Patent Application
20200287204
This application claims priority to Japanese Patent Application No. 2019-039928 filed on Mar. 5, 2019, incorporated herein by reference in its entirety.
The present disclosure relates to a negative electrode active substance material and an electricity storage device.
In related art, it is known that a Si negative electrode for a lithium ion secondary battery has a theoretical capacity of about 4,199 mAh/g, which is about 10 times higher than a theoretical capacity of a general graphite negative electrode of 372 mAh/g, and further increase in capacity and energy density is possible. On the other hand, the volume of silicon (Li4.4Si) that has stored lithium ions expands to about four times the volume of the silicon before storing lithium ions. In such a silicon negative electrode, a Li storage place which is a place where the silicon reacts with Li due to the restraint pressure is partially formed, and increase in the restraint pressure or deterioration of the charge and discharge cycle may be caused to occur due to the fact that the Li reaction place grows abnormally in the direction of the restraint pressure or the like. With respect to such a problem, for example, an all-solid state lithium ion battery which includes a negative electrode using free Si particles having a specific particle diameter as a negative electrode active substance, a solid electrolyte, a positive electrode, and a restraint member for restraining the solid electrolyte and the negative electrode, and in which the restraint pressure of the restraint member is in a range of 0.1 MPa or more and 45 MPa or less has been proposed (See, for example, Japanese Unexamined Patent Application Publication No. 2018-106984 (JP 2018-106984 A)). In this all-solid state lithium ion battery, it is possible to achieve both a reduction in restraint pressure and a capacity retention rate by adjusting the particle diameter of the Si particles. In addition, a silicon material which includes a crystalline silicon phase and a crystalline silicide phase containing one or more of Fe, Co, and Ni as an active substance has been proposed (See, for example, Japanese Unexamined Patent Application Publication No. 2013-253012 (JP 2013-253012 A), Japanese Unexamined Patent Application Publication No. 2012-82125 (JP 2012-82125 A), Japanese Unexamined Patent Application Publication No. 2015-95301 (JP 2015-95301 A)). This silicon material is said to have high capacity and effective cycle characteristics.
However, in the lithium ion battery of above-described JP 2018-106984 A, although the restraint pressure can be further reduced by controlling the particle diameter of the Si powder that is the negative electrode active substance, the reduction is not yet sufficient, and it has been needed to suppress the volume change. In particular, it has been difficult to suppress the local Li reaction place, reduce the restraint pressure, improve the capacity retention rate, or the like even by controlling the particle diameter of the Si powder that is the negative electrode active substance. In addition, in the silicon materials of above-described JP 2013-253012 A, JP 2012-82125 A, and JP 2015-95301 A, it is described that the silicide phase is complexed to further suppress the expansion of the silicon phase, but the effect is not yet sufficient, and it has been needed to further suppress the volume change. For example, in an all-solid state lithium ion battery, by applying the restraint pressure to a laminate of a positive electrode, a negative electrode, and a solid electrolyte layer, contact between active substance particles and a solid electrolyte is maintained, and battery performance may be improved. In a case when the restraint pressure is increased, the restraint member becomes large and the energy density of the entire battery decreases, and thus it is desired that the restraint pressure is decreased and the size of the restraint member is reduced. However, when the restraint pressure is decreased, the battery capacity retention rate of the battery performance decreases. Therefore, it has been an issue to achieve both a decrease in the restraint pressure and an improvement in the battery capacity.
The present disclosure has been made in consideration of such a problem, and a main object of the present disclosure is to provide a novel negative electrode active substance material and an electricity storage device that can further decrease the restraint pressure and increase the capacity.
After diligent studies to solve the above-mentioned problems, the present inventors have found that a powder obtained by melting and pulverizing a mixture in which a specific element is added to Si in a eutectic or a hypoeutectic composition is able to further suppress the volume change and further increase the capacity, and the present disclosure has been completed.
A first aspect of the present disclosure relates to a negative electrode active substance material used for an electricity storage device. The negative electrode active substance material used for an electricity storage device includes a silicon phase and a silicide phase represented by a basic composition formula MSi2, where M is one or more of Cr, Ti, Zr, Nb, Mo, and Hf. The negative electrode active substance material has a structure in which the silicide phase is dispersed in the silicon phase.
A second aspect of the present disclosure relates to an electricity storage device including a positive electrode, a negative electrode including the negative electrode active substance material described above, and an ion conduction medium interposed between the positive electrode and the negative electrode for conducting ions.
