Patent Application
20240128462
The present disclosure relates to a coated positive electrode active material, a positive electrode material, and a battery.
Japanese Unexamined Patent Application Publication No. 2006-244734 discloses a solid-state battery including a halide that includes indium and serves as a solid electrolyte. International Publication No. 2019/146308 discloses a battery that includes a halide, an electrode active material, and a coating material disposed on the surface of the electrode active material. Journal of The Electrochemical Society, 163(10) A2399-A2406 (2016) discloses a secondary battery including an electrolyte solution including tris(trimethylsilyl) phosphite and triallyl phosphate.
One non-limiting and exemplary embodiment provides a positive electrode active material that may improve the cycle characteristics of a battery.
In one general aspect, the techniques disclosed here feature a coated positive electrode active material including a positive electrode active material and a coating material that covers at least a part of a surface of the positive electrode active material, wherein the coating material includes a phosphoric acid ester, and the phosphoric acid ester includes at least one selected from the group consisting of an alkyl group, an alkenyl group, and an alkynyl group.
Additional benefits and advantages of the disclosed embodiments will become apparent from the specification and drawings. The benefits and/or advantages may be individually obtained by the various embodiments and features of the specification and drawings, which need not all be provided in order to obtain one or more of such benefits and/or advantages.
There has been room for improvement of the cycle characteristics of solid-state lithium-ion secondary batteries known in the related art in terms of the oxidative decomposition of a solid electrolyte. In order to address the above issue, a method in which the surface of a positive electrode active material is covered with an oxide is reported. However, an oxide that covers the surface of a positive electrode active material may inhibit the conduction of lithium ions and electrons and cause capacity reduction or the like. Accordingly, batteries that include a positive electrode active material the surface of which is covered with a coating material are not likely to have consistent battery characteristics, such as cycle characteristics. Although a method in which the surface of an active material is covered with a metal is also reported, it is not possible to limit the oxidative decomposition of a solid electrolyte to a sufficient degree.
A coated positive electrode active material according to a first aspect of the present disclosure includes:
At least a part of the surface of the coated positive electrode active material according to the first aspect is covered with the coating material including a phosphoric acid ester. The coating material including a phosphoric acid ester enables the surface of the positive electrode active material to be covered with a thin coating film with efficiency. Furthermore, even with such a thin coating film, the likelihood of the oxidative decomposition of a solid electrolyte occurring when the solid electrolyte is brought into contact with the positive electrode active material may be reduced with effect. Thus, the coated positive electrode active material according to the first aspect may effectively limit the oxidative decomposition of a solid electrolyte and an increase in internal resistance and consequently improve the cycle characteristics of a battery.
According to a second aspect of the present disclosure, for example, in the coated positive electrode active material according to the first aspect, the phosphoric acid ester may include an alkenyl group, and the alkenyl group may include at least one selected from the group consisting of a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group.
The coated positive electrode active material according to the second aspect may further improve the cycle characteristics of a battery.
According to a third aspect of the present disclosure, for example, in the coated positive electrode active material according to the first or second aspect, the phosphoric acid ester may include triallyl phosphate.
The coated positive electrode active material according to the third aspect may further improve the cycle characteristics of a battery.
According to a fourth aspect of the present disclosure, for example, in the coated positive electrode active material according to any one of the first to third aspects, a maximum peak belonging to P2p in an X-ray photoelectron spectrum of the coating material may be located at a binding energy higher than 133.3 eV.
The coated positive electrode active material according to the fourth aspect may further improve the cycle characteristics of a battery.
According to a fifth aspect of the present disclosure, for example, in the coated positive electrode active material according to any one of the first to fourth aspects, a molar ratio of O to P in the coating material may be lower than 4.
The coated positive electrode active material according to the fifth aspect may further improve the cycle characteristics of a battery.
According to a sixth aspect of the present disclosure, for example, in the coated positive electrode active material according to any one of the first to fifth aspects, the positive electrode active material may include a lithium transition metal complex oxide.
The coated positive electrode active material according to the sixth aspect may further improve the cycle characteristics of a battery.
According to a seventh aspect of the present disclosure, for example, in the coated positive electrode active material according to the sixth aspects, the lithium transition metal complex oxide may have a layered rocksalt crystal structure and may be represented by Formula (2),
LiNixCoyMe1−x−yO2 (2)
where x and y satisfy 0≤x<1, 0≤y≤1, and 0≤1−x−y≤0.35, and Me represents at least one selected from the group consisting of Al and Mn.
The coated positive electrode active material according to the seventh aspect may improve the charge-discharge capacity of a battery.
A positive electrode material according to an eighth aspect of the present disclosure includes:
The positive electrode material according to the eighth aspect may improve the cycle characteristics of a battery.
A battery according to a ninth aspect of the present disclosure includes:
The battery according to the ninth aspect may have improved cycle characteristics.
A coated positive electrode active material according to Embodiment 1 of the present disclosure includes a positive electrode active material and a coating material that covers at least a part of the surface of the positive electrode active material. The coating material includes a phosphoric acid ester. The phosphoric acid ester includes at least one selected from the group consisting of an alkyl group, an alkenyl group, and an alkynyl group. Hereinafter, the phosphoric acid ester included in the coating material is also referred to as “compound A”.
In the case where the coating material includes the compound A, the surface of the positive electrode active material can be covered with a thin coating film with efficiency. Consequently, a battery having low internal resistance and excellent cycle characteristics may be readily produced. Moreover, the likelihood of a solid electrolyte being decomposed when brought into contact with the positive electrode active material in the battery can be reduced. This may improve the cycle characteristics of the battery.
