Patent Application
20240021806
The present disclosure mainly relates to an improvement of a negative electrode for a non-aqueous electrolyte secondary battery.
Non-aqueous electrolyte secondary batteries, especially lithium ion secondary batteries, because of their high voltage and high energy density have been expected as promising power sources for small consumer applications, power storage devices, and electric cars. With increasing demand for a higher battery energy density, a material containing silicon (Si) that forms an alloy with lithium has been expected to be utilized as a negative electrode active material having a high theoretical capacity density.
Patent Literature 1 proposes a negative electrode active material (hereinafter sometimes referred to as LSX) comprising a lithium silicate phase represented by Li2zSiO2+z where 0<z<2, and silicon particles dispersed in the lithium silicate phase.
The LSX, as compared to SiOx in which silicon particles are dispersed in the SiO2 phase, has a small irreversible capacity, and can improve the initial charge-discharge efficiency.
However, the lithium silicate phase in the LSX is poor in alkali resistance (stability against Li), and in some cases, may still cause a side reaction with Li ions during charge in the early stage. Therefore, further improvement in initial charge-discharge efficiency has been required.
In view of the above, one aspect of the present disclosure relates to a negative electrode active material for a non-aqueous electrolyte secondary battery, including: composite particles containing a lithium aluminate phase, and a silicon phase dispersed in the lithium aluminate phase.
Another aspect of the present disclosure relates to a non-aqueous electrolyte secondary battery, including: a positive electrode; a negative electrode; and a non-aqueous electrolyte, wherein the negative electrode includes the above-described negative electrode active material for a non-aqueous electrolyte secondary battery.
According to the present disclosure, it is possible to suppress the deterioration in initial charge-discharge efficiency of a non-aqueous electrolyte secondary battery.
[Negative Electrode Active Material for Non-Aqueous Electrolyte Secondary Battery]
A negative electrode active material for a non-aqueous electrolyte secondary battery according to an embodiment of the present disclosure includes composite particles containing a lithium aluminate phase, and a silicon phase dispersed in the lithium aluminate phase (hereinafter sometimes simply referred to as “LAX particles”).
The lithium aluminate phase in the LAX particles is more excellent in alkali resistance than the lithium silicate phase in the LSX particles in which a silicon phase is dispersed in the lithium silicate phase. Therefore, in the LAX particles, the side reaction with Li ions during initial charge is less likely to occur than in the LSX particles, and the deterioration of the negative electrode active material due to the side reaction and the decrease in initial capacity resulting therefrom are suppressed. That is, the reduction in initial charge-discharge efficiency is highly suppressed.
The LAX particles, practically, may not contain either lithium silicate or SiO2. The LAX particles may contain lithium silicate and SiO2, but preferably in a small amount. The sum of the contents of lithium silicate and SiO2 in the LAX particles may be, for example, 3 mass % or less.
In the LAX particles, it is preferable that a content proportion MAl of aluminum in all elements other than oxygen is 10 mass % or more and 47 mass % or less, and a content proportion MLi of lithium in all elements other than oxygen is 0.7 mass % or more and 13.5 mass % or less. When the aluminum content proportion MAl and the lithium content proportion MLi are within the ranges as above, an aluminate phase having excellent stability and ion conductivity can be easily obtained. The above stability includes both chemical stability (alkali resistance) and thermal stability. The content proportion MAl of aluminum is more preferably 11.5 mass % or more and 45.5 mass % or less. The content proportion MLi of lithium is more preferably 1.0 mass % or more and 9.5 mass % or less.
In addition, in view of easily obtaining a lithium aluminate phase having excellent stability and ion conductivity, the ratio MAl/MLi of the content proportion MAI of aluminum to the content proportion MLi of lithium is preferably 2 or greater and 20 or less. The MAI/MLi is more preferably 4 or greater and 12 or less.
In view of achieving both high capacity and improved cycle characteristics, in the LAX particles, the content proportion MSi of silicon in all elements other than oxygen is, for example, preferably 40 mass % or more and 90 mass % or less, more preferably 50.8 mass % or more and 85.5 mass % or less. The above content proportion MSi of silicon is the amount of Si constituting the silicon phase in the LAX particles.
In an X-ray diffraction (XRD) pattern of the composite particles obtained by XRD measurement, a peak attributed to the lithium aluminate phase can be observed around 2θ=x°. The x° is at least one selected from the group consisting of 19.4°, 22.3°, 31.9°, 34.3°, and 37.5°. For the X ray for the XRD measurement, Kα ray of Cu is used. In the present specification, around x° means, for example, being within the range of x±1°.
An Al2O3 phase may be dispersed in the lithium aluminate phase. The fine, highly crystalline Al2O3 phase can be distributed like islands in the matrix of the aluminate phase. In this case, expansion and cracking of the aluminate phase associated with expansion and contraction of the silicon phase can be suppressed, and the cycle characteristics tend to be improved. In this case, a peak attributed to the Al2O3 phase can be observed around 20=25.4° in the X-ray diffraction pattern of the composite particles obtained by X-ray diffraction measurement. The content of the Al2O3 phase in the LAX particles is, for example, 0 mass % or more and 10 mass % or less.