According to the present disclosure, it is possible to provide a novel negative electrode active substance material and an electricity storage device that further reduces the restraint pressure and increases the capacity. The reason why such effects are obtained is presumed as follows. For example, by dispersing a silicide phase in a silicon phase to have a framework structure, the Li storage place in the silicon negative electrode can be made uniform, and the volume change can be further suppressed. In particular, this effect is limited in a silicide phase that contains Fe or the like, but it is presumed that the effect is higher in a silicide phase that is represented by a basic composition formula MSi2 and that contains Cr, Ti, Zr, Nb, Mo, and Hf. It is also presumed that the capacity is further improved by having such a two-phase structure. With such a structure, it is possible to provide a novel negative electrode active substance material capable of reducing the restraint pressure, improving the capacity retention rate in a charge and discharge cycle, and improving the charge and discharge capacity or the like.
Features, advantages, and technical and industrial significance of exemplary embodiments of the disclosure will be described below with reference to the accompanying drawings, in which like signs denote like elements, and wherein:
Negative Electrode Active Substance Material
A negative electrode active substance material of the present disclosure is used for an electricity storage device. The negative electrode active substance material used for an electricity storage device includes a silicon phase and a silicide phase represented by a basic composition formula MSi2, where M is one or more of Cr, Ti, Zr, Nb, Mo, and Hf. The negative electrode active substance material may have a structure in which the silicide phase is dispersed in the silicon phase. In the negative electrode active substance material, the element M may be a eutectic composition or a hypoeutectic composition of the silicon phase and the silicide phase. Such a composition is preferable since a structure in which a silicon phase and a silicide phase are dispersed can be easily obtained. The element M is preferably included in a range of 2 mol % or more and 25 mol % or less with respect to an entirety of the silicon phase and the silicide phase. The content of the element M is preferably in this range since the restraint pressure can be further reduced and the capacity can be increased. The content of the element M is more preferably 5 mol % or more and may be 7 mol % or more. In addition, the content of the element M is preferably 15 mol % or less and may be 12 mol % or less.
In the negative electrode active substance material of the present disclosure, the silicide phase preferably contains two or more elements M. It is preferable to include two or more silicide phases since the restraint pressure can be further reduced and the capacity can be increased. In particular, the silicide phase preferably contains at least Zr as the element M and further contains one or more of Cr and Hf. This combination can further reduce the restraint pressure and increase the capacity. In this case, Zr is preferably included in a range of 5 mol % or more and 10 mol % or less with respect to the entirety of the silicon phase and the silicide phase and that one or more of Cr and Hf is preferably included in a range of 5 mol % or more and 15 mol % or less with respect to the entirety of the silicon phase and the silicide phase.
In the negative electrode active substance material of the present disclosure, the volume proportion of the silicide phase is preferably in a range of 5% by volume to 90% by volume and more preferably in a range of 10% by volume to 50% by volume with respect to the entirety of the silicon phase and the silicide phase. The volume proportion can be determined by performing elemental analysis of the material and using the principle of leverage in a state graph from the obtained ratio of the elements.
Method for Producing Negative Electrode Active Substance Material
Next, a method for producing a negative electrode active substance material will be described. In this producing method, predetermined amounts of a lumpy Si raw material and a lumpy element M raw material (metal lump) forming a silicide phase are weighed, an ingot is prepared by argon arc melting (about 1,500° C.), the prepared ingot is crushed, and then a silicon alloy powder can be obtained. The element M can be, for example, one or more of Cr, Ti, Zr, Nb, Mo, and Hf. The blending ratio of the raw material is preferably, for example, in a range in which the element M is a eutectic composition or a hypoeutectic composition of the silicon phase and the silicide phase. In addition, the blending ratio of the raw materials is preferably in a range in which the element M is 2 mol % or more and 25 mol % or less with respect to the entirety of the silicon phase and the silicide phase. The ingot can be pulverized with, for example, a ball mill. The particle size of the silicon alloy may be, for example, in a range in which an average particle diameter is 20 μm or more and 50 μm or less. The powdery silicon alloy obtained in this manner can be used as a negative electrode active substance material.