The detailed reasons for which ease of coating of the surface of the positive electrode active material can be increased when the coating material includes the compound A are unknown. It is considered that one of the reasons for which the ease of coating is increased is, in the case where the positive electrode active material includes a transition metal, the interaction between at least one selected from the group consisting of an alkyl group, an alkenyl group, and an alkynyl group included in the compound A and the transition metal included in the positive electrode active material. It is considered that the presence of the double or triple bond included in the alkyl, alkenyl, or alkynyl group increases the energy of the p orbital and enables the compound A and the transition metal to easily bind to each other.
In consideration of the interaction between the transition metal included in the positive electrode active material and the compound A, in the case where the compound A includes an alkenyl group, the double bond of the alkenyl group is desirably located at a position closer to the terminal of the alkenyl group. Similarly, in the case where the compound A includes an alkynyl group, the triple bond of the alkynyl group is desirably located at a position closer to the terminal of the alkynyl group. In order to increase, for example, ease of dissolving the compound A in an organic solvent and the likelihood of the compound A adhering onto the surface of the positive electrode active material, the number of carbon atoms included in the alkyl, alkenyl, or alkynyl group may be, for example, 1 to 5. From the same viewpoints as above, the alkyl, alkenyl, or alkynyl group may be linear.
In the case where the compound A includes two or more selected from the group consisting of an alkyl group, an alkenyl group, and an alkynyl group, the structures of the two or more selected from the group consisting of an alkyl group, an alkenyl group, and an alkynyl group may be the same as or different from each other.
Specifically, the alkenyl group may include at least one selected from the group consisting of a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), an isopropenyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group. In order to increase, for example, ease of dissolving the compound A in an organic solvent and the likelihood of the compound A adhering onto the surface of the positive electrode active material, in particular, the alkenyl group may be an allyl group or a 3-butenyl group. The alkenyl group may be an allyl group.
The compound A may have, for example, the structure represented by Formula (I) below.
In Formula (I), R1, R2, and R3 each independently represent a hydrogen atom or an organic group, and at least one selected from the group consisting of R1, R2, and R3 is an alkyl, alkenyl, or alkynyl group. At least one selected from the group consisting of R1, R2, and R3 may be an alkenyl group. All of R1, R2, and R3 may be alkenyl groups. In the case where the compound A represented by Formula (I) includes a plurality of alkenyl groups, the structures of the alkenyl groups may be the same as or different from one another. Some of the hydrogen atoms included in the alkenyl group may be replaced with a halogen atom, such as a chlorine atom. The number of carbon atoms included in the alkenyl group is, for example, 1 to 5. The alkenyl group may be either linear or branched. The alkenyl group may have a structure represented by CH2═CH—(CH2)n—, where n may be 0 or more and 3 or less and may be 1. The alkenyl group may be at least one selected from the group consisting of a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group.
In Formula (I), one selected from the group consisting of R1, R2, and R3 may be an alkenyl group, and two selected from the group consisting of R1, R2, and R3 may be hydrocarbon groups other than an alkenyl group. Alternatively, two selected from the group consisting of R1, R2, and R3 may be alkenyl groups, and one selected from the group consisting of R1, R2, and R3 may be a hydrocarbon group other than an alkenyl group. Examples of the hydrocarbon group other than an alkenyl group include an alkyl group. Some of the hydrogen atoms included in the hydrocarbon group other than an alkenyl group may be replaced with a halogen atom, such as a chlorine atom. In the case where the compound A represented by Formula (I) includes two hydrocarbon groups other than an alkenyl group, the hydrocarbon groups other than an alkenyl group may be the same as or different from each other. In the case where the compound A includes an alkyl group, the number of carbon atoms included in the alkyl group is, for example, 2 to 5. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.
The compound A may include at least one selected from the group consisting of a phosphoric acid monoester, a phosphoric acid diester, and a phosphoric acid triester. The compound A may include a phosphoric acid triester. The compound A may include triallyl phosphate. In the case where the coating material includes triallyl phosphate, the ease of coating of the positive electrode active material can be increased with efficiency while the resistance of the positive electrode is limited to a low level, even when the content of triallyl phosphate in the coating material is low. The compound A may be triallyl phosphate.
The coating material may include the compound A as a principal component. The term “principal component” used herein refers to a component the content of which is the highest in terms of mass proportion.
The above-described structure may further improve the cycle characteristics of a battery.
The coating material may be composed only of the compound A.
The coating material may cover 30% or more, 60% or more, or 90% or more of the surface of the positive electrode active material. The coating material may cover substantially the entirety of the surface of the positive electrode active material.
The coating material may be brought into direct contact with the surface of the positive electrode active material.
The thickness of the coating material may be, for example, 100 nm or less or 10 nm or less. The coating material may be formed on the surface of the positive electrode active material in an island-like manner. The coating material may be used in a trace amount close to the detection limit When the presence of the compound A in the positive electrode is confirmed, it is considered that the compound A is deposited on the positive electrode active material in a certain amount and the improvement of cycle characteristics can be confirmed accordingly. In particular, when the thickness of the coating material is 10 nm or less, the capacity reduction due to resistance increase may be limited in addition to the improvement of cycle characteristics. The presence of the compound A is determined by X-ray photoelectron spectroscopy. In particular, when the thickness of the coating is 10 nm or less, a signal resulting from the compound A and a signal resulting from, for example, the transition metal included in the positive electrode active material are detected simultaneously. The thickness of the coating material may be 5 nm or less.