Here,
In both LAX2 and 4, a peak attributed to the Si (111) plane of the silicon phase is observed around 20=28°. In the Al-rich LAX2, a peak attributed to the Al2O3 phase is observed around 20=25.4°.
In
In LAX4, peaks belonging to LiAlO2 and Li5AlO4 of the lithium aluminate phase are observed around 2θ=22.3° and 2θ=34.3° (peaks of (iv) and (v) in
The composite particles have a sea-island structure in which fine silicon phases are dispersed like islands in a sea of the lithium aluminate phase. The lithium aluminate phase has favorable ion conductivity, and through the lithium aluminate phase, absorption and release of lithium ions by the silicon phase are smoothly carried out. By controlling the amount of silicon phase dispersed in the lithium aluminate phase, a higher capacity can be achieved. The expansion and contraction of the silicon phases can be relaxed by the lithium aluminate phase. Therefore, a higher battery capacity and improved cycle characteristics can be both easily achieved. In view of relaxing the expansion and contraction of the silicon phases, the lithium aluminate phase may be amorphous.
In the composite particles, a plurality of primary particles each containing a lithium aluminate phase and a silicon phase are bonded together, constituting a secondary particle. The average particle diameter of the composite particles (secondary particles) is, for example, 1 μm or more and 25 μm or less, and may be 4 μm or more and 15 μm or less. In the particle diameter ranges as above, the stress that occurs along with the changes in volume of the composite particles during charge and discharge tends to be relaxed, and favorable cycle characteristics are likely to be obtained. The surface area of the composite particles also can be an appropriate size, and the reduction in capacity due to a side reaction with the non-aqueous electrolyte is also suppressed. The average particle diameter of the composite particles means a particle diameter (volume average particle diameter) at 50% cumulative volume in a particle size distribution measured by a laser diffraction scattering method. As the measurement instrument, for example, “LA-750” available from Horiba, Ltd. (HORIBA) can be used. When the surface of the composite particles is covered with a conductive layer, since the thickness of the conductive layer is practically so small as not to influence the average particle diameter of the composite particles, the average particle diameter of the composite particles with the conductive layer may be regarded as the average particle diameter of the composite particles.
The composite particles can be taken out from the battery in the following manner. First, the battery in a fully discharged state is disassembled, to take out the negative electrode, and the negative electrode is washed with anhydrous ethyl methyl carbonate or dimethyl carbonate, to remove the non-aqueous electrolyte component. As described later, the negative electrode has a negative electrode current collector and a negative electrode mixture layer supported on its surfaces. The negative electrode mixture layer is peeled off from the copper foil, and ground in a mortar, to obtain a sample powder. Next, the sample powder is dried in a dry atmosphere for 1 hour, and immersed in a weakly boiled 6M hydrochloric acid for 10 minutes, to remove elements derived from components other than the composite particles. Next, the sample powder is washed with ion-exchanged water, and filtered, followed by drying at 200° C. for 1 hour. This is followed by heating to 900° C. in an oxygen atmosphere to remove the conductive layer, and thus, the composite particles only can be isolated. The fully discharged state means a state in which the depth of discharge (DOD) is 90% or more (the state of charge (SOC) is 10% or less).
(Lithium aluminate phase) The lithium aluminate contains lithium (Li), aluminum (Al), and oxygen (O). The atomic ratio O/Al of O to Al in the lithium aluminate is, for example, 1.6 or greater and 4 or less. The atomic ratio Li/Al of Li to Al in the lithium aluminate is, for example, ⅕ or greater and 5 or less. When the atomic ratios of O/Al and Li/Al are within the ranges as above, it is advantageous in the stability and the ion conductivity of the lithium aluminate phase.
The composition of the lithium aluminate can be represented by the formula: LiuAlO(3+u)2. In view of the ease of production, the stability, the ion conductivity, and others, u in the formula is, for example, greater than 0 and 5 or less, or may be greater than 0 and 1 or less. For example, when u=⅕, the composition can be represented by LiAl5O8, and when u=½, by Li2Al4O7. When u=1, the composition can be represented by LiAlO2, and when u=5, by Li5AlO4. In view of the ease of production, the stability, the ion conductivity, and other, the lithium aluminate phase preferably contains at least one selected from the group consisting of LiAl5O8, Li2Al4O7, LiAlO2 and Li5AlO4. In particular, the lithium aluminate phase more preferably contains LiAlO2 as a major component. Herein, the “major component” refers to a component that occupies 50 mass % or more of the mass of the whole lithium aluminate phase, and may occupy 70 mass % or more.
The lithium aluminate phase may further contain another element M, in addition to Li, Al, and O. The element M may be at least one selected from the group consisting of, for example, sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), zirconium (Zr), iron (Fe), boron (B), phosphorus (P), and lanthanum (La). When the aluminate phase contains the element M, the stability and the lithium ion conductivity of the aluminate phase are further improved. Moreover, the side reaction due to contact between the aluminate phase and the non-aqueous electrolyte is suppressed. In view of the chemical resistance to non-aqueous electrolyte and the structural stability of the aluminate phase, the element M preferably includes at least one selected from the group consisting of Zr, Fe, P, and B. La can further improve the initial charge-discharge efficiency.