Electricity Storage Device
The electricity storage device of the present disclosure includes a positive electrode, a negative electrode including the negative electrode active substance material described above, and an ion conduction medium interposed between the positive electrode and the negative electrode for conducting ions. The electricity storage device may be a secondary battery using alkali metal ions as a carrier. Examples of the alkali metals include lithium, sodium, and potassium, and among these, lithium is preferable. In addition, examples of the electricity storage devices include an alkali metal ion secondary battery, a hybrid capacitor, and an air battery. Here, a lithium ion secondary battery will be mainly described. Since the lithium ion secondary battery further suppresses the volume change in the negative electrode active substance material, it is more preferable that the lithium ion secondary battery is an all-solid state lithium ion secondary battery in which an ion conduction medium is a solid electrolyte. In the all-solid state lithium secondary battery, it is known that the contactability between the positive electrode and the solid electrolyte interface, and the contactability between the negative electrode and the solid electrolyte interface greatly affect the battery performance, and thus it is highly significant to use the negative electrode active substance material of the present disclosure that has a small restraint pressure variation for the all-solid state battery.
The positive electrode may be formed by, for example, mixing a positive electrode active substance and as necessary, a conductive material, a binder, a solid electrolyte, and the like, adding a suitable solvent to form a paste-like positive electrode mixture, coating the positive electrode mixture on the surface of a current collector, drying the coated surface, and as necessary, compressing to increase the electrode density. As the positive electrode active substance, a sulfide containing a transition metal element, an oxide containing lithium and a transition metal element, or the like can be used. Specifically, transition metal sulfides such as TiS2, TiS3, MoS3, and FeS2, a lithium-manganese complex oxide having a basic composition formula of Li(1-x)MnO2 (0<x<1, the same applies hereinafter), Li(1-x)Mn2O4, or the like, a lithium-cobalt complex oxide having a basic composition formula of Li(1-x)CoO2 or the like, a lithium-nickel complex oxide having a basic composition formula of Li(1-x)NiO2 or the like, a lithium-nickel-cobalt-manganese complex oxide having a basic composition formula of Li(1-x)NiaCobMncO2 (a+b+c=1), Li(1-x)NiaCobMncO4 (a+b+c=2), or the like, or the like can be used. Among these, a transition metal complex oxide of lithium, for example, LiNi1/3Co1/3Mn1/3O2 is preferable. The “basic composition formula” is intended to include other elements.
The conductive material is not particularly limited as long as it is an electron conductive material that does not adversely affect the battery performance of the positive electrode. For example, graphite such as a natural graphite (a scaly graphite, a scaly flaky graphite) and an artificial graphite, acetylene black, carbon black, Ketjen black, carbon whisker, needle coke, carbon fiber, a metal (copper, nickel, aluminum, silver, gold, or the like), and the like can be used alone or a mixture of two or more thereof can be used. Among these, carbon black and acetylene black are preferable as the conductive material from the viewpoints of electron conductivity and coatability. The binder plays a role in binding the active substance particles and the conductive material particles. For example, fluorine-containing resins such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and fluororubber, or thermoplastic resins such as polypropylene and polyethylene, an ethylene propylene diene rubber (EPDM), a sulfonated EPDM rubber, a natural butyl rubber (NBR), and the like can be used alone or as a mixture of two or more thereof. In addition, an aqueous dispersion of a cellulose-based binder which is an aqueous binder or a styrene butadiene rubber (SBR) can also be used. As the solvents in which the positive electrode active substance, the conductive material, and the binder are dispersed, organic solvents such as include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methylethylketone, cyclohexanone, methyl acetate, methyl acrylate, diethylenetriamine, N,N-dimethylaminopropylamine, ethylene oxide, and tetrahydrofuran can be used. In addition, a dispersant, a thickener, or the like may be added to water, and the active substance may be slurried with a latex such as SBR. As the thickener, for example, polysaccharides such as carboxymethyl cellulose and methylcellulose can be used alone or as a mixture of two or more thereof. Examples of the coating method include roller coating such as an applicator roll, screen coating, a doctor blade method, spin coating, and a bar coater. Any of these can be used to obtain a suitable thickness and shape. Examples of the current collector include stainless steel, Ni, Cr, Au, Pt, Al, Fe, Ti, and Zn. The current collector may be a current collector obtained by plating and depositing Ni, Cr, C, or the like on a metal foil. Examples of the shape of the current collector include a foil shape, a film shape, a sheet shape, a net shape, a punched or expanded shape, a lathed shape, a porous shape, a foamed shape, and a formed body of fibers. The thickness of the current collector is, for example, 1 μm to 500 μm.