The thickness of the coating material may be 1 nm or more.
The method for measuring the thickness of the coating material is not limited. For example, the thickness of the coating material may be directly measured with a transmission electron microscope.
For covering the surface of the positive electrode active material with the coating material, for example, a liquid-phase method may be used. Examples of the liquid-phase method include spray coating and dip coating. The surface of the positive electrode active material can be readily covered with the compound A by bringing a solution prepared by dissolving the compound A in an organic solvent with the complex oxide and subsequently performing drying. At least one selected from the group consisting of ethanol, tetralin, ethylbenzene, mesitylene, pseudocumene, xylene, cumene, dibutyl ether, anisole, 1,2,4-trichlorobenzene, chlorobenzene, 2,4-dichlorobenzene, o-chlorotoluene, 1,3-dichlorobenzene, p-chlorotoluene, 1,2-dichlorobenzene, 1,4-dichlorobutane, 3,4-dichlorotoluene, tetraethyl orthosilicate, dimethyl carbonate, and the like may be used as an organic solvent.
The content of the compound A in the solution may be 5% by mass or less, may be 0.25% by mass or more and 2% by mass or less, and may be 0.25% by mass or more and 1.25% by mass or less. For example, the content of the compound A may fall within the above range in the preparation of the solution. In such a case, the surface of the positive electrode active material can be covered with the compound A in a sufficient manner and, consequently, the cycle characteristics of a battery may be readily improved.
By the above-described method, the surface of the positive electrode active material can be covered with the coating material in a sufficient manner and the possibility of the positive electrode active material and an electrolyte coming into contact with each other may be reduced to a sufficient degree.
As a result of the progress of polymerization of the phosphoric acid ester included in the coating material, the valence of phosphorus included in the coating material may become smaller than that of normal phosphoric acid. The molar ratio of O to P in the coating material may be lower than 4.
The maximum peak belonging to P2p in the X-ray photoelectron spectrum of the coating material may be located at a higher binding energy than the peak belonging to P2p in the X-ray photoelectron spectrum of trilithium phosphate. The maximum peak belonging to P2p in the X-ray photoelectron spectrum of the coating material may be located at a binding energy higher than 133.3 eV.
The positive electrode active material may include a lithium transition metal complex oxide. The transition metal included in the lithium transition metal complex oxide may be at least one selected from the group consisting of nickel (Ni), cobalt (Co), manganese (Mn), iron (Fe), copper (Cu), chromium (Cr), titanium (Ti), niobium (Nb), zirconium (Zr), vanadium (V), tantalum (Ta), and molybdenum (Mo).
The lithium transition metal complex oxide can be produced by, for example, mixing a lithium compound with a compound including a transition metal which is prepared by coprecipitation or the like and heat-treating the resulting mixture under predetermined conditions. The lithium transition metal complex oxide commonly forms secondary particles, which are formed as a result of aggregation of a plurality of primary particles. The average size (D50) of particles of the lithium transition metal complex oxide is, for example, 1 μm or more and 20 μm or less. Note that the term “average particle size (D50)” used herein refers to the particle size (volume-average particle size) at which a cumulative volume reaches 50% in a volume-basis particle size distribution measured by laser diffraction scattering.
The lithium transition metal complex oxide may include a metal other than transition metals. The metal other than transition metals may include at least one selected from the group consisting of aluminum (Al), magnesium (Mg), calcium (Ca), strontium (Sr), zinc (Zn), and silicon (Si). The above complex oxide may further include, in addition to metals, boron (B) and the like.
In order to increase capacity, the transition metal may include at least one selected from the group consisting of Ni and Co. The lithium transition metal complex oxide may include Ni and at least one selected from the group consisting of Co, Mn, Al, Ti, and Fe. In order to increase capacity and power, in particular, the lithium transition metal complex oxide may include Ni and at least one selected from the group consisting of Co, Mn, and Al and may include Ni, Co, and at least one selected from the group consisting of Mn and Al. In the case where the lithium transition metal complex oxide includes Co in addition to Li and Ni, the likelihood of the phase transition of the complex oxide, which includes Li and Ni, occurring during charge and discharge can be reduced, the stability of the crystal structure can be enhanced, and the cycle characteristics may be readily improved consequently. In the case where the lithium transition metal complex oxide further includes at least one selected from the group consisting of Mn and Al, thermal stability may be enhanced.
In order to improve cycle characteristics and increase power, the lithium transition metal complex oxide included in the positive electrode active material may include a lithium transition metal complex oxide that has a layered rocksalt crystal structure and includes at least one selected from the group consisting of Ni and Co and may include a lithium transition metal complex oxide that has a spinel crystal structure and includes Mn. In order to increase capacity, the lithium transition metal complex oxide may be a complex oxide that has a layered rocksalt crystal structure and includes Ni and a metal other than Ni, wherein the atomic ratio of Ni to the metal other than Ni is 0.3 or more (hereinafter, this complex oxide is also referred to as “nickel-based complex oxide).
The lithium transition metal complex oxide may have a layered rocksalt crystal structure and a composition represented by Formula (1) below.
LiNiαMe′1−αO2 (1)
where α satisfies 0≤α<1, and Me′ represents at least one element selected from the group consisting of Co, Mn, Al, Ti, and Fe.
