CN113036111B - Negative electrode active material and battery - Google Patents

Negative electrode active material and battery Download PDF

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Publication number
CN113036111B
CN113036111B CN202011300535.2A CN202011300535A CN113036111B CN 113036111 B CN113036111 B CN 113036111B CN 202011300535 A CN202011300535 A CN 202011300535A CN 113036111 B CN113036111 B CN 113036111B
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active material
electrode active
negative electrode
phase
material layer
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CN113036111A (en
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早稻田哲也
若杉悟志
吉田淳
足立真辉
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Toyota Motor Corp
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/362—Composites
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Manufacturing & Machinery (AREA)

Abstract

The main object of the present disclosure is to provide a negative electrode active material with small volume change caused by charge and discharge. In the present disclosure, the above-described problems are solved by providing a negative electrode active material including primary particles having a Si phase, a metal silicide phase, i.e., MSi phase (M is a transition metal element), and first voids.

Description

Negative electrode active material and battery
Technical Field
The present disclosure relates to a negative electrode active material and a battery.
Background
In recent years, development of batteries has been widely performed. For example, the automotive industry is pushing the development of batteries for electric vehicles or hybrid vehicles. In addition, si particles are known as active materials for batteries.
For example, patent document 1 discloses porous silicon particles having voids as a negative electrode active material. Patent document 2 discloses particles in which a Si phase is dispersed in a metal silicide phase as a negative electrode active material. Patent document 3 discloses, as a negative electrode active material, composite particles including particles composed of a Si phase and particles composed of a metal silicide phase.
Prior art literature
Patent document 1 Japanese patent laid-open publication No. 2013-203626
Patent document 2 Japanese patent laid-open No. 2015-095301
Patent document 3 Japanese patent laid-open publication No. 2013-235682
Disclosure of Invention
The Si particles have a large theoretical capacity and are effective for increasing the energy density of the battery. On the other hand, si particles have a large volume change during charge and discharge.
The present disclosure has been made in view of the above-described actual circumstances, and a main object thereof is to provide a negative electrode active material with little change in volume due to charge and discharge.
In order to solve the above-described problems, the present disclosure provides a negative electrode active material including primary particles having a Si phase, a metal silicide phase, i.e., a MSi phase (M is a transition metal element), and first voids.
According to the present disclosure, the primary particles have Si phase, metal silicide phase, i.e., MSi phase, and first voids, and thus can form a negative electrode active material with small volume change due to charge and discharge.
In the above publication, the proportion of the transition metal element may be 2mol% or more and less than 50mol% based on the total of the Si element and the transition metal element contained in the primary particles.
In the above publication, the proportion of the first voids of the primary particles may be 3% or more.
In the above publication, the above transition metal element may be at least one of W, mo, cr, V, nb, fe, ti, zr, hf and Os.
In the above publication, the above transition metal element may be at least one of Cr, ti, zr, hf and Os.
In the above publication, the negative electrode active material may be a secondary particle having a second void and formed by agglomerating a plurality of the primary particles.
In addition, in the present disclosure, there is provided a battery including a positive electrode active material layer, a negative electrode active material layer, and an electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer, wherein the negative electrode active material layer contains the negative electrode active material.
According to the present disclosure, since the negative electrode active material layer contains the negative electrode active material, a battery in which an increase in binding voltage due to charge and discharge is suppressed can be formed.
In the above disclosure, the negative electrode active material layer may contain the negative electrode active material, and β/α may be 0.02 to 0.5 inclusive, where α (μm) is the thickness of the negative electrode active material layer in the stacking direction and β (μm) is the average particle diameter of the secondary particles.
According to the present disclosure, the thickness of the anode active material layer in the stacking direction and the average particle diameter of the secondary particles are in a predetermined relationship, so that a battery in which an increase in binding pressure due to charge and discharge is more suppressed can be formed.
In the present disclosure, an effect of being able to obtain a negative electrode active material with small volume change due to charge and discharge can be exhibited.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of a battery of the present disclosure.
Fig. 2 is a cross-sectional SEM image of the negative electrode active material (primary particles) obtained in example 4.
Fig. 3 is a cross-sectional SEM image of the negative electrode active material (primary particles) obtained in comparative example 4.
Fig. 4 is a graph showing mechanical strength obtained by the Phase-Field method (Phase Field method).
Description of the reference numerals
1 … Positive electrode active material layer
2 … electrolyte layer
3 … anode active material layer
4 … positive electrode collector
5 … negative electrode collector
6 … battery shell
10 … battery
Detailed Description
Hereinafter, the negative electrode active material and the battery of the present disclosure will be described in detail.
A. Negative electrode active material
The anode active material of the present disclosure includes primary particles having a Si phase, a metal silicide phase, i.e., MSi phase (M is a transition metal element), and first voids.
According to the present disclosure, the primary particles have Si phase, metal silicide phase, i.e., MSi phase, and first voids, and thus can form a negative electrode active material with small volume change due to charge and discharge.