The negative electrode may include the current collector and a negative electrode active substance layer provided adjacent to the current collector. The negative electrode active substance layer may include the conductive material, the binder, the solid electrolyte, and the like in addition to the negative electrode active substance material described above. The active substance layer of the negative electrode is similar to the positive electrode, and preferably contains more active substance particles, and may contain the active substance particles in a range of 60% by volume or more and 98% by volume or less. The negative electrode may be formed by bringing the negative electrode active substance and the current collector into close contact with each other. For example, the negative electrode may be formed by mixing a negative electrode active substance, a conductive material, and a binder, adding a suitable solvent to form a paste-like negative electrode mixture, coating the negative electrode mixture on the surface of a current collector, drying the coated surface, and as necessary, compressing to increase the electrode density. In addition, as the conductive material, the binder, the solvent, and the like used for the negative electrode, those exemplified for the positive electrode can be used. Examples of the current collector of the negative electrode include Cu, stainless steel, Ni, Cr, Au, Pt, Al, Fe, Ti, Zn, calcinated carbon, a conductive polymer, and a conductive glass. The shape of the current collector may be the same as that of the positive electrode.
In the electricity storage device, examples of the solid electrolytes include an inorganic solid electrolyte and a polymer solid electrolyte. The solid electrolyte is not limited to the following composition and structure, and any solid electrolyte may be used as long as Li ions can migrate. A solid electrolyte partially substituted or having a different compositional ratio can be used as long as the solid electrolyte is a compound having a basic skeleton exemplified below. Examples of the inorganic solid electrolytes include Li3N, Li14Zn(GeO4)4 called LISICON, a sulfide Li3.25Ge0.25P0.75S4, a perovskite type La0.5Li0.5TiO3, (La2/3Li3xA1/3-2x)TiO3 (A: atomic vacancy), a garnet type Li7La3Zr2O12, LiTi2(PO4)3 and Li1.3M0.3Ti1.7(PO3)4 (M=Sc, Al) that are called a NASICON type, Li7P3S11 obtained from glass having a composition of a glass ceramic 80Li2S.20P2S5 (mol %), Li10Ge2PS2 that is a sulfide-based material having a high conductivity, a glass-based inorganic solid electrolyte such as Li2S—SiS2, Li2S—SiS2—LiI, Li2S—SiS2—Li3PO4, Li2S—SiS2—Li4SiO4, Li2S—P2S5, Li3PO4—Li4SiO4, and Li3BO4—Li4SiO4, and an electrolyte including SiO2, GeO2, B2O3, or P2O5 as a glass-based material and Li2O as a network modifying material. Examples of thio-LISICON solid electrolytes include a Li2S—GeS2-based electrolyte, a Li2S—GeS2—ZnS-based electrolyte, a Li2S—Ga2S2-based electrolyte, a Li2S—GeS2—Ga2S3-based electrolyte, a Li2S—GeS2—P2S5-based electrolyte, a Li2S—GeS2—SbS5-based electrolyte, a Li2S—GeS2—Al2S3-based electrolyte, a Li2S—SiS2-based electrolyte, a Li2S—P2S5-based electrolyte, a Li2S—Al2S3-based electrolyte, a LiS—SiS2—Al2S3-based electrolyte, and a Li2S—SiS2—P2S5-based electrolyte.
Examples of the polymer solid electrolytes include a complex of polyethylene oxide (PEO) and an alkali metal, in which the polymer is not limited to PEO as long as it is a polymer. Examples of unit structures of polymer materials that dissolve a lithium salt include polyether-based structures such as PPO and poly(propylene oxide) (PEO), a polyamine-based structure such as poly(ethylene imine) (PEI), PAN: poly (acrylonitrile), and a polysulfide-based structure such as poly(alkylene sulfide) (PAS). Examples of lithium salts include LiTFSI:(LiN(SO2CF3)2), LiPEI:(COCF2SO2NLi)n, and LiPPI:(COCF(CF3OCF2CF2SO2NLi))n. In addition, a gel polymer electrolyte using polyvinylidene difluoride (PVdF), PAN, hexafluoropropylene (HFP), or the like may be mentioned. Further, as an organic ionic plastic electrolyte, an electrolyte having a plastic crystal phase may be mentioned. Examples of representative molecules of the plastic crystal phases include tetrachloromethane, cyclohexane, and succinonitrile. Trifluoromethylsulfonylamide (Tf2N) and LiBF4 may be added to these plastic crystal phases, or a combination of salts having a plastic crystal phase formed of an aliphatic quaternary ammonium and a perfluoroanion may be used. An organic and inorganic hybrid ion gel in which an ionic liquid and a glass component are mixed at the molecular level, that is, an organic boron-based ion gel electrolyte using cellulose, an organic boron-based ion gel electrolyte using amylose, and a multiple borons-substituted macrocycle derived from cyclodextrin, and the like may be mentioned.