The element M may be forming a compound. The compound may be, for example, an oxide of the element M, or an aluminate of the element M, depending on the kind of the element M. In the lithium aluminate phase, the content of the element M is, for example, 0.3 mol % or more and 3 mol % or less, relative to the total amount of the elements other than oxygen.
The lithium aluminate phase may further contain a very small amount of chromium (Cr), nickel (Ni), manganese (Mn), copper (Cu), molybdenum (Mo), or other elements.
The contents of Li, Al, and the element M in the lithium aluminate phase can be measured, for example, by analyzing a cross section of the negative electrode mixture layer.
First, the battery in a fully discharged state is disassembled, to take out the negative electrode, and the negative electrode is washed with anhydrous ethyl methyl carbonate or dimethyl carbonate, to remove the non-aqueous electrolyte component, and dried. This is followed by processing with a cross section polisher (CP) to obtain a cross section of the negative electrode mixture layer. Next, a scanning electron microscope (SEM) is used to observe the cross section of the negative electrode mixture layer.
The content of each element can be then determined by any of the following methods. From the content of each element, the composition of the lithium aluminate phase can be calculated.
<EDX>
From a cross-sectional backscattered electron image of the negative electrode mixture layer, 10 composite particles having a maximum diameter of 5 μm or more are randomly selected, to perform an elemental mapping analysis by energy dispersive X-ray (EDX) on each particle. The area occupied by the target element is calculated using an image analysis software. The observation magnification is desirably 2000 to 20,000 times. The measured values of the area occupied by the predetermined element contained in the 10 particles are averaged. From the obtained average value, the content of the target element can be calculated.
Desirable cross-sectional SEM-EDX analysis measurement conditions are shown below.
<SEM-EDX Measurement Conditions>
<AES>
From a cross-sectional backscattered electron image of the negative electrode mixture layer, 10 composite particles having a maximum diameter of 5 μm or more are randomly selected, to perform a qualitative/quantitative analysis on each particle using an Auger electron spectroscopy (AES) analyzer (e.g., JAMP-9510F, available from JEOL Corporation). The measurement conditions may be set, for example, the acceleration voltage to be 10 kV, the beam current to be 10 nA, and the analysis region to be 20 μmϕ. The contents of a predetermined element contained in the 10 particles are averaged, to determine its content.
The EDX and AES analyses are performed within 1 μm or more inward from the peripheral edge of the cross section of the composite particle.
<ICP>
A sample of the composite particles is completely dissolved in a heated acid solution (a mixed acid of hydrofluoric acid, nitric acid, and sulfuric acid), and the residue of dissolution, carbon, is removed by filtration. Then, the obtained filtrate is analyzed by inductively coupled plasma emission spectroscopy (ICP), to measure a spectral intensity of each element. Subsequently, using a commercially available standard solution of the element, a calibration curve is drawn, from which the content of each element in the composite particles is calculated.
Other techniques can be used for quantification of each element, such as electron microanalyzer (EPMA), laser ablation ICP mass analysis (LA-ICP-MS), and X-ray photoelectron spectroscopy (XPS).
The contents of B, Na, K, and Al in the composite particles can be quantitatively analyzed in accordance with JIS R3105 (1995) (method for chemical analysis of borosilicate glass).
The content of Ca in the composite particles can be quantitatively analyzed in accordance with JIS R3101 (1995) (methods for chemical analysis of soda-lime-magnesia-silica glass).
The carbon content in the composite particles may be measured using a carbon/sulfur analyzer (e.g., EMIA-520 available from HORIBA, Ltd.). A sample is weighed out on a magnetic board, to which an auxiliary agent is added. The sample is inserted into a combustion furnace (carrier gas: oxygen) heated to 1350° C. The amount of carbon dioxide gas generated during combustion is detected by infrared absorption spectroscopy. A calibration curve is obtained using carbon steel (carbon content: 0.49%) available from Bureau of Analysed Samples. Ltd., from which a carbon content in the sample is determined (a high-frequency induction heating furnace combustion and infrared absorption method).
The oxygen content in the composite particles may be measured using an oxygen/nitrogen/hydrogen analyzer (e.g., EGMA-830, available from HORIBA, Ltd.). A sample is placed in a Ni capsule, which is put together with Sn pellets and Ni pellets serving as a flux, into a carbon crucible heated at a power of 5.75 kW, to detect a released carbon monoxide gas. From a calibration curve obtained using a standard sample Y2O3, an oxygen content in the sample is determined (an inert gas melting and non-dispersive infrared absorption method).
The amount of Si constituting the silicon phase in the composite particles can be quantified using Si-NMR.
Desirable Si-NMR measurement conditions are shown below.
<Si-NMR Measurement Conditions>
<Silicon phase>
The silicon phase is a phase of elementary silicon (Si), and repeatedly absorbs and releases lithium ions thereinto and therefrom during charge and discharge of the battery. The capacity develops through the Faradaic reaction in which the silicon phase is involved. The silicon phase, due to its large capacity, undergoes a great degree of expansion and contraction during charge and discharge. However, since the silicon phase is dispersed in the lithium aluminate phase, the stress due to the expansion and contraction of the silicon phase is relaxed.