Batteries require high energy densities. Therefore, the use of Si materials excellent in capacity characteristics as active materials has been studied. However, when a Si material having a diamond crystal structure is used particularly in an all-solid-state battery, cracks may be generated in the electrode during repeated charge and discharge, and the battery life may be shortened. In addition, since a large stress is applied to the binding member of the battery in the charged state, a binding structure having high rigidity is required, and the binding jig may be enlarged. As a result, the energy density of the entire battery may be reduced. Accordingly, various studies have been made on suppression of expansion of Si material due to charge and discharge.
For example, patent document 1 discloses Si particles having voids therein, and patent document 3 discloses composite particles having voids between primary particles. However, these voids may be crushed by the pressing pressure at the time of manufacturing the electrode, and there is room for improvement in suppressing the expansion of Si particles. Patent document 2 discloses particles in which an Si phase is dispersed in a metal silicide phase, but there is still room for improvement in suppressing expansion of Si particles because cracks may occur at the interface between the metal silicide phase and the Si phase during charging.
On the other hand, the primary particles of the negative electrode active material of the present disclosure have a Si phase, a metal silicide phase, i.e., MSi phase, and first voids. Thus, even when the electrode is manufactured by pressing, the metal silicide phase functions as a pillar, and the first void can be maintained. As a result, expansion of Si particles can be suppressed. In general, when the primary particles have voids (first voids), the resistance tends to increase. However, since the metal silicide phase has electron conductivity, even if the metal silicide phase has the first voids, an increase in resistance can be suppressed.
1. Primary particles
The primary particles of the present disclosure have a Si phase, a metal silicide phase, i.e., MSi phase, and a first void.
(1) Si phase
The primary particles in the present disclosure have a Si phase. The Si phase is a phase of Si simple substance.
The area ratio (%) of the Si phase in the primary particles may be, for example, 30% or more, 40% or more, or 50% or more. On the other hand, the area ratio of the Si phase may be, for example, 90% or less, 80% or less, or 70% or less. The area ratio of the Si phase may be smaller than that of the MSi phase described later, and may be the same or larger, but from the viewpoint of capacity, the area ratio of the Si phase is preferably larger.
The area ratio of the Si phase can be obtained by observation with, for example, SEM (scanning electron microscope). A cross section of the negative electrode active material was observed in SEM, and a photograph of the particles was taken. The Si phase was strictly discriminated from the obtained photograph by image analysis software, and the area was determined. Then, the area ratio (%) was calculated according to the following formula. The number of samples is preferably large, for example, 20 or more, and may be 30 or more, 50 or more, or 100 or more.
Area ratio (%) =100× (Si phase area)/(primary particle area)
(2) MSi phase
The primary particles in the present disclosure have MSi phases. The MSi phase is a metal silicide phase, and M is a transition metal element described later. The ratio of M (transition metal element) and Si (Si element) in the MSi phase is not particularly limited as long as it is a ratio capable of forming a metal silicide.
The transition metal element M in the MSi phase is preferably at least one of W, mo, cr, V, nb, fe, ti, zr, hf and Os. Further, among these elements, at least one of Cr, ti, zr, hf and Os is particularly preferable. The transition metal element M in the MSi phase may be one or two or more of the above elements.
The proportion of the transition metal element M is, for example, 2mol% or more, or 5mol% or more, or 10mol% or more, or 20mol% or more, based on the total of the Si element and the transition metal element M contained in the primary particles. On the other hand, the proportion of the transition metal element M is, for example, less than 50mol%, and may be 40mol% or less, or may be 30mol% or less. The "Si element contained in the primary particles" includes both Si element in the Si phase and Si element in the MSi phase. The proportion of the transition metal element M can be confirmed by, for example, high-frequency Inductively Coupled Plasma (ICP) emission spectrometry.
The area ratio (%) of MSi phase in the primary particles is, for example, 5% or more, and may be 10% or more, or may be 20% or more. On the other hand, the area ratio of the MSi phase is, for example, 60% or less, 50% or less, or 40% or less. The area ratio of the MSi phase can be obtained by the following calculation formula, similarly to the area ratio of the Si phase.
Area ratio (%) =100× (MSi phase area)/(primary particle area)
(3) First gap
The primary particles in the present disclosure have a first void. The ratio of the first voids (first void ratio) is, for example, 3% or more, may be 5% or more, may be 10% or more, or may be 20% or more. On the other hand, the proportion of the first voids is, for example, 60% or less, 50% or less, 40% or less, or 30% or less. The ratio of the first voids can be obtained by the following equation in the same manner as the area ratio of the Si phase.
First void ratio (%) =100× (first void portion area)/(primary particle area)
The first void area in the above formula may be, for example, 1nm 2 The above can be 5nm 2 The above can be 10nm 2 Above, may be 100nm 2 The above. On the other hand, the first void area in the above formula may be 500nm, for example 2 Hereinafter, 300nm may be used 2 The following is given. The first void area may be calculated using image analysis software as described above.