The ion conduction medium may be a general non-aqueous electrolyte containing a supporting salt, a non-aqueous gel electrolyte, or the like. As the solvent for the non-aqueous electrolyte, a carbonate an ester, an ether, a nitrile, a furan, a sulfolane, a dioxolane, and the like are mentioned, and these can be used alone or as a mixture. Examples of the supporting salts include LiPF6, LiBF4, LiAsF6, LiCF3SO3, LiN(CF3SO2)2, LiC(CF3SO2)3, LiSbF6, LiSiF6, LiAlF4, LiSCN, LiClO4, LiCl, LiF, LiBr, LiI, and LiAlCl4. Among these, one or more of salts selected from the group consisting of inorganic salts such as LiPF6, LiBF4, LiAsF6, and LiClO4, and organic salts such as LiCF3SO3, LiN(CF3SO2)2, and LiC(CF3SO2)3 are preferably combined to be used from the viewpoint of electrical characteristics. The concentration of the supporting salt in the non-aqueous electrolyte is preferably 0.1 mol/L or more and 5 mol/L or less, and more preferably 0.5 mol/L or more and 2 mol/L or less. In a case where the concentration for dissolving the supporting salt is 0.1 mol/L or more, a sufficient current density can be obtained, and in a case where the concentration is 5 mol/L or less, the electrolyte can be further stabilized. In addition, a flame retardant such as a phosphorus-based retardant or a halogen-based retardant may be added to the non-aqueous electrolyte.
The shape of the electricity storage device is not particularly limited, and examples thereof include a coin type, a button type, a sheet type, a laminated type, a cylindrical type, a flat type, and a square type. In addition, a plurality of such batteries may be connected in series and applied to a large battery used for an electric vehicle or the like. The structure of the electricity storage device is not particularly limited, but, for example, the structure shown in
As described above in detail, according to the present disclosure, it is possible to provide a novel negative electrode active substance material and an electricity storage device that further reduces the restraint pressure and increases the capacity. The reason why such effects are obtained is presumed as follows. For example, by dispersing a silicide phase in a silicon phase to have a framework structure, the Li storage place in the silicon negative electrode can be made uniform, and the volume change can be further suppressed. In particular, this effect is limited in a silicide phase that contains Fe or the like, but it is presumed that the effect is higher in a silicide phase that is represented by a basic composition formula MSi2 and that contains Cr, Ti, Zr, Nb, Mo, and Hf. It is also presumed that the capacity is further improved by having such a two-phase structure. With such a structure, it is possible to provide a novel negative electrode active substance material capable of reducing the restraint pressure, improving the capacity retention rate in a charge and discharge cycle, and improving the charge and discharge capacity or the like.
The present disclosure is not limited to the above-described embodiments at all, and the present disclosure can be implemented in various aspects as long as the aspect belongs to the technical scope of the present disclosure.
Hereinafter, examples in which the negative electrode active substance materials of the present disclosure are specifically produced will be described as Experimental Examples. Experimental Examples 1 to 13 correspond to Example of the present disclosure, and Experimental Examples 14 and 15 correspond to Comparative Example.
Preparation of Positive Electrode
Butyl butyrate, a butyl butyrate solution containing 5% by mass of a PVdF-based binder, LiNi1/3Co1/3Mn1/3O2 particles having a particle diameter of 6 μm as a positive electrode active substance, a glass ceramic including Li2S—P2S5 as a solid electrolyte, and a vapor-grown carbon fiber (VGCF) as a conductive auxiliary agent were added in a polypropylene container, and then the mixture was stirred for 30 seconds with an ultrasonic dispersion apparatus (UH-50 manufactured by SMT CO., LTD.). Next, the container was shaken with a shaker (TTM-1 manufactured by SHIBATA SCIENTIFIC TECHNOLOGY LTD.) for 3 minutes and further stirred with an ultrasonic dispersion apparatus for 30 seconds. Thereafter, the container was further shaken for 3 minutes with the shaker to obtain a slurry. The slurry was applied on an aluminum foil (manufactured by Showa Denko K.K.) by a blade method using an applicator. Thereafter, a positive electrode having a positive electrode mixture layer (thickness of about 50 μm) on the aluminum foil was obtained by drying on a hot plate at 100° C. for 30 minutes.