The silicon phase can be constituted of a plurality of crystallites. The crystallite size of the silicon phase is preferably 30 nm or less. When the crystallite size of the silicon phase is 30 nm or less, the changes in volume of the silicon phase associated with expansion and contraction during charge and discharge can be reduced, and the cycle characteristics can be further improved. For example, the isolation of a silicon phase caused by the formation of gaps around the silicon phase due to contraction of the silicon phase can be suppressed, and the reduction in the charge-discharge efficiency can be suppressed. The lower limit of the crystallite size of the silicon phase is not limited, but is, for example, 1 nm or more.
The crystallite size of the silicon phase is more preferably 10 nm or more and 30 nm or less, particularly preferably 15 nm or more and 25 nm less. When the crystallite size of the silicon phase is 10 nm or more, the surface area of the silicon phase can be kept small, and the deterioration of the silicon phase accompanied by the generation of irreversible capacity hardly occurs. When the crystallite size of the silicon phase is 30 nm or less, the expansion and contraction of the silicon phase can be easily made uniform, the stress generated in the composite particles can be easily relaxed, and the cycle characteristics can be improved. The crystallite size of the silicon phase is calculated from the Scherrer formula, using a half-width of a diffraction peak attributed to the (111) plane of the silicon phase (elementary Si) in an X-ray diffraction pattern.
The silicon phase in the composite particles contained in the battery before initial charge is, for example, particulate. The average particle diameter of the particulate silicon phases is preferably 500 nm or less, more preferably 200 nm or less, furthermore preferably 50 nm or less. After the initial charge, the average particle diameter of the silicon phases is preferably 400 nm or less, more preferably 100 nm or less. By using finer silicon phases, the changes in volume of the composite particles during charge and discharge are reduced, and the structural stability of the composite particles can be further improved. The average particle diameter of the silicon phases is measured by observing a cross-sectional SEM image of a composite particle. Specifically, the average particle diameter of the silicon phases is obtained by averaging the maximum diameter of 100 randomly-selected silicon phases.
In view of achieving a higher capacity, the content of the silicon phase in the composite particles is preferably 30 mass % or more, more preferably 35 mass % or more, further more preferably 55 mass % or more. In this case, the diffusibility of lithium ions is favorable, and excellent load characteristics can be obtained. On the other hand, in view of improving the cycle characteristics, the content of the silicon phase in the composite particles is preferably 95 mass % or less, more preferably 75 mass % or less, further more preferably 70 mass % or less. In this case, the exposed surface of the silicon phase without being covered with the silicate phase decreases, and the reaction between the non-aqueous electrolyte and the silicon phase tends to be suppressed.
(Conductive Layer)
A conductive layer containing a conductive material may be formed on at least part of the surface of the composite particles (secondary particles). This can improve the conductivity of the composite particles. The thickness of the conductive layer is preferably practically so small as not to influence the average particle diameter of the composite particles. In view of reliable conductivity and diffusibility of lithium ions, the thickness of the conductive layer is preferably 1 to 200 nm, more preferably 5 to 100 nm. The thickness of the conductive layer can be measured by cross-sectional observation of the composite particles using a SEM or TEM.
The conductive material is preferably a conductive carbon material. Examples of the conductive carbon material include an amorphous carbon, graphite, graphitizable carbon (soft carbon), and non-graphitizable carbon (hard carbon). In particular, an amorphous carbon is preferred in that a thin conductive layer covering the surface of the composite particles can be easily formed. Examples of the amorphous carbon includes carbon black, calcined pitch, coke, and activated carbon. Examples of the graphite includes natural graphite, artificial graphite, and graphitized mesophase carbon.
[Method for Producing Composite Particles]
The composite particles are produced by, for example, a production method including the following first to fourth steps.
(First Step)
The first step includes: for example, a step 1a of mixing an aluminum compound, a lithium compound, and, as needed, a compound containing an element M, to obtain a mixture; and a step 1b of baking the mixture, to obtain a raw material aluminate. The baking in the step 1b is performed, for example, in an oxidizing atmosphere. The baking temperature in the step 1b is preferably 400° C. or higher and 1200° C. or lower, more preferably 800° C. or higher and 1100° C. or lower.
As the aluminum compound, aluminum oxide (Al2O3), aluminum hydroxide, aluminum carbonate, and the like can be used. The aluminum compound may be used singly or in combination of two or more kinds.
As the lithium compound, lithium carbonate, lithium oxide, lithium hydroxide, lithium hydride, and the like can be used. The lithium compound may be used singly or in combination of two or more kinds.
As the compound containing an element M, an oxide, hydroxide, hydride, halide, carbonate, oxalate, nitrate, sulfate, and the like of the element M can be used. The compound containing an element M may be used singly or in combination of two or more kinds.
In the first step, the aluminum compound not having reacted with the lithium compound in the process of producing a raw material aluminate can remain in the raw material aluminate. When the aluminum compound is used in a larger amount than the lithium compound, the aluminum compound tends to remain. When the aluminum compound remaining in the raw material aluminate is Al2O3, an Al2O3 phase dispersed in a lithium aluminate phase can be formed in the finally obtained composite particles.