In Formula (1), in the case where a falls within the above range, the effect of Ni to increase capacity and the effect of the element Me′ to enhance stability may be both achieved in a balanced manner
In Formula (1), α may be 0.5 or more or may be 0.75 or more.
The lithium transition metal complex oxide may have a layered rocksalt crystal structure and a composition represented by Formula (2) below.
LiNixCoyMe1−x−yO2 (2)
where x and y satisfy 0≤x<1, 0<y≤1, and 0≤1−x−y≤0.35, and Me represents at least one selected from the group consisting of Al and Mn.
As described above, the first solid electrolyte material 100 includes a halide solid electrolyte. The first solid electrolyte material 100 may consist essentially of Li, M, and X. The expression “the first solid electrolyte material 100 consists essentially of Li, M, and X” used herein means that the ratio (i.e., molar fraction) of the total amount of substance of Li, M, and X to the total amount of substance of all the elements constituting the first solid electrolyte material 100 is 90% or more. For example, the above ratio (i.e., molar fraction) may be 95% or more. The first solid electrolyte material 100 may be composed only of Li, M, and X. The first solid electrolyte material 100 does not necessarily include sulfur.
In order to enhance ionic conductivity, M may include at least one element selected from the group consisting of the Group 1 elements, the Group 2 elements, the Group 3 elements, the Group 4 elements, and the lanthanoid elements.
M may also include the Group 5 elements, the Group 12 elements, the Group 13 elements, and the Group 14 elements.
Examples of the Group 1 elements include Na, K, Rb, and Cs. Examples of the Group 2 elements include Mg, Ca, Sr, and Ba. Examples of the Group 3 elements include Sc and Y. Examples of the Group 4 elements include Ti, Zr, and Hf. Examples of the lanthanoid elements include La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
Examples of the Group 5 elements include Nb and Ta. Examples of the Group 12 elements include Zn. Examples of the Group 13 elements include Al, Ga, and In. Examples of the Group 14 elements include Sn.
In order to further enhance ionic conductivity, M may include at least one element selected from the group consisting of Na, K, Mg, Ca, Sr, Ba, Sc, Y, Zr, Hf, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
In order to further enhance ionic conductivity, M may include at least one element selected from the group consisting of Mg, Ca, Sr, Y, Sm, Gd, Dy, and Hf.
In order to further enhance ionic conductivity, X may include at least one element selected from the group consisting of Br, Cl, and I.
In order to further enhance ionic conductivity, X may include Br, Cl, and I.
The first solid electrolyte material 100 may be Li3YX6. The first solid electrolyte material 100 may be Li3YBr6. The first solid electrolyte material 100 may be Li3YBrx1Cl6−x1 where x1 satisfies 0≤x1<6. The first solid electrolyte material 100 may be Li3YBrx2Cly2I6−x2−y2 where x2 and y2 satisfy 0≤x2, 0≤y2, and 0≤x2+y2≤6.
The first solid electrolyte material 100 may be Li3YBr6, Li3YBr2Cl4, or Li3YBr2Cl2I2.
The first solid electrolyte material 100 may further include a sulfide solid electrolyte, an oxide solid electrolyte, a polymeric solid electrolyte, or a complex hydride solid electrolyte.
Examples of the sulfide solid electrolyte include Li2S—P2S5, Li2S—SiS2, Li2S—B2S3, Li2S—GeS2, Li3.25Ge0.25P0.75S4, Li10GeP2S12, and Li6PS5Cl. LiX′, Li2O, MOq, LipM′Oq, and the like may be added to the above sulfide solid electrolytes, where X′ represents at least one selected from the group consisting of F, Cl, Br, and I, M′ represents at least one selected from the group consisting of P, Si, Ge, B, Al, Ga, In, Fe, and Zn, and p and q are integers independent from each other.
Examples of the oxide solid electrolyte include NASICON-type solid electrolytes, such as LiTi2(PO4)3 and element substitution products thereof; perovskite-type solid electrolytes, such as (LaLi)TiO3; LISICON-type solid electrolytes, such as Li14ZnGe4O16, Li4SiO4, LiGeO4, and element substitution products thereof; garnet-type solid electrolytes, such as Li7La3Zr2O12 and element substitution products thereof; Li3N and H-substitution products thereof; Li3PO4 and N-substitution products thereof; and glass and glass ceramics that include a Li—B—O compound, such as LiBO2 or Li3BO3, as a base and Li2SO4, Li2CO3, or the like added to the base.
The polymeric solid electrolyte may be, for example, a compound formed by the reaction of a high-molecular-weight compound with a lithium salt. The high-molecular-weight compound may have an ethylene oxide structure. Since a polymeric solid electrolyte having an ethylene oxide structure is capable of containing a large amount of lithium salt, ionic conductivity may be further enhanced. Examples of the lithium salt include LiPF6, LiBF4, LiSbF6, LiAsF6, LiSO3CF3, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiN(SO2CF3)(SO2C4F9), and LiC(SO2CF3)3. Only one lithium salt selected from the above lithium salts may be used alone. Alternatively, two or more lithium salts selected from the above lithium salts may be used in a mixture.
Examples of the complex hydride solid electrolyte include LiBH4—LiI and LiBH4—P2S5.
The shape of the first solid electrolyte material 100 is not limited and may be, for example, acicular, spherical, or spheroidal. For example, the shape of the first solid electrolyte material 100 may be particulate.