Preparation of Negative Electrode
For a negative electrode active substance Si alloy, a silicon alloy ingot was prepared by blending a predetermined amount of silicon manufactured by Kojundo Chemical Lab. Co., Ltd. and an element M, and performing argon arc melting. The ingot was crushed with a tungsten mortar, and a silicon alloy powder was prepared by a ball mill. The particle size was adjusted from the obtained Si alloy powder and was measured using a particle size distribution measuring apparatus (Scirocco 2,000 manufactured by Malvern Panalytical Ltd.) based on a laser diffraction and light scattering method, and the resultant was used as a negative electrode active substance. The average particle diameter (D50) of the Si alloy particles contained in the negative electrode is 5 μm to 15 μm, D10 is 1 μm to 2 μm, and D90 is 10 μm to 20 μm. In the measured volume-based particle size distribution, the particle diameter corresponding to a cumulative 10% by volume from the fine particle side was set as D10, the particle diameter corresponding to a cumulative 50% by volume was set as D50, and the particle diameter corresponding to 90% by volume cumulative was set as D90. Butyl butyrate, a butyl butyrate solution containing 5% by mass of a PVdF-based binder, free Si particles having a different average particle diameter or a Si alloy powder as a negative electrode active substance, and a glass ceramic including Li2S—P2S5 as a solid electrolyte were added in a polypropylene container, and then the mixture was stirred for 30 seconds with an ultrasonic dispersion apparatus (UH-50 manufactured by SMT CO., LTD.). Next, the container was shaken with a shaker (TTM-1 manufactured by SHIBATA SCIENTIFIC TECHNOLOGY LTD.) for 30 seconds to obtain a slurry. The slurry was applied on a copper foil by a blade method using an applicator. Thereafter, a negative electrode having a negative electrode mixture layer (thickness of about 30 μm) on the copper foil was obtained by drying on a hot plate at 100° C. for 30 minutes.
Preparation of Solid Electrolyte Layer
Li2S (manufactured by Nippon Chemical Industry CO., LTD.) and P2S5 (manufactured by Sigma-Aldrich Co. LLC) were used as starting materials, weighed so that the molar ratio was Li2S:P2S5=3:1, and mixed using an agate mortar. Thereafter, the mixture and heptane were put into a container, and mechanical milling was performed using a planetary ball mill for 40 hours to obtain a Li2S—P2S5-based solid electrolyte. Heptane, a heptane solution containing 5% by mass of a butadiene rubber (BR) binder, and a glass ceramic including LiI—LiBr—Li2S—P2S5 as a solid electrolyte were added in a polypropylene container, and then the mixture was stirred for 30 seconds with an ultrasonic dispersion apparatus (UH-50 manufactured by SMT CO., LTD.). Next, the container was shaken with a shaker (TTM-1 manufactured by SHIBATA SCIENTIFIC TECHNOLOGY LTD.) for 30 seconds to obtain a slurry. The slurry was applied on a base material (aluminum foil) by a blade method using an applicator. Thereafter, a solid electrolyte layer (thickness of about 15 μm) was formed on the base material by drying on a hot plate at 100° C. for 30 minutes.
Preparation of All-Solid State Lithium Ion Battery
The solid electrolyte layer and the positive electrode were laminated so that the solid electrolyte layer was in contact with the positive electrode mixture layer, and pressed at 1 ton/cm2. Thereafter, the base material was peeled off to obtain a two-layer body including the solid electrolyte layer and the positive electrode. Next, the two-layer body and the negative electrode were laminated so that the solid electrolyte layer of the two-layer body was in contact with the negative electrode mixture layer, and pressed at 6 ton/cm2 to obtain a laminate having the solid electrolyte between the positive electrode and the negative electrode. The obtained laminate (cell) was restrained at a predetermined restraint pressure (1.4 MPa) using a screw-fastening type restraint member (see
A predetermined amount of a lumpy Cr raw material of 2 mm to 5 mm manufactured by Kojundo Chemical Lab. Co., Ltd. was mixed with a lumpy Si raw material of 2 mm to 5 mm manufactured by Kojundo Chemical Lab. Co., Ltd., and an ingot was prepared by argon arc melting (about 1,500° C.). The ingot was crushed with a tungsten mortar, and a silicon alloy powder was prepared by a ball mill and used as a Si alloy active substance for a negative electrode. Si alloy active substances for a negative electrode in which the content of Cr was 10 mol %, 5 mol %, and 14 mol % were respectively set as Experimental Examples 1 to 3.