In addition, the negative electrode active material of the present disclosure preferably maintains the above-described first porosity in the electrode and the battery. As this also suppresses swelling in the electrode and the battery.
The position of the first void in the primary particles is not particularly limited, and may be near the surface of the primary particles or near the center of the primary particles.
(4) Primary particles
The composition of the primary particles of the present disclosure is not particularly limited if it has the above-described elements, phases, and first voids.
The above-mentioned phases of the primary particles may exist as one continuous phase or may exist as a plurality of discontinuous phases, but the latter is preferable. Since this can suppress local expansion of the anode active material. When the Si phase, MSi phase, and first voids are present as a plurality of discontinuous phases, the cross section of the primary particles can be observed as a pattern in which the Si phase, MSi phase, and first voids are dispersed, for example, like a stripe pattern. In the relation between the Si phase and the MSi phase, the cross section of the primary particles can be observed as a sea-island structure in which the Si phase is sea and the metal silicide phase (MSi phase) is island. In the case of the sea-island structure, the number of MSi phases (islands) in the primary particles may be 10 or more, 50 or more, or 100 or more. On the other hand, the number of islands is, for example, 500 or less. The island area may be 1nm 2 The above can be 5nm 2 The above can be 10nm 2 Above, may be 100nm 2 The above. On the other hand, the island area is 500nm, for example 2 Hereinafter, 300nm may be used 2 The following is given. The first void area may be calculated using image analysis software, for example, as described above.
The primary particles may have only the Si phase, MSi phase, and first voids, or may have other phases. Examples of the other phase include a Li phase. The proportion (area ratio) of the other phase in the primary particles may be, for example, 5% or less, 3% or less, or 1% or less.
The average primary particle diameter of the negative electrode active material is, for example, 50nm or more, and may be 100nm or more, or 150nm or more. On the other hand, the average primary particle diameter of the negative electrode active material is, for example, 3000nm or less, 1500nm or less, or 1000nm or less. The average primary particle diameter of the negative electrode active material can be obtained by observation with an SEM, for example. The number of samples is preferably 20 or more, for example, 50 or more, or 100 or more. The average primary particle diameter of the anode active material can be appropriately adjusted by, for example, appropriately changing the production conditions of the anode active material and/or performing classification treatment.
2. Secondary particles
The negative electrode active material of the present disclosure may be a secondary particle having a second void and formed by agglomerating a plurality of the primary particles. Since, in the case where the anode active material is the above-described secondary particles, expansion of the anode active material layer and the battery can be further suppressed by the voids (first voids) of the primary particles and the second voids of the secondary particles. The second void is a void excluding the void (first void) of the primary particles among voids inside the secondary particles observed when the cross-sectional view of the secondary particles is taken.
The proportion of the second voids (second void ratio) is, for example, 3% or more, may be 5% or more, may be 10% or more, or may be 20% or more. On the other hand, the second void ratio is, for example, 60% or less, may be 50% or less, may be 40% or less, or may be 30% or less. The second void fraction can be obtained by the following expression, similarly to the void fraction of the primary particles (first void fraction).
Second void ratio (%) =100× (second void portion area)/(secondary particle area)
In relation to the thickness (α) of the negative electrode active material layer in the stacking direction, which will be described later, the average particle diameter (β) of the secondary particles is preferably a value in which β/α satisfies a predetermined range. Beta/alpha is, for example, 0.02 or more, may be 0.1 or more, or may be 0.2 or more. On the other hand, β/α is, for example, 0.5 or less, may be 0.4 or less, or may be 0.3 or less. Specific ranges of the average particle diameter of the secondary particles will be described later.
3. Negative electrode active material
The negative electrode active material of the present disclosure contains the above primary particles. The negative electrode active material may be the primary particles described above, or may be secondary particles in which the primary particles are aggregated. In addition, the structure of the tertiary particles may be a domain having a plurality of secondary particles.
As the shape of the negative electrode active material of the present disclosure, for example, a particle shape can be exemplified. The average secondary particle diameter (β) of the negative electrode active material of the present disclosure is, for example, 1 μm or more, may be 2 μm or more, may be 5 μm or more, or may be 7 μm or more. On the other hand, the average secondary particle diameter of the negative electrode active material is, for example, 60 μm or less, and may be 40 μm or less, and particularly preferably 20 μm or less. The measurement and adjustment of the average secondary particle diameter are the same as those of the primary particles.
The negative electrode active material of the present disclosure is generally used for a battery. The battery is described in detail in "b.
The method for producing the negative electrode active material of the present disclosure is not particularly limited, and examples thereof include: a preparation step of preparing a precursor containing Si element, transition metal element and Li element; and a Li extraction step of extracting Li element from the precursor to obtain the negative electrode active material.
The preparation step is a step of preparing a precursor containing Si element, transition metal element, and Li element. The precursor may be purchased or may be self-prepared. In the case of self-modulation, for example, a method of mixing a Si element source with a transition metal element source to prepare a Si alloy, and adding a Li element source to the Si alloy to mix them can be mentioned. The amounts of the Si element and the transition metal element contained in the precursor are not particularly limited as long as the negative electrode active material of the present disclosure can be obtained, and may be appropriately adjusted. The amount of Li element is not particularly limited either. The transition metal element is the above-mentioned transition metal element M.