In the case where, for example, the shape of the first solid electrolyte material 100 is particulate (e.g., spherical), the median diameter of the first solid electrolyte material 100 may be 100 μm or less. In the case where the median diameter of the first solid electrolyte material 100 is 100 μm or less, the coated positive electrode active material 150 and the first solid electrolyte material 100 can be dispersed in the positive electrode material 1000 in a suitable manner and, consequently, the charge-discharge characteristics of a battery including the positive electrode material 1000 may be improved.
The median diameter of the first solid electrolyte material 100 may be 100 μm or less. In such a case, the coated positive electrode active material 150 and the first solid electrolyte material 100 can be dispersed in the positive electrode material 1000 in a further suitable manner
The first solid electrolyte material 100 may have a smaller median diameter than the coated positive electrode active material 150. In such a case, the coated positive electrode active material 150 and the first solid electrolyte material 100 can be dispersed in the positive electrode material 1000 in a further suitable manner
The median diameter of the coated positive electrode active material 150 may be 0.1 μm or more and 100 μm or less.
When the median diameter of the coated positive electrode active material 150 is 0.1 μm or more, the coated positive electrode active material 150 and the first solid electrolyte material 100 can be dispersed in the positive electrode material 1000 in a suitable manner and, consequently, the charge-discharge characteristics of a battery including the positive electrode material 1000 may be enhanced. When the median diameter of the coated positive electrode active material 150 is 100 μm or less, the rate at which lithium diffuses in the coated positive electrode active material 150 is increased and, consequently, it may become possible to operate a battery including the positive electrode material 1000 at high powers.
The coated positive electrode active material 150 may have a larger median diameter than the first solid electrolyte material 100. In such a case, the coated positive electrode active material 150 and the first solid electrolyte material 100 can be dispersed in the positive electrode material 1000 in a suitable manner
Embodiment 3 is described below. Note that description of the items described in Embodiment 1 or 2 above is omitted herein.
The battery 2000 according to Embodiment 3 includes a positive electrode 201 that includes the positive electrode material 1000 described in Embodiment 2 above, a negative electrode 203, and a solid electrolyte layer 202 interposed between the positive electrode 201 and the negative electrode 203.
The battery 2000 may be a solid-state battery.
When the surface of a positive electrode active material included in a secondary battery including an electrolyte solution is covered with a phosphoric acid ester, the phosphoric acid ester dissolves in the electrolyte solution and adheres also to the negative electrode-side portion disadvantageously. Since phosphoric acid becomes decomposed at, for example, a potential of a negative electrode that includes graphite as an active material, capacity reduction or degradation of cycle characteristics may occur. In contrast, in the case where a phosphoric acid ester is used as a material for covering a positive electrode active material of a solid-state battery as in the present disclosure, there is no risk of phosphoric acid or phosphoric acid ester coming into contact with the negative electrode-side portion and becoming decomposed.
The positive electrode 201 includes a material capable of occluding and releasing a metal ion (e.g., lithium ion). The positive electrode 201 includes a coated positive electrode active material 150 and a first solid electrolyte material 100.
The ratio of the volume of the positive electrode active material 110 included in the positive electrode 201 to the total volume of the positive electrode active material 110 and the first solid electrolyte material 100 included in the positive electrode 201, that is, the volume ratio Vp, may be 0.3 or more and 0.95 or less. When the volume ratio Vp is 0.3 or more, the battery 2000 is likely to have a sufficiently high energy density. When the volume ratio Vp is 0.95 or less, it becomes easier to operate the battery 2000 at high powers.
The thickness of the positive electrode 201 may be 10 μm or more and 500 μm or less.
When the thickness of the positive electrode 201 is 10 μm or more, the battery 2000 may have a sufficiently high energy density. When the thickness of the positive electrode 201 is 500 μm or less, it may become possible to operate the battery 2000 at high powers.
The positive electrode 201 may include a binder. The binder is used to enhance the integrity of the materials constituting the positive electrode 201. Examples of the binder include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, an aramid resin, polyamide, polyimide, polyamide imide, polyacrylonitrile, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polyhexyl acrylate, polymethacrylic acid, polymethyl methacrylate, polyethyl methacrylate, polyhexyl methacrylate, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoro polypropylene, a styrene butadiene rubber, and carboxymethyl cellulose. The binder may be a copolymer of two or more materials selected from the group consisting of tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene. Alternatively, a mixture of two or more selected from the above materials may be used as a binder.
The positive electrode 201 may include a conductant agent. The conductant agent is used to enhance electron conductivity. Examples of the conductant agent include graphite materials, such as natural graphite and artificial graphite; carbon black materials, such as acetylene black and Ketjenblack; conductive fibers, such as a carbon fiber and a metal fiber; carbon fluorides; metal powders, such as an aluminum powder; conductive whiskers, such as a zinc oxide whisker and a potassium titanate whisker; conductive metal oxides, such as titanium oxide; and conducting polymers, such as polyaniline, polypyrrole, and polythiophene. The use of a carbon conductant agent may reduce the costs. The above conductant agents may be used alone or in combination of two or more.
The positive electrode 201 may further include a positive electrode current collector.
The positive electrode current collector may be, for example, a metal foil. Examples of the metal constituting the positive electrode current collector include aluminum, titanium, an alloy including the above metal elements, and a stainless steel. The thickness of the positive electrode current collector is, for example, but not limited to, 3 μm or more and 50 μm or less. The metal foil may be coated with carbon or the like.