A Si alloy active substance for a negative electrode obtained through the same process as in Experimental Example 1, except that a sponge-like Ti raw material of 2 mm to 5 mm manufactured by Kojundo Chemical Lab. Co., Ltd. was mixed as a raw material so that the Ti content was 14 mol %, was set as Experimental Example 4.
Si alloy active substances for a negative electrode obtained through the same process as in Experimental Example 1, except that a linear Zr raw material having a diameter of 1 mm and a length of about 20 mm manufactured by Nilaco Corporation was mixed as a raw material so that Zr content was 5 mol % and 9 mol %, were respectively set as Experimental Examples 5 and 6.
Si alloy active substances for a negative electrode obtained through the same process as in Experimental Example 1, except that a lumpy Nb raw material of 2 mm to 5 mm manufactured by Kojundo Chemical Lab. Co., Ltd. was mixed as a raw material so that the Nb content was 5 mol %, was set as Experimental Example 7. A Si alloy active substance for a negative electrode obtained through the same process as in Experimental Example 1, except that a lumpy Mo raw material of 1 mm to 5 mm manufactured by Kojundo Chemical Lab. Co., Ltd. was mixed as a raw material so that the Mo content was 5 mol %, was set as Experimental Example 8.
Si alloy active substances for a negative electrode obtained through the same process as in Experimental Example 1, except that a sponge-like Hf raw material of 5 mm to 10 mm manufactured by Kojundo Chemical Lab. Co., Ltd. was mixed as a raw material so that the Hf content was 5 mol % and 11 mol %, were respectively set as Experimental Examples 9 and 10.
A Si alloy active substance for a negative electrode obtained through the same process as in Experimental Example 1, except that a lumpy Cr raw material of 2 mm to 5 mm and a sponge-like Hf raw material of 2 mm to 5 mm manufactured by Kojundo Chemical Lab. Co., Ltd. were mixed as raw materials so that the Cr content was 7 mol % and the Zr content was 7 mol %, was set as Experimental Example 11. A Si alloy active substance for a negative electrode obtained through the same process as in Experimental Example 1, except that a sponge-like Hf raw material of 5 mm to 10 mm manufactured by Kojundo Chemical Lab. Co., Ltd. and a linear Zr raw material having a diameter of 1 mm and a length of 20 mm manufactured by Nilaco Corporation were mixed as raw materials so that the Hf content was 6 mol % and the Zr content was 4 mol %, was set as Experimental Example 12. A Si alloy active substance for a negative electrode obtained through the same process as in Experimental Example 1, except that a lumpy Cr raw material of 1.7 mm to 4 mm manufactured by Kojundo Chemical Lab. Co., Ltd. and a linear Zr raw material having a diameter of 1 mm and a length of 10 mm manufactured by Nilaco Corporation were mixed as raw materials so that the Cr content was 13 mol % and the Zr content was 9 mol %, was set as Experimental Example 13.
Experimental Example 14 used Si particles having an average particle diameter of about 1 μm to 5 μm as a Si alloy active substance for a negative electrode.
A Si alloy active substance for a negative electrode obtained through the same process as in Experimental Example 1, except that a lumpy Ni raw material of 2 mm to 5 mm manufactured by Kojundo Chemical Lab. Co., Ltd. was mixed as a raw material so that the Ni content was 10 mol %, was set as Experimental Example 15.
SEM Observation and Elemental Analysis
The obtained negative electrode active substance was subjected to an element mapping by a scanning electron microscope (SEM) observation and an EDX analysis to observe the distribution state of the elements. For the SEM observation and the element mapping, a scanning electron microscope (S-3600N manufactured by Hitachi, Ltd.) and an energy dispersive X-ray analyzer (EDAX) were used. The acceleration voltage was set to 15 kV.