(Second Step)
The second step has, for example, a step of pulverizing a mixture of the lithium aluminate and a raw material silicon while applying a shearing force to the mixture, to obtain a fine-grained composite intermediate. Here, for example, the raw material aluminate and a raw material silicon are mixed in a predetermined mass ratio, and the mixture is pulverized into fine particles while being stirred, using a pulverizer like a ball mill.
As the raw material silicon, coarse-grained silicon particles of about several μm to several tens of μm in average particle diameter can be used. The finally obtained silicon particles are preferably controlled such that the crystallite size thereof calculated by using the Scherrer formula from the half width of a diffraction peak belonging to the Si (111) plane in an X-ray diffraction pattern is 10 nm or more.
The second step is not limited to the above. For example, without using a pulverizer, silicon nanoparticles and nanoparticles of raw material aluminate may be synthesized, and mixed together.
(Third Step)
The third step has, for example, a step of baking the fine-grained composite intermediate, while applying a pressure to the composite intermediate using a hot press or the like, to obtain a sintered body. The baking of the composite intermediate is performed, for example, in an inert atmosphere (e.g., an atmosphere of argon, nitrogen, etc.). The baking temperature is preferably 450° C. or higher and 1000° C. or lower. Within the above temperature range, fine silicon particles can be easily dispersed in the aluminate phase with low crystallinity. The raw material aluminate is stable in the above temperature range and hardly reacts with silicon. The baking temperature is preferably 550° C. or higher and 900° C. or lower, more preferably 650° C. or higher and 850° C. or lower. The baking time is, for example, 1 hour or more and 10 hours or less.
(Fourth Step)
The fourth step is a step of pulverizing the sintered body to have a desired particle size distribution, to obtain composite particles containing an aluminate phase and silicon phases dispersed in the aluminate phase. The composite particles are pulverized to have an average particle diameter of, for example, 1 to 25 μm.
(Fifth Step)
The method for producing composite particles may further include a fifth step of forming a conductive layer by covering at least part of the surface of the composite particles with a conductive material. The conductive material is preferably electrochemically stable, and is preferably a conductive carbon material. Examples of the method of covering the surface of the composite particles with a conductive carbon material include: a CVD method using a hydrocarbon gas, such as acetylene and methane, as a raw material; and a method in which coal pitch, petroleum pitch, phenolic resin, or the like is mixed with the composite particles and heated, to be carbonized. Alternatively, carbon black may be allowed to adhere to the surface of the composite particles. In the fifth step, for example, a mixture of the composite particles and a conductive carbon material may be heated at a temperature of 700° C. or higher and 950° C. or lower in an inert atmosphere (e.g., an atmosphere of argon, nitrogen, etc.), thereby to form a conductive layer on the surface of the composite particles.
Here,
A composite particle 20 includes a base particle 23 comprising a secondary particle formed of a plurality of primary particles 24 aggregated together. The base particle 23 (primary particle 24) includes a lithium aluminate phase 21, and silicon phases 22 dispersed in the lithium aluminate phase 21. The base particle 23 has a sea-island structure in which fine silicon phases are dispersed in a matrix of the lithium aluminate phase 21.
In addition, fine Al2O3 phases 28 can be dispersed in the lithium aluminate phase 21. At least part of the surface of the base particle 23 can be covered with a conductive layer 26. The lithium aluminate phase 21 may contain an element M. With repeated charge and discharge, the particulate silicon phases 22 adjacent to each other are connected with each other, to form a network of silicon phases.
[Non-Aqueous Electrolyte Secondary Battery]
A non-aqueous electrolyte secondary battery according to an embodiment of the present disclosure has a positive electrode, a negative electrode, and a non-aqueous electrolyte. The negative electrode includes the above-described negative electrode active material for a non-aqueous electrolyte secondary battery.
A detailed description of the non-aqueous electrolyte secondary battery will be given below.
[Negative Electrode]
The negative electrode may have a negative electrode current collector, and a negative electrode mixture layer supported on a surface of the negative electrode current collector. The negative electrode mixture layer can be formed by applying a negative electrode slurry of a negative electrode mixture dispersed in a dispersion medium, onto a surface of the negative electrode current collector, followed by drying. The dry applied film may be rolled as needed. The negative electrode mixture layer may be formed on a surface on one side or both sides of the negative electrode current collector.
The negative electrode mixture contains a negative electrode active material as an essential component, and can contain a binder, a conductive agent, a thickener, and the like as optional components. The negative electrode active material contains at least the above-described composite particles.
The negative electrode active material preferably further includes a carbon material that electrochemically absorbs and releases lithium ions. The composite particles expand and contract in volume associated with charge and discharge. Therefore, increasing the proportion thereof in the negative electrode active material can increase the risk of a contact failure to occur associated with charge and discharge, between the negative electrode active material and the negative electrode current collector. However, by using the composite particles in combination with a carbon material, it becomes possible to achieve excellent cycle characteristics while imparting a high capacity of the silicon particles to the negative electrode. In view of achieving a higher capacity and improved cycle characteristics, the proportion of the carbon material in the sum of the composite particles and the carbon material is preferably 98 mass % or less, more preferably 70 mass % or more and 98 mass % or less, further more preferably 75 mass % or more and 95 mass % or less.