The Li extraction step is a step of extracting Li element from the precursor to form a first void, thereby obtaining the negative electrode active material. As a method for extracting Li, for example, a method in which a Li extraction solvent such as ethanol or acetic acid is reacted with a precursor for a predetermined time is given.
Through the steps described above, a negative electrode active material as primary particles can be produced. The porosity of the primary particles can be adjusted by changing, for example, the amount of Li element in the precursor in the preparation step, the type of Li extraction solvent in the Li extraction step, and the reaction time between the Li extraction solvent and the precursor. For example, by increasing the amount of Li element in the precursor, the void fraction can be improved.
In addition, in the present disclosure, there can be provided a method for producing a negative electrode active material, which is a method for producing a plurality of secondary particles in which the primary particles are aggregated and have a second void, the method including: a preparation step of preparing a micelle solution containing water, a surfactant, a template material and a polymerization initiator; a polymerization step of adding the primary particles to the micelle solution to perform polymerization reaction; and a heat treatment step of heat-treating the micelle solution after the polymerization reaction. By such a method, a negative electrode active material having a second void inside the secondary particle can be produced. The negative electrode active material of the secondary particles may be produced by, for example, adding a solvent such as butyl butyrate to a powder material containing the primary particles and a binder, and granulating the mixture.
B. Battery cell
Fig. 1 is a schematic cross-sectional view showing an example of a battery in the present disclosure. The battery 10 shown in fig. 1 has: a positive electrode active material layer 1, a negative electrode active material layer 2, an electrolyte layer 3 formed between the positive electrode active material layer 1 and the negative electrode active material layer 2, a positive electrode current collector 4 for collecting current from the positive electrode active material layer 1, a negative electrode current collector 5 for collecting current from the negative electrode active material layer 2, and a battery case 6 accommodating these components. In the present disclosure, the anode active material layer 2 contains the anode active material described above.
According to the present disclosure, by including the negative electrode active material layer described above, a battery capable of suppressing an increase in binding voltage due to charge and discharge can be formed.
1. Negative electrode active material layer
The negative electrode active material layer is a layer containing at least the negative electrode active material. The negative electrode active material is the same as that described in the above "a. Negative electrode active material", and therefore, description thereof is omitted here.
The negative electrode active material layer may contain only the negative electrode active material described above, or may further contain another negative electrode active material. In the latter case, the proportion of the negative electrode active material may be, for example, 50% by weight or more, 70% by weight or more, or 90% by weight or more, based on the total negative electrode active material.
The proportion of the negative electrode active material in the negative electrode active material layer is, for example, 20% by weight or more, and may be 30% by weight or more, or may be 40% by weight or more. On the other hand, the proportion of the negative electrode active material is, for example, 80% by weight or less, and may be 70% by weight or less, or may be 60% by weight or less.
In addition, the anode active material layer may further contain at least one of a solid electrolyte, a conductive material, and a binder as necessary. The type of the solid electrolyte is described in detail in "3. Electrolyte layer" described later. The proportion of the solid electrolyte in the anode active material layer is, for example, 1% by weight or more, and may be 10% by weight or more, or 20% by weight or more. On the other hand, the proportion of the solid electrolyte in the negative electrode active material layer is, for example, 60 wt% or less, or 50 wt% or less.
Examples of the conductive material include a carbon material and metal particles. Specific examples of the carbon material include particulate carbon materials such as Acetylene Black (AB) and Ketjen Black (KB), and fibrous carbon materials such as carbon fibers, carbon Nanotubes (CNT), carbon Nanofibers (CNF) and Vapor Grown Carbon Fibers (VGCF). Examples of the metal particles include Ni, cu, fe, and SUS. The proportion of the conductive material in the anode active material layer is, for example, 1% by weight or more, or may be 5% by weight or more. On the other hand, the proportion of the conductive material is, for example, 30% by weight or less, or 20% by weight or less.
Examples of the binder include rubber-based binders such as butadiene rubber, hydrogenated butadiene rubber, styrene Butadiene Rubber (SBR), hydrogenated styrene butadiene rubber, nitrile butadiene rubber, hydrogenated nitrobutadiene rubber, and ethylene propylene rubber, fluorinated binders such as polyvinylidene fluoride (PVDF), polyvinylidene fluoride-polyhexafluoropropylene copolymer (PVDF-HFP), polytetrafluoroethylene, and fluororubber, polyolefin-based thermoplastic resins such as polyethylene, polypropylene, and polystyrene, imide-based resins such as polyimide, and polyamide-based resins such as polyamide, acrylate resins such as polymethacrylate, and polyethylacrylate, and methacrylic resins such as polymethyl methacrylate and polyethyl methacrylate. The proportion of the binder in the anode active material layer is, for example, 1% by weight or more and 30% by weight or less.
