In the cobalt-copper-tin oxide represented by formula (1), formula (2) or formula (3).
2. The negative electrode material for a secondary battery according to claim 1, wherein the cobalt-copper-tin oxide represented by formula (1), formula (2), or formula (3) has a spinel structure, a perovskite structure, a sodium chloride structure, or a chalcopyrite structure.
3. A negative electrode for a secondary battery, comprising:
a current collector; and
an anode material layer disposed on the current collector and comprising the anode material for a secondary battery according to any one of claims 1 to 2.
4. A secondary battery, characterized by comprising:
a positive electrode;
a negative electrode disposed apart 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 of 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 area, and wherein the electrolyte is disposed in the receiving area.
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