In the case where the positive electrode 201 further includes a positive electrode current collector, the coated positive electrode active material 150 that includes the positive electrode active material 110 and the coating material 120 formed on the surface of the positive electrode active material 110 can be prepared by mixing the positive electrode active material 110 with the first solid electrolyte material 100 to prepare a positive electrode mixture, dispersing the positive electrode mixture in a disperse medium to form a positive electrode slurry, adding the compound A to the positive electrode slurry, applying the resulting mixture onto the surface of the positive electrode current collector, and drying the resulting coating film. The dried coating film may be rolled as needed. The coating film composed of the positive electrode mixture may be disposed on either one or both of the surfaces of the positive electrode current collector. The positive electrode mixture may further include a binder, a conductant agent, or the like. The disperse medium may include, for example, at least one selected from the group consisting of tetralin, ethylbenzene, mesitylene, pseudocumene, xylene, cumene, dibutyl ether, anisole, 1,2,4-trichlorobenzene, chlorobenzene, 2,4-dichlorobenzene, o-chlorotoluene, 1,3-dichlorobenzene, p-chlorotoluene, 1,2-dichlorobenzene, 1,4-dichlorobutane, 3,4-dichlorotoluene, and tetraethyl orthosilicate.
The negative electrode 203 includes a material capable of occluding and releasing a metal ion (e.g., lithium ion). The negative electrode 203 includes, for example, a negative electrode active material. The negative electrode 203 may include a negative electrode active material 130 and a second solid electrolyte material 140.
The negative electrode active material 130 may include a carbon material capable of occluding and releasing a lithium ion. Examples of the carbon material capable of occluding and releasing a lithium ion include graphite materials (e.g., natural graphite and artificial graphite), graphitizable carbon (i.e., soft carbon), and non-graphitizable carbon (i.e., hard carbon). Among these, graphite is desirable because it enhances the charge-discharge stability and has a low irreversible capacity.
The negative electrode active material 130 may include an alloying material. The alloying material is a material that includes at least one metal capable of alloying with lithium. Examples of the alloying material include silicon, tin, indium, a silicon alloy, a tin alloy, an indium alloy, and a silicon compound. The silicon compound may be a composite material that includes a lithium ion conduction phase and silicon particles dispersed in the above phase. The lithium ion conduction phase may be a silicate phase, such as a lithium silicate phase, a silicon oxide phase in which the proportion of silicon dioxide is 95% by mass or more, a carbon phase, or the like.
In the case where a lithium alloy or a lithium-occluding metal is used as a negative electrode active material 130, the negative electrode 203 does not necessarily include the second solid electrolyte material 140 and may be composed only of the negative electrode active material 130.
The negative electrode active material 130 may include a lithium titanium oxide. The lithium titanium oxide may include at least one material selected from Li4Ti5O12, Li7T15O12, and LiTi2O4.
As a negative electrode active material 130, the alloying material and the carbon material, or the lithium titanium oxide and the carbon material may be used in combination.
The content of the second solid electrolyte material 140 in the negative electrode 203 may be the same as or different from the content of the negative electrode active material 130 in the negative electrode 203.
The ratio of the volume of the negative electrode active material 130 to the total volume of the negative electrode active material 130 and the second solid electrolyte material 140 in the negative electrode 203, that is, the volume ratio Vn, may be 0.3 or more and 0.95 or less. When the volume ratio Vn is 0.3 or more, the battery 2000 is likely to have a sufficiently high energy density. When the volume ratio Vn is 0.95 or less, it becomes easier to operate the battery 2000 at high powers.
The second solid electrolyte material 140 may be a material having the same composition as the above first solid electrolyte material 100 and may be a material having a composition different from that of the above first solid electrolyte material 100.
The second solid electrolyte material 140 may be a material described above as an example of the first solid electrolyte material 100. The second solid electrolyte material 140 may be a material having the same composition as the first solid electrolyte material 100 and may be a material having a composition different from that of the above first solid electrolyte material 100.
The thickness of the negative electrode 203 may be 10 μm or more and 500 μm or less.
When the thickness of the negative electrode 203 is 10 μm or more, the battery 2000 may have a sufficiently high energy density. When the thickness of the negative electrode 203 is 500 μm or less, it may become possible to operate the battery 2000 at high powers.
The negative electrode 203 may further include a negative electrode current collector. The negative electrode current collector may be composed of the same material as the positive electrode current collector. The thickness of the negative electrode current collector is, for example, but not limited to, 3 to 50 μm. In the case where a lithium alloy or a lithium-occluding metal is used as a negative electrode active material 130, the lithium alloy or lithium-occluding metal may be used as both negative electrode active material and negative electrode current collector.
The negative electrode 203 may include a negative electrode current collector and a negative electrode mixture layer supported on the surface of the negative electrode current collector. The negative electrode mixture layer can be formed by, for example, mixing the negative electrode active material 130 with the second solid electrolyte material 140 to prepare a negative electrode mixture, dispersing the negative electrode mixture in a disperse medium to form a negative electrode slurry, applying the negative electrode slurry onto the surface of the negative electrode current collector, and drying the resulting coating film. The dried coating film may be rolled as needed. The negative electrode mixture layer may be disposed on either one or both of the surfaces of the negative electrode current collector.
The negative electrode mixture may further include a binder, a conductant agent, a thickener, or the like. The binder and conductant agent may be the same as those used for preparing the positive electrode 201.