Examples of the carbon material include graphite, graphitizable carbon (soft carbon), and non-graphitizable carbon (hard carbon). In particular, preferred is graphite, in terms of its excellent stability during charge and discharge and small irreversible capacity. The graphite means a material having a graphite-like crystal structure, examples of which include natural graphite, artificial graphite, and graphitized mesophase carbon particles. The carbon material may be used singly or in combination of two or more kinds.
Examples of the negative electrode current collector include a non-porous conductive substrate (e.g., metal foil) and a porous conductive substrate (e.g., mesh, net, punched sheet). The negative electrode current collector may be made of, for example, stainless steel, nickel, a nickel alloy, copper, or a copper alloy. The negative electrode current collector may have any thickness. In view of the balance between high strength and lightweight of the negative electrode, the thickness is preferably 1 to 50 μm, more preferably 5 to 20 μm.
The binder may be a resin material, examples of which include: fluorocarbon resin, such as polytetrafluoroethylene and polyvinylidene fluoride (PVDF); polyolefin resin, such as polyethylene and polypropylene; polyamide resin, such as aramid resin; polyimide resin, such as polyimide and polyamide-imide; acrylic resin, such as polyacrylic acid, methyl polyacrylate, and ethylene-acrylic acid copolymer; vinyl resin, such as polyacrylonitrile and polyvinyl acetate; polyvinyl pyrrolidone; polyether sulfone; and a rubbery material, such as styrene-butadiene copolymer rubber (SBR). The binder may be used singly or in combination of two or more kinds.
Examples of the conductive agent include: carbons, such as acetylene black; conductive fibers, such as carbon fibers and metal fibers; fluorinated carbon; metal powders, such as aluminum; conductive whiskers, such as zinc oxide and potassium titanate; conductive metal oxides, such as titanium oxide; and organic conductive materials, such as phenylene derivatives. The conductive agent may be used singly or in combination of two or more kinds.
Examples of the thickener include: cellulose derivatives (e.g., cellulose ethers), such as carboxymethyl cellulose (CMC) and modified products thereof (including salts such as Na salts), and methyl cellulose; saponificated products of polymers having vinyl acetate units, such as polyvinyl alcohol; and polyethers (e.g., polyalkylene oxide, such as polyethylene oxide). The thickener may be used singly or in combination of two or more kinds.
Examples of the dispersion medium include: water; alcohols, such as ethanol; ethers, such as tetrahydrofuran; amides, such as dimethylformamide; N-methyl-2-pyrrolidone (NMP); and a mixed solvent of these.
[Positive Electrode]
The positive electrode may include a positive electrode current collector, and a positive electrode mixture layer supported on a surface of the positive electrode current collector. The positive electrode mixture layer can be formed by applying a positive electrode slurry of a positive electrode mixture dispersed in a dispersion medium, onto a surface of the positive electrode current collector, followed by drying. The dry applied film may be rolled as needed. The positive electrode mixture layer may be formed on a surface on one side or both sides of the positive electrode current collector. The positive electrode mixture contains a positive electrode active material as an essential component, and can contain a binder, a conductive agent, and the like as optional components. The dispersion medium of the positive electrode slurry may be NMP or the like.
The positive electrode active material may be, for example, a lithium-containing composite oxide. Examples thereof include LiaCoO2, LiaNiO2, LiaMnO2, LiaCobNi1-bO2, LiaCobMe1-bOc, LiaNi1-bMebOc, LiaMn2O4, LiaMn2-bMebO4, LiMePO4, and Li2MePO4F, where Me is at least one selected from the group consisting of Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B. Here, a=0 to 1.2, b=0 to 0.9, and c=2.0 to 2.3. The value a representing the molar ratio of lithium is subjected to increase and decrease during charge and discharge.
In particular, preferred is a lithium-nickel composite oxide represented by LiaNibMe1-bO2, where Me is at least one selected from the group consisting of Mn, Co, and Al, 0<a≤1.2, and 0.3≤b≤1. In view of achieving a higher capacity, preferably, 0.85≤b<1. In view of the stability of the crystal structure, more preferred is LiaNibCocAldO2 containing Co and Al as elements represented by Me, where 0<a≤1.2, 0.85≤b<1, 0<c<0.15, 0<d≤0.1, and b+c+d=1.
The binder and the conductive agent may be like those exemplified for the negative electrode. The conductive agent may be graphite, such as natural graphite and artificial graphite.
The form and the thickness of the positive electrode current collector may be respectively selected from the forms and the ranges corresponding to those of the negative electrode current collector. The positive electrode current collector may be made of, for example, stainless steel, aluminum, an aluminum alloy, or titanium.
[Non-Aqueous Electrolyte]
The non-aqueous electrolyte contains a non-aqueous solvent, and a lithium salt dissolved in the non-aqueous solvent. The concentration of the lithium salt in the non-aqueous electrolyte is preferably, for example, 0.5 mol/L or more and 2 mol/L or less. By controlling the lithium salt concentration within the range as above, a non-aqueous electrolyte having excellent ion conductivity and moderate viscosity can be obtained. The lithium salt concentration, however, is not limited to the above.