The thickness of the negative electrode active material layer is, for example, 0.1 μm or more and 1000 μm or less. In the case where the secondary particles are contained in the anode active material layer, the thickness (α) of the anode active material layer is preferably a value at which the β/α satisfies a predetermined numerical range.
2. Positive electrode active material layer
The positive electrode active material layer is a layer containing at least a positive electrode active material. In addition, the positive electrode active material layer may further contain at least one of a solid electrolyte, a conductive material, and a binder as necessary.
Examples of the positive electrode active material include oxide active materials. Examples of the oxide active material used in the lithium ion battery include LiCoO 2 、LiMnO 2 、Li 2 NiMn 3 O 8 、LiVO 2 、LiCrO 2 、LiFePO 4 、LiCoPO 4 、LiNiO 2 、LiNi 1/3 Co 1/3 Mn 1/3 Mn 1/3 O 2 And an oxide active material. In addition, for example, a material containing LiNbO may be formed on the surface of the active material 3 And a coating layer of a Li ion-conductive oxide.
The proportion of the positive electrode active material in the positive electrode active material layer is, for example, 20% by weight or more, and may be 30% by weight or more, or may be 40% by weight or more. On the other hand, the proportion of the positive electrode active material is, for example, 80% by weight or less, and may be 70% by weight or less, or may be 60% by weight or less.
The types and proportions of the solid electrolyte, the conductive material, and the binder used for the positive electrode active material layer are the same as those described in the above "1. Negative electrode active material layer", and therefore description thereof is omitted here.
The thickness of the positive electrode active material layer is, for example, 0.1 μm or more and 1000 μm or less.
3. Electrolyte layer
The electrolyte layer is a layer formed between the positive electrode active material layer and the negative electrode active material layer. The electrolyte constituting the electrolyte layer may be a liquid electrolyte (electrolyte solution) or a solid electrolyte, but the latter is preferable.
As the solid electrolyte, typical examples include inorganic solid electrolytes such as sulfide solid electrolytes, oxide solid electrolytes, nitride solid electrolytes, and halide solid electrolytes; organic polymer electrolytes such as polymer electrolytes.
Examples of the sulfide solid electrolyte having lithium ion conductivity include solid electrolytes containing Li element, X element (X is at least one of P, as, sb, si, ge, sn, B, al, ga, in), and S element. In addition, the sulfide solid electrolyte may further contain at least one of an O element and a halogen element. Examples of the halogen element include an F element, a Cl element, a Br element, and an I element.
Examples of the sulfide solid electrolyte include Li 2 S-P 2 S 5 、Li 2 S-P 2 S 5 -LiI、Li 2 S-P 2 S 5 -GeS 2 、Li 2 S-P 2 S 5 -Li 2 O、Li 2 S-P 2 S 5 -Li 2 O-LiI、Li 2 S-P 2 S 5 -LiI-LiBr、Li 2 S-SiS 2 、Li 2 S-SiS 2 -LiI、Li 2 S-P 2 S 5 -LiBr、Li 2 S-SiS 2 -LiCl、Li 2 S-SiS 2 -B 2 S 3 -LiI、Li 2 S-SiS 2 -P 2 S 5 -LiI、Li 2 S-B 2 S 3 、Li 2 S-P 2 S 5 -Z m S n (wherein m and n are positive numbers, Z is one of Ge, zn and Ga), li 2 S-GeS 2 、Li 2 S-SiS 2 -Li 3 PO 4 、Li 2 S-SiS 2 -Li x MO y (wherein x and y are positive numbers. M is any of P, si, ge, B, al, ga, in).
In addition, examples of the oxide solid electrolyte having lithium ion conductivity includeSuch as a solid electrolyte containing Li element, Y element (Y is at least one of Nb, B, al, si, P, ti, zr, mo, W, S), and O element. Specific examples include Li 7 La 3 Zr 2 O 12 、Li 7-x La 3 (Zr 2-x Nb x )O 12 (0≤x≤2)、Li 5 La 3 Nb 2 O 12 A garnet-like solid electrolyte; (Li, la) TiO 3 、(Li,La)NbO 3 、(Li,Sr)(Ta,Zr)O 3 A perovskite-type solid electrolyte; li (Al, ti) (PO 4 ) 3 、Li(Al,Ga)(PO 4 ) 3 Sodium super ion conductor (NASICON) solid electrolyte; li (Li) 3 PO 4 、LIPON(Li 3 PO 4 A compound in which a part of O is replaced with N), and the like; li (Li) 3 BO 3 、Li 3 BO 3 A Li-B-O solid electrolyte such as a compound in which part of O is replaced with C.
The binder is the same as that described in the above "1. Negative electrode active material layer", and therefore, description thereof is omitted.
4. Other constructions
The battery of the present disclosure has at least the above-described anode active material layer, cathode active material layer, and electrolyte layer. Further, a positive electrode collector for collecting current from the positive electrode active material layer and a negative electrode collector for collecting current from the negative electrode active material layer are generally provided. Examples of the material of the positive electrode current collector include SUS, aluminum, nickel, iron, titanium, and carbon. On the other hand, examples of the material of the negative electrode current collector include SUS, copper, nickel, and carbon.