The solid electrolyte layer 202 is interposed between the positive electrode 201 and the negative electrode 203.
The solid electrolyte layer 202 is a layer including a solid electrolyte material.
As a solid electrolyte material included in the solid electrolyte layer 202, the materials described above as examples of the first and second solid electrolyte materials 100 and 140 may be used. The solid electrolyte layer 202 may include a solid electrolyte material having the same composition as the first solid electrolyte material 100 or the second solid electrolyte material 140. The solid electrolyte layer 202 may be composed of a material different from the first solid electrolyte material 100 or the second solid electrolyte material 140.
The solid electrolyte layer 202 may include two or more selected from the materials described above as examples of the solid electrolyte materials. For example, the solid electrolyte layer may include a halide solid electrolyte and a sulfide solid electrolyte.
The solid electrolyte layer 202 may include first and second electrolyte sublayers. The first electrolyte sublayer may be interposed between the positive electrode 201 and the negative electrode 203, while the second electrolyte sublayer is interposed between the first electrolyte sublayer and the negative electrode 203. The first electrolyte sublayer may include a material having the same composition as the first solid electrolyte material 100. The second electrolyte sublayer may include a material having a composition different from that of the first solid electrolyte material 100. The second electrolyte sublayer may include a material having the same composition as the second solid electrolyte material 140.
The solid electrolyte layer 202 may include a binder as needed. As a binder, the materials described above as examples of the binder included in the positive electrode 201 may be used.
The solid electrolyte layer 202 may be composed of any of the materials described above as examples of the first and second solid electrolyte materials 100 and 140.
The solid electrolyte layer 202 can be formed by, for example, dispersing the solid electrolyte material in a disperse medium to prepare a solid electrolyte slurry, drying the slurry to form a sheet-like body, and transferring the sheet-like body onto the surface of the positive electrode 201 or the negative electrode 203. The solid electrolyte layer 202 can be also formed by applying the solid electrolyte slurry directly onto the surface of the positive electrode 201 or the negative electrode 203 and drying the resulting coating film.
Although methods for forming the positive electrode 201, the negative electrode 203, and the solid electrolyte layer 202 using slurries are described above, the method for producing the battery 2000 is not limited to coating. The battery 2000 according to Embodiment 3 may be produced by, for example, preparing a material for forming the positive electrode, a material for forming the electrolyte layer, and a material for forming the negative electrode and subsequently preparing a multilayer body that includes a positive electrode, an electrolyte layer, and a negative electrode that are stacked on top of one another in this order by a publicly known method. For example, the battery 2000 can be formed by preparing a positive electrode including the positive electrode active material 110, the first solid electrolyte material 100, and a conductant agent, the solid electrolyte layer, and a negative electrode that includes the negative electrode active material 130, the second solid electrolyte material 140, and a conductant agent by powder compaction and bonding the above components to one another.
The present disclosure is specifically described with reference to Examples and Comparative Examples below. It should be noted that the present disclosure is not limited to Examples below.
In an argon atmosphere having a dew point of −80° C. and an oxygen concentration of about 10 ppm (hereinafter, referred to as “dry argon atmosphere”), specific amounts of powders of raw materials, that is, LiBr, YBr3, LiCl, and YCl3 were weighed such that the molar ratio between the raw materials was Li:Y:Br:Cl=3:1:2:4. The above materials were mixed with one another in a mortar while being pulverized. The resulting mixture was subjected to a milling treatment for 25 hours at 600 rpm with a planetary ball mill Hereby, a Li3YBr2Cl4 powder, which is a first solid electrolyte material of Example 1, was prepared.
The composition of the first solid electrolyte material prepared in Example 1 was determined by inductively-coupled plasma (ICP) emission spectrometry using an inductively-coupled plasma (ICP) optical emission spectrometer (“iCAP7400” produced by Thermo Fisher Scientific). The results confirmed that the deviation of the Li/Y molar ratio from the ratio between the amounts of components charged was 3% or less. That is, the ratio between the amounts of raw material powders charged into the planetary ball mill and the ratio between the amounts of components of the first solid electrolyte material prepared in Example 1 were substantially the same as each other.
The pressure-molding die 300 included an upper punch 301, a die 302, and a lower punch 303. The die 302 was composed of insulative polycarbonate. The upper and lower punches 301 and 303 were composed of a conductive stainless steel.
The ionic conductivity of the first solid electrolyte material prepared in Example 1 was measured using the pressure-molding die 300 illustrated in
In a dry atmosphere having a dew point of −30° C. or less, a powder of the first solid electrolyte material prepared in Example 1 (the solid electrolyte material powder 101 in
With the pressure being applied to the solid electrolyte material, the upper and lower punches 301 and 303 were connected to a potentiostat equipped with a frequency response analyzer (“VersaSTAT4” produced by Princeton Applied Research). The upper punch 301 was connected to the working electrode and the potential measuring terminal, while the lower punch 303 was connected to the counter electrode and the reference electrode. The impedance of the first solid electrolyte material was determined at room temperature. The ionic conductivity of the first solid electrolyte material was determined by electrochemical impedance spectroscopy.
The ionic conductivity of the first solid electrolyte material of Example 1 at 22° C. was 1.5×10−3 S/cm. The first solid electrolyte material was used also in Example 2 and Comparative Examples 1 and 2.
The positive electrode active material used was complex oxide particles that had a layered rocksalt structure and a composition of LiNi0.5Co0.3Mn0.2O2 (average particle size (D50): 4.4 μm; hereinafter, this complex oxide is referred to as “NCM”).