Examples of the non-aqueous solvent include cyclic carbonic acid esters, chain carbonic acid esters, cyclic carboxylic acid esters, and chain carboxylic acid esters. The cyclic carbonic acid esters are exemplified by propylene carbonate (PC) and ethylene carbonate (EC). The chain carbonic acid esters are exemplified by diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC). The cyclic carboxylic acid esters are exemplified by γ-butyrolactone (GBL) and γ-valerolactone (GVL). The chain carboxylic acid esters are exemplified by methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and propyl propionate. The non-aqueous solvent may be used singly or in combination of two or more kinds.
Examples of the lithium salt include: LiClO4, LiBF4, LiPF6, LiAlCl4, LiSbF6, LiSCN, LiCF3SO3, LiCF3CO2, LiAsF6, LiB10Cl10, lithium lower aliphatic carboxylate, LiCl, LiBr, LiI, borates, and imides. Examples of the borates include lithium bis(1,2-benzenediolate(2-)-O,O′) borate, lithium bis(2,3-naphthalenediolate(2-)-O,O′) borate, lithium bis(2,2′-biphenyldiolate(2-)-O,O′) borate, and lithium bis(5-fluoro-2-olate-1-benzenesulfonate-0,0′) borate. Examples of the imides include lithium bisfluorosulfonyl imide (LiN(FSO2)2), lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)2), lithium trifluoromethanesulfonyl nonafluorobutanesulfonyl imide (LiN(CF3SO2)(C4F9SO2)), and lithium bis(pentafluoroethanesulfonyl)imide (LiN(C2F5SO2)2). Preferred among them is LiPF6. The lithium salt may be used singly or in combination of two or more kinds.
[Separator]
Usually, it is desirable to interpose a separator between the positive electrode and the negative electrode. The separator is excellent in ion permeability and has moderate mechanical strength and electrically insulating properties. The separator may be, for example, a microporous thin film, a woven fabric, or a nonwoven fabric. The separator is preferably made of, for example, polyolefin, such as polypropylene or polyethylene.
In an exemplary structure of the non-aqueous electrolyte secondary battery, an electrode group formed by winding the positive electrode and the negative electrode with the separator interposed therebetween is housed together with the non-aqueous electrolyte in an outer body. The structure is not limited thereto, and a different form of electrode group may be adopted. For example, a stacked-type electrode group formed by stacking the positive electrode and the negative electrode with the separator interposed therebetween may be adopted. The non-aqueous electrolyte secondary battery may be in any form, such as cylindrical type, prismatic type, coin type, button type, or laminate type.
In the following, a structure of a prismatic non-aqueous electrolyte secondary battery which is an example of a non-aqueous electrolyte secondary battery according to the present disclosure will be described with reference to
The battery includes a bottomed prismatic battery case 4, and an electrode group 1 and a non-aqueous electrolyte housed in the battery case 4. The electrode group 1 has a long negative electrode, a long positive electrode, and a separator interposed therebetween and preventing them from directly contacting with each other. The negative electrode current collector of the negative electrode is electrically connected, via a negative electrode lead 3, to a negative electrode terminal 6 provided at a sealing plate 5. The negative electrode terminal 6 is electrically insulated from the sealing plate 5 by a resin gasket 7. The positive electrode current collector of the positive electrode is electrically connected, via a positive electrode lead 2, to the back side of the sealing plate 5. In other words, the positive electrode is electrically connected to the battery case 4 serving as a positive electrode terminal. The sealing plate 5 is fitted at its periphery to the opening end of the battery case 4, and the fitted portion is laser-welded. The injection port for non-aqueous electrolyte is provided in the sealing plate 5 and is closed with a sealing plug 8 after injection.
The present disclosure will be specifically described below with reference to Examples and Comparative Examples. It is to be noted, however, the present invention is not limited to the following Examples.
[Preparation of Composite Particles (LAX Particles)]
(First Step)
A raw material aluminate was prepared by mixing Al2O3 and Li2CO3, and baking the mixture in air at 950° C. for 10 hours. In the mixture, the molar ratio of Al2O3 to Li2CO3 was set as shown in Table 1. The raw material aluminate was pulverized to have an average particle diameter of 10 μm.
(Second Step)
Next, the raw material aluminate (average particle diameter: 10 μm) and a raw material silicon (3N, average particle diameter: 10 μm) were mixed. In the mixture, the mass ratio of the raw material aluminate to the raw material silicon was set as shown in Table 1.
The mixture was placed in a pot (made of SUS, volume: 500 mL) of a planetary ball mill (P-5, available from Fritsch Co., Ltd.), together with 24 SUS balls (diameter: 20 mm). In the pot with the lid closed, the mixture was pulverized at 200 rpm for 50 hours in an inert atmosphere.
(Third Step)
Next, the powdered mixture was taken out in an inert atmosphere, which was then baked at 800° C. for 4 hours, in an inert atmosphere, with a pressure applied by a hot press, to give a sintered body of the mixture.
(Fourth Step)
The obtained sintered body was crushed, and passed through a 40-μm mesh, to give composite particles.