In addition, the battery of the present disclosure may further have a binding jig that applies a binding pressure to the positive electrode active material layer, the electrolyte layer, and the negative electrode active material layer in the thickness direction. As the binding jig, a known jig may be used. The binding pressure is, for example, 0.1MPa or more, and may be 1MPa or more, or may be 5MPa or more. On the other hand, the binding pressure is, for example, 100MPa or less, and may be 50MPa or less, or may be 20MPa or less.
5. Battery cell
The battery of the present disclosure is preferably a lithium ion battery. In addition, the battery of the present disclosure may be either a liquid-based battery or an all-solid battery, but the latter is preferable. Because it can better enjoy the effect of the present disclosure of suppressing the increase in the binding pressure caused by charge and discharge.
In addition, the battery of the present disclosure may be either a primary battery or a secondary battery, with secondary batteries being preferred. This is useful as a vehicle-mounted battery, for example, because it can be repeatedly charged and discharged. Secondary batteries also include the use of secondary batteries as primary batteries (use for primary charging purposes only).
The battery of the present disclosure may be a single battery or a stacked battery. The laminated battery may be a monopolar laminated battery (parallel laminated battery) or a bipolar laminated battery (series laminated battery). Examples of the shape of the battery include coin type, laminate type, cylindrical type, and square type.
The present disclosure is not limited to the above embodiments. The above-described embodiments are examples, and those having substantially the same technical ideas as described in the scope of the claims of the present disclosure and exerting the same effects are all included in the technical scope of the present disclosure.
Examples
Example 1
(Synthesis of negative electrode active material (primary particles))
(1) Fabrication of metal silicide
2-5 mm bulk Si (manufactured by high purity chemical) and 2-5 mm bulk transition metal (Cr) are mixed and melted by argon arc to prepare ingots. The ratio of Si element to Cr element is represented by X=2 in (100-X) Si- (X) M in Table 1 below. The ingot was crushed with a tungsten mortar and crushed with a ball mill to obtain Si alloy powder (metal silicide).
(2) Preparation of porous Metal silicide (negative electrode active Material)
To 0.65g of Si contained in the Si alloy powder thus obtained, 0.60g of metallic Li (manufactured by Bencheng Metal) was added. Then, an agate mortar was used for mixing under Ar atmosphere to obtain a LiSi precursor. 250ml of ethanol (NACALAAI TESQUE) at 0℃was added to 1.0g of the obtained LiSi precursor, and the mixture was reacted in a glass reactor under Ar atmosphere for 120 minutes. Then, the liquid and solid reactant a were separated by suction filtration, and the solid reactant a was recovered. To 0.5g of the recovered solid reactant A was added 50ml of acetic acid (produced by NACALAAI TESQUE), and the mixture was reacted in a glass reactor under an atmospheric atmosphere for 60 minutes. Then, the liquid and solid reactant B were separated by suction filtration, and the solid reactant B was recovered. The solid reactant B was vacuum-dried at 100 ℃ for 2 hours to prepare a porous metal silicide (anode active material).
(production of evaluation cell)
0.7g of 0.75Li as a solid electrolyte 2 S-0.25P 2 S 5 0.6g of the negative electrode active material having an average particle diameter (average primary particle diameter) of 3 μm, 0.06g of VGCF as a conductive material, and 0.24g of a butyl butyrate solution containing a PVDF-based resin at 5% by weight as a binder were added to a polypropylene container. After the container was subjected to ultrasonic treatment for 30 seconds in an ultrasonic dispersing apparatus, the container was subjected to vibration treatment for 30 minutes by an oscillator, thereby obtaining a negative electrode mixture. The negative electrode mixture obtained was applied to a current collector (copper foil) by a doctor blade method using an applicator, and naturally dried for 60 minutes. The negative electrode precursor thus obtained was dried on a hot plate adjusted to 100 ℃ for 30 minutes to prepare a negative electrode.
0.3g of 0.75Li as a solid electrolyte 2 S-0.25P 2 S 5 2g of LiNi as a positive electrode active material 1/3 Co 1/ 3 Mn 1/3 O 2 0.03g of VGCF as a conductive material, and 0.3g of a butyl butyrate solution containing 5 wt% of PVDF-based resin as a binder were added to a polypropylene container. After the container was subjected to ultrasonic treatment for 30 seconds in an ultrasonic dispersing apparatus, the container was subjected to vibration treatment for 30 minutes by an oscillator, thereby obtaining a positive electrode mixture. The positive electrode mixture obtained was applied to a current collector (aluminum foil) by a doctor blade method using an applicator, and naturally dried for 60 minutes. The positive electrode precursor thus obtained was dried on a hot plate adjusted to 100 ℃ for 30 minutes to prepare a positive electrode.