The method for covering the positive electrode active material with a coating material is described below; the method is not limited to the following method.
In p-chlorotoluene, 2-wt % triallyl phosphate was dispersed to prepare a mixed solution. In a dry atmosphere having a dew point of −40° C. or less, 0.5 g of the positive electrode active material was mixed with 200 μL of the mixed solution in a mortar. Subsequently, drying was performed at 90° C. for 5 minutes. Hereby, the surface of the positive electrode active material was covered with the coating material.
A surface analysis was conducted by X-ray photoelectron spectroscopy.
In a dry argon atmosphere, specific amounts of the first solid electrolyte material, the coated positive electrode active material, and a vapor-grown carbon fiber (“VGCF” produced by Showa Denko K. K.) used as a conductant agent were weighed such that the mass ratio between the above materials was 34:64:2. The above materials were mixed with one another in an agate mortar to form a positive electrode mixture. Note that “VGCF” is a registered trademark of Showa Denko K. K.
In an insulative cylinder, 13.1 mg of the positive electrode mixture, 80 mg of the first solid electrolyte material, and 80 mg of a solid electrolyte material Li6PS5Cl (produced by MSE) were stacked on top of one another. The above materials were pressure-molded at a pressure of 720 MPa into a multilayer body including a positive electrode and a solid electrolyte layer. On the surface of the solid electrolyte layer which was opposite to the surface on which the positive electrode was disposed, metal In (thickness: 200 μm), metal Li (thickness: 300 μm), and metal In (thickness: 200 μm) were stacked on top of one another. Subsequently, pressure molding was performed at a pressure of 80 MPa. Hereby, a multilayer body including a positive electrode, a solid electrolyte layer, and a negative electrode was prepared. Then, a stainless steel current collector was attached to the upper and lower ends of the multilayer body, that is, the positive and negative electrodes. A current collection lead was attached to each of the current collectors. Finally, the inside of the insulative cylinder was isolated from the outside atmosphere and hermetically sealed using an insulative ferrule. Hereby, a battery of Example 1 was prepared.
The battery prepared in Example 1 was subjected to the following charge-discharge test.
The battery was placed in a thermostat kept at 25° C.
The battery was charged at a constant current of 130 μA to a potential of 3.68 V with respect to Li/In and subsequently charged at a constant voltage. The current at which constant-voltage charging was to be finished was set to 26 μA.
The battery was then discharged at a constant current of 130 μA to a potential of 1.88 V with respect to Li/In and subsequently discharged at a constant voltage. The current at which constant-voltage discharging was to be finished was set to 26 μA.
The battery was subjected to a cycle test with the above charge and discharge being considered as one cycle. Table 1 lists the 1st-cycle discharge capacity and the 50th-cycle discharge retention.
Note that the 50th-cycle discharge retention is the ratio of the discharge capacity measured in the 50th cycle to the discharge capacity measured in the 1st cycle.
A battery of Example 2 was prepared as in the preparation of the battery of Example 1, except that, in the preparation of the coated positive electrode active material, a 2-wt % triallyl phosphate was dispersed in p-chlorotoluene to prepare a mixed solution, 0.5 g of the positive electrode active material was mixed with 100 μL of the mixed solution in a mortar in a dry atmosphere having a dew point of −40° C. or less, and subsequently drying was performed at 90° C. for 5 minutes.
A charge-discharge test was conducted as in Example 1. Table 1 lists the 1st-cycle discharge capacity and the 50th-cycle discharge retention of the battery prepared in Example 2.
A battery of Comparative Example 1 was prepared as in the preparation of the battery of Example 1, except that the positive electrode mixture of Comparative Example 1 was prepared by weighing specific amounts of the first solid electrolyte material, NCM used as a positive electrode active material, and the conductant agent “VGCF” such that the mass ratio between the above material was 34:64:2 and mixing the materials with one another in a mortar. That is, the positive electrode active material used in Comparative Example 1 was not covered with a coating material.
A charge-discharge test was conducted as in Example 1. Table 1 lists the 1st-cycle discharge capacity and the 50th-cycle discharge retention of the battery prepared in Comparative Example 1.
The 1st-cycle discharge capacity and the 50th-cycle discharge retention of the battery prepared in Comparative Example 1 were low compared with Examples 1 and 2. This is because, since the positive electrode active material was not covered with a coating material, resistance was increased as a result of oxidative decomposition of a solid electrolyte and discharge capacity was reduced accordingly. As illustrated in
A battery was prepared as in the preparation of the battery of Example 1, except that the surface of NCM, that is, the positive electrode active material, was covered with a 2-nm Al2O3 film formed by a gas phase method instead of triallyl phosphate.
A charge-discharge test was conducted as in Example 1. Table 1 lists the 1st-cycle discharge capacity and the 50th-cycle discharge retention of the battery prepared in Comparative Example 2.
The 1st-cycle discharge capacity and the 50th-cycle discharge retention of the battery prepared in Comparative Example 2 were low compared with Examples 1 and 2. Moreover, as illustrated in
The solid-state battery according to the present disclosure may be suitably used as, for example, a power source for mobile devices, such as a smart phone, a power unit for vehicles, such as an electric vehicle, a power source for automobile-installed equipment, or a device capable of storing natural energy, such as solar energy.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-098356 | Jun 2021 | JP | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2022/019756 | May 2022 | US |
| Child | 18527310 | US |