(Fifth Step)
The composite particles were mixed with coal pitch (MCP250, available from JFE Chemical Corporation). The mixture was baked at 800° C. for 5 hours in an inert atmosphere, to form a conductive layer containing a conductive carbon material on the surface of the composite particles. The covering amount of the conductive layer was set to 5 mass %, relative to the total mass of the composite particles and the conductive layer. Then, using a sieve, composite particles (LAX particles in which silicon phases are dispersed in a lithium aluminate phase) with an average particle diameter of 5 μm having a conductive layer were obtained.
In an XRD pattern of the LAX particles obtained by XRD measurement, peaks belonging to a silicon phase and a lithium aluminate phase were confirmed. With respect to the particles of LAX1 to LAX3 and LAX6 to LAX8, a peak attributed to Al2O3 phase was observed. The crystallite size of the silicon phase in the LAX particles determined by the already-described method was 15 nm.
Based on the composition of the lithium aluminate phase determined by the already-described method and the amount of Si constituting the silicon phase in the LAX particles, the Li content proportion MLi, the Si content proportion MSi and the Al content proportion MAl in the LAX particles were determined. The values of respective content proportions are shown in Table 1.
[Production of Negative Electrode]
The composite particles having a conductive layer and graphite were mixed in a mass ratio of 5:95, and used as a negative electrode active material. To a negative electrode mixture containing the negative electrode active material, a Na salt of CMC, and SBR in a mass ratio of 97.5:1:1.5, water was added, and stirred, to prepare a negative electrode slurry. Next, the negative electrode slurry was applied onto a surface of a copper foil, and the applied film was dried, and then rolled, to produce a negative electrode with a negative electrode mixture layer having a density of 1.5 g/cm 3 formed on both sides of the copper foil.
[Production of Positive Electrode]
To a positive electrode mixture containing lithium cobaltate, acetylene black, and PVDF in a mass ratio of 95:2.5:2.5, NMP was added, and stirred, to prepare a positive electrode slurry. Next, the positive electrode slurry was applied onto a surface of an aluminum foil, and the applied film was dried, and then rolled, to produce a positive electrode with a positive electrode mixture layer having a density of 3.6 g/cm 3 formed on both sides of the aluminum foil.
[Preparation of Non-Aqueous Electrolyte]
To a mixed solvent containing EC and DEC in a volume ratio of 3:7, LiPF6 was dissolved at a concentration of 1.0 mol/L, to prepare a non-aqueous electrolyte.
[Fabrication of Non-Aqueous Electrolyte Secondary Battery]
The positive and negative electrodes, each with a tab attached, were wound with a separator interposed therebetween, thereby to form an electrode group with the tab positioned at the outermost layer. The electrode group was inserted into an outer body made of aluminum laminated film and dried under vacuum at 105° C. for 2 hours. Then, the non-aqueous electrolyte was injected, and the opening of the outer body was sealed, to complete a non-aqueous electrolyte secondary battery. LAX1 to 10 and A1 to A10 in Table 1 correspond to the composite particles and batteries of Examples 1 to 10.
In the second step, a raw material silicate was used in place of the raw material aluminate, and the raw material silicate (average particle diameter: 10 μm) and a raw material silicon (3N, average particle diameter: 10 μm) were mixed in a mass ratio of 25:75. The raw material silicate was prepared by mixing SiO2 and Li2CO3 in a molar ratio of SiO2:Li2CO3=70:30, and baking the mixture in air at 950° C. for 10 hours. The raw material silicate was pulverized to have an average particle diameter of 10 μm.
Except for the above, in the same manner as in Example 1, composite particles having a conductive layer (LSX particles in which a silicon phase is dispersed in a lithium silicate phase) were prepared.
In an XRD pattern of the LSX particles obtained by XRD measurement, peaks belonging to a lithium silicate phase (Li2Si2O5 and Li2SiO3) and a silicon phase were confirmed. The crystallite size of the silicon phase in the LSX particles was 15 nm.
A battery B1 was fabricated in the same manner as in Example 1, except that the LSX particles having a conductive layer were used in place of the LAX1 particles having a conductive layer.
With respect to the batteries obtained above, the initial charge-discharge efficiency was determined by the following method.
[Initial Charge-Discharge Efficiency]
<Charge>
At 25° C., a constant-current charge was performed at a current of 1 It (800 mA) until the voltage reached 4.2 V, and then a constant-voltage charge was performed at a voltage of 4.2 V until the current reached 1/20 It (40 mA).
<Discharge>
After the rest for 10 minutes, at 25° C., a constant-current discharge was performed at 1 It (800 mA) until the voltage reached 2.75 V.
For each battery, the charge capacity and the discharge capacity were determined from the above charge and discharge, and the ratio of the discharge capacity to the charge capacity was determined as an initial charge-discharge efficiency. In Table 1, the value of the initial charge-discharge efficiency of each battery is shown as a relative value, with the value of the initial charge-discharge efficiency in the battery B1 of Comparative Example 1 taken as 100.
In the batteries A1 to A10 including LAX particles, a higher initial charge-discharge efficiency was achieved than that in the battery B1 including LSX particles. Especially in the batteries A2 to A4 and A7 to A9, a further higher initial charge-discharge efficiency was achieved.
The non-aqueous electrolyte secondary battery of the present disclosure is useful as a main power source for mobile communication devices, portable electronic devices, and other similar devices.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-199066 | Nov 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/034842 | 9/22/2021 | WO |