0.4g of 0.75Li having an average particle diameter of 2 μm as a solid electrolyte 2 S-0.25P 2 S 5 And 0.05g of a heptane solution containing 5 wt% of ABR-based resin as a binder were added to the polypropylene container. After the container was subjected to ultrasonic treatment for 30 seconds in an ultrasonic dispersing apparatus, the container was subjected to vibration treatment for 30 minutes by an oscillator to obtain a paste. The obtained paste was applied to a substrate (aluminum foil) by a doctor blade method using an applicator, and dried on a hot plate adjusted to 100 ℃ for 30 minutes to prepare a solid electrolyte layer.
The negative electrode, the solid electrolyte layer, and the positive electrode obtained as described above were contacted and laminated in this order. The laminate was subjected to a pressure of 200MPa at 130 ℃ for 3 minutes to prepare a battery for evaluation (all-solid-state battery).
Examples 2 to 6
The Cr amount was changed so that the proportion of the transition metal element in the anode active material became the values of table 1. The amount of Li in the above "(2) preparation of porous metal silicide (negative electrode active material)" was adjusted to the value of the first porosity in table 1. Except for this, an evaluation battery was produced in the same manner as in example 1.
Comparative example 1
An evaluation cell was produced in the same manner as in example 1, except that Si particles were used as the negative electrode active material.
Comparative example 2
An evaluation battery was produced in the same manner as in example 1, except that "(1) production of metal silicide" was not performed and "(2) production of porous metal silicide (negative electrode active material) was only performed" in example 1.
Comparative example 3
An evaluation battery was produced in the same manner as in example 1, except that "(2) production of a porous metal silicide (negative electrode active material)" was not performed in example 1, "production of a metal silicide was performed only" (1).
Comparative example 4
The negative electrode active material was produced according to the method of patent document 2 (japanese patent laid-open No. 2015-095301). An evaluation battery was produced in the same manner as in example 1, except that the negative electrode active material was used. The transition metal element contained in the metal silicide phase was the same as in example 1.
Comparative examples 5 and 6
The Cr amount was changed so that the proportion of the transition metal element in the anode active material became 50mol%. The amount of Li in the above "(2) preparation of porous metal silicide (negative electrode active material)" was adjusted to the value of the first porosity in table 1. Except for this, an evaluation battery was produced in the same manner as in example 1.
[ evaluation 1]
(first void fraction)
Cross-sectional SEM images of the negative electrode active materials (negative electrode active materials before production of the evaluation battery) produced in examples 1 to 6 and comparative examples 1 to 6 were obtained. Based on the obtained SEM image, the first void fraction was calculated by the following calculation formula. The void fractions are shown in Table 1. Fig. 2 and 3 show primary particle images of example 4 and comparative example 4.
First void ratio (%) =100× (first void portion area)/(primary particle area)
As shown in fig. 2, in the negative electrode active material of the present disclosure (example 4), it was confirmed that the Si phase, the MSi phase, and the first voids were present inside the primary particles. As shown in fig. 2, the Si phase, MSi phase, and first voids are present as a plurality of discontinuous phases, respectively, and the cross section of the negative electrode active material is a patch pattern. On the other hand, as shown in fig. 3, in comparative example 4, the first void was not confirmed at all.
(binding pressure rise)
The evaluation batteries produced in examples 1 to 6 and comparative examples 1 to 6 were each bound at a predetermined pressure, and were energized at a constant current of 0.1C up to a predetermined voltage to perform primary charging. In the initial charge, the battery restraint pressure was monitored, and the restraint pressure in the charged state was measured. The amount of increase in binding pressure was evaluated relatively at a value of 1.00 in comparative example 1. The results are shown in Table 1.
(resistance)
For each of the evaluation batteries produced in examples 1 to 6 and comparative examples 1 to 6, the resistance at 25℃and 60% of SOC (State of Charge) was obtained. Specifically, after charging to a voltage of 3.7V at 0.245mA, discharging for 5 seconds at 7.35mA, the internal resistance was calculated from the voltage change. The resistance was evaluated relatively with the value of comparative example 1 being 1.00. The results are shown in Table 1.
TABLE 1
As shown in table 1, in comparative example 2 having no MSi phase (metal silicide phase) and having the first voids, the increase in the binding voltage was not suppressed, and the resistance was also high. This is considered to be because the metal silicide phase is not present, and therefore, the first void is crushed in the pressing step at the time of manufacturing the electrode. In comparative examples 3 and 4 having Si phase and metal silicide phase and having no first void, cracks were generated at the interface between the metal silicide phase and Si phase during charging, and the increase of the binding voltage could not be suppressed.
On the other hand, in the evaluation batteries (examples 1 to 6) using the negative electrode active material (primary particles) of the present disclosure, the increase in the binding pressure was significantly suppressed. This is considered to be because the metal silicide phase functions as a pillar and can maintain the first void. Further, as is clear from comparative example 2, when the first void is provided, the resistance tends to increase. However, since the metal silicide phase has electron conductivity, the increase in resistance can be suppressed in the evaluation batteries of examples 1 to 6. In comparative examples 5 and 6, in which the proportion of the transition metal element was 50mol%, only the metal silicide phase was formed, and the Si phase was not formed.