Volume Ratio of Silicide Phase
From the blended compositional ratio, the volume proportion of the silicide phase was determined using the principle of leverage in a state graph (see
Performance Evaluation of All-Solid State Lithium Ion Battery
Preliminary charge and discharge were performed at a rate of 0.1 C to 1 C at a potential of 3.0 V to 4.55 V with an initial restraint pressure of 1.25 MPa. Furthermore, charge and discharge were performed in the initial five cycles under the following conditions, the capacity was confirmed, and the restraint pressure variation was calculated. First, as a preliminary charge, the battery was charged at constant current and constant voltage up to 4.55 V at a time rate of 0.1 C. Next, as a preliminary discharge, the battery was discharged to 3.0 V at constant current and constant voltage at a time rate of 1 C. Subsequently, as the first to the fifth charge, the battery was charged up to 4.35 V at constant current and constant voltage at a time rate of 0.33 C. In addition, as the first to the fifth discharge, the battery was discharged to 3.0 V at constant current and constant voltage at a time rate of 0.33 C. Then, the restraint pressure variation and the capacity were calculated based on the charge and discharge results. In the above charge and discharge, the restraint pressure variations (MPa) of the first and the second cycle were determined, and the discharge capacities (mAh) and the capacity retention rates (%) of the first and the fifth cycle were determined.
Measurement of Restraint Pressure Variation
Variations in the restraint pressure of the cells of Experimental Examples 1 to 15 were measured. During the above-described charge and discharge cycle, a pressure sensor (a small-sized compression load cell manufactured by Kyowa Electronic Instruments Co., Ltd.) was inserted between the restraint member and the battery case, and the pressure was measured at predetermined time intervals.
Examination of Si Alloy Composition for Negative Electrode
Next, the measurement results of Experimental Examples 2 and 13 will be discussed. Table 1 collectively shows the restraint pressure variations (MPa) of the first and the second cycle and the discharge capacities (mAh) and the capacity retention rates (%) of the first and the fifth cycle in Experimental Examples 1 to 15.
Further, the negative electrode active substances of Experimental Examples 11 to 13 containing a plurality of types of elements M will be discussed. It was found the restraint pressure variations of the first and the second cycle in Experimental Examples 11 to 13 are respectively 2.56 MPa to 2.76 MPa and 1.38 MPa to 1.48 MPa, which are further reduced than in Experimental Example 14 and 15. On the other hand, the capacity retention rates after five cycles in Experimental Examples 11 to 13 have values between 98.4% and 98.8%, which are higher than that in Experimental Example 14, and the capacity retention rate is improved. It was considered that a lamellar structure was formed by a eutectic reaction with complex (Cr, Ti)Si2, (Hf, Zr)Si2, and (Cr, Zr)Si2 silicide which were formed of Si and respectively (Cr, Ti), (Hf, Zr), and (Cr, Zr), thereby reducing the restraint pressure variation and improving the capacity retention rate.
As described above, it was found that the negative electrode active substance material preferably includes a silicon phase and a silicide phase represented by a basic composition formula MSi2, where M is one or more of Cr, Ti, Zr, Nb, Mo, and Hf and that the negative electrode active substance material may have a structure in which the silicide phase is dispersed in the silicon phase. In addition, it was found that the element M is preferably a eutectic composition or a hypoeutectic composition of a silicon phase and a silicide phase, preferably in a range of 2 mol % or more and 25 mol % or less, and more preferably in a range of 5 mol % or more and 15 mol % or less with respect to the entirety of the silicon phase and the silicide phase. In particular, it was found that the silicide phase containing at least Zr as the element M and further containing one or more of Cr and Hf further reduces the restraint pressure and has a preferred capacity and a preferred capacity retention rate. In this case, it was found that Zr is more preferably included in a range of 5 mol % or more and 10 mol % or less with respect to the entirety of the silicon phase and the silicide phase and that one or more of Cr and Hf is preferably included in a range of 5 mol % or more and 15 mol % or less with respect to the entirety of the silicon phase and the silicide phase.
The present disclosure is not limited to the above-described Examples at all, and the present disclosure can be implemented in various aspects as long as the aspect belongs to the technical scope of the present disclosure.
The present disclosure can be used in the technical field of a secondary battery.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019-039928 | Mar 2019 | JP | national |