From the above, it was confirmed that the negative electrode active material (primary particles) of the present disclosure is small in volume change due to charge and discharge, and therefore, the battery using the negative electrode active material can suppress an increase in binding voltage.
Example 7
(Synthesis of negative electrode active material (secondary particles))
A micelle solution was prepared by heating a solution obtained by mixing water, a surfactant (cetyltrimethylammonium bromide), a template material (styrene) and a polymerization initiator (2, 2' -azo (2, 4-dimethylvaleronitrile)). Then, the primary particles (first void ratio: 60%) prepared in example 4 and an organic solvent (octane) were added to the micelle solution, and a reaction (polymerization reaction) was performed for 3 hours. The polymerization reaction is ended by cooling. Then, the primary particles were subjected to heat treatment at 500 ℃ to prepare secondary particles in which the primary particles were aggregated. The average particle diameter of the secondary particles was appropriately adjusted so that the ratio (β/α) of the average particle diameter of the secondary particles to the thickness of the anode active material layer in the stacking direction became the value of table 2. In addition, the secondary particles produced by such a method have voids (second voids) inside thereof.
(production of Battery)
Using the secondary particles as the anode active material, the average particle diameter of the secondary particles and the thickness of the anode active material layer were adjusted so that the ratio (β/α) of the average particle diameter (β) of the secondary particles to the thickness (α) in the stacking direction of the anode active material became the values of table 2. An evaluation battery was produced in the same manner as in example 1, except for the above.
Examples 8 to 11
The average particle diameter of the secondary particles and the thickness of the anode active material layer were adjusted so that β/α became the values of table 2. An evaluation cell was produced in the same manner as in example 7, except for the above.
[ evaluation 2]
(binding pressure rise)
The increase in the binding pressure of each of the evaluation batteries produced in examples 7 to 11 was measured in the same manner as in evaluation 1. The amount of increase in binding pressure was evaluated relatively at a value of 1.00 in example 7. The results are shown in Table 2.
(resistance)
The resistances of the evaluation cells prepared in examples 7 to 11 were calculated in the same manner as in evaluation 1. The resistance was evaluated relatively at a value of 1.00 in example 7. The results are shown in Table 2.
TABLE 2
As shown in table 2, the larger β/α is, the smaller the binding pressure rise amount is. This is considered to be because the average particle diameter of the secondary particles is relatively large, and thus the voids between the secondary particles in the negative electrode active material layer are increased, and expansion of the negative electrode active material can be absorbed. On the other hand, if β/α becomes excessively large, the battery resistance increases sharply. This is thought to be due to the fact that the gaps between the secondary particles are relatively excessively large, and the Li ion conductivity between the secondary particles is lowered. From the above, it is considered that β/α is preferably 0.02 or more and 0.5 or less in the battery in view of the suppression effect of the binding pressure increase amount and the increase in resistance.
(mechanical Strength of Metal silicide)
The mechanical strength of Si and various metal silicides was calculated from simulations based on the Phase-Field method. The results are shown in FIG. 4. Further, the rounded metal silicide in the figure is a metal silicide which undergoes phase separation so as not to react with Li. It is considered that if the metal silicide has a mechanical strength higher than that of silicon (Si), the metal silicide can sufficiently function as a pillar in the primary particles. In addition, it is considered that the metal silicide which is phase-separated and does not react with Li easily maintains the structure as a pillar.

Claims (2)

1. A negative electrode active material for use in an all-solid-state battery, comprising primary particles having a Si phase, a metal silicide phase, i.e., a MSi phase, and first voids, wherein M is a Cr element,
the primary particles are produced by a preparation process and a Li extraction process,
in the preparation step, a Si alloy is prepared by mixing a Si element source with a transition metal element, and a Li element source is added to the Si alloy to mix them, thereby preparing a precursor containing Si element, transition metal element and Li element,
in the Li extraction step, a Li extraction solvent is reacted with the precursor for a predetermined time, whereby Li element is extracted from the precursor to form the first void,
the Si phase, the MSi phase, and the first void are present as a plurality of discontinuous phases, respectively, and the cross section of the primary particle has a speckle pattern in which the Si phase, the MSi phase, and the first void are dispersed when observed by a scanning electron microscope,
the ratio of the Cr element to the total of the Si element and the Cr element contained in the primary particles is 2mol% or more and less than 50mol%,
the proportion of the first voids in the primary particles is 3% or more and 60% or less,
the negative electrode active material is a secondary particle formed by agglomerating a plurality of the primary particles and having a second void.
2. An all-solid battery having a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer,
the negative electrode active material layer contains the negative electrode active material according to claim 1,
when the thickness of the negative electrode active material layer in the stacking direction is α and the average particle diameter of the secondary particles is β, β/α is 0.1325 to 0.5, where α and β are each a μm.
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