Patent Application
20130071757
The present invention relates to a solid electrolyte material having excellent Li ion conductivity.
In accordance with a rapid spread of information relevant apparatuses and communication apparatuses such as a personal computer, a video camera and a portable telephone in recent years, as a power source thereof the development of a battery to be utilized has been emphasized. The development of a high-output and high-capacity battery for an electric automobile or a hybrid automobile has been advanced also in the automobile industry. A lithium battery has been presently noticed from the viewpoint of a high energy density among various kinds of batteries.
Liquid electrolyte containing a flammable organic solvent is used for a presently commercialized lithium battery, so that the installation of a safety device for restraining temperature rise during a short circuit and the improvement in structure and material for preventing the short circuit are necessary therefor. On the contrary, a lithium battery all-solidified by replacing the liquid electrolyte with a solid electrolyte layer is conceived to intend the simplification of the safety device and be excellent in production cost and productivity for the reason that the flammable organic solvent is not used in the battery.
A Li—La—Ti—O-based solid electrolyte material (LLT) has been known as a solid electrolyte material used for an all solid state lithium battery. For example, in Patent Literature 1, a solid electrolyte membrane having lithium ion conductivity is disclosed, which has a composition of LaXLiYTiZO3 (0.4≦X≦0.6, 0.4≦Y≦0.6, 0.8≦Z≦1.2, Y<X) and is an amorphous structure.
Further, in Patent Literature 2, a solid electrolyte layer composed of a solid electrolyte comprising a complex oxide containing Li, La and Ti is disclosed, wherein the solid electrolyte layer comprises an amorphous layer, a crystalline layer, and a lattice defect layer. In addition, in Patent Literature 2, it is described that the composition of a solid electrolyte material is preferably La2/3-xLi3xTiO3 (0.03≦x≦0.167). This solid electrolyte material is synthesized by performing planetary ball milling and burning, and corresponds to so-called bulk body, not a thin membrane.
Further, in Patent Literature 3, a perovskite type complex oxide represented by LixLayTizO3 (x, y, and z satisfy 0.08≦x≦0.75, 0.8≦z≦1.2, x+3y+4z=6) is disclosed. Further, in Examples of Patent Literature 4, a lithium ion conductor represented by Li0.34La0.51TiO2.94 is disclosed. Further, in Examples of Patent Literature 5, a perovskite type oxide represented by Li0.26La0.57TiO3 is disclosed.
A solid electrolyte material having excellent Li ion conductivity has been demanded from the viewpoint of achieving higher output of a battery. The present invention has been made in view of the above-mentioned actual circumstances, and a main object thereof is to provide a solid electrolyte material having excellent Li ion conductivity.
To attain the object, the present invention provides a solid electrolyte material represented by a general formula: Lix(La1-aM1a)y(Ti1-bM2b)zOδ, characterized in that “x”, “y”, and “z” satisfy relations of x+y+z=1, 0.652≦x/(x+y+z)≦0.753, and 0.167≦y/(y+z)≦0.232; “a” is 0≦a≦1; “b” is 0≦b≦1; “δ” is 0.8≦δ≦1.2; “M1” is at least one selected from the group consisting of Sr, Na, Nd, Pr, Sm, Gd, Dy, Y, Eu, Tb, and Ba; and “M2” is at least one selected from the group consisting of Mg, W, Mn, Al, Ge, Ru, Nb, Ta, Co, Zr, Hf, Fe, Cr, and Ga.
A solid electrolyte material having excellent Li ion conductivity may be obtained for the reason that the present invention has the above-mentioned general formula. In addition, the solid electrolyte material of the present invention has the advantages such as to have high lithium content and be stable in the atmosphere.
In the above-mentioned present invention, the solid electrolyte material is preferably amorphous. The reason therefor is to allow resistance increase in the grain boundary to be prevented.
In the above-mentioned present invention, the solid electrolyte material is preferably in thin film form. The reason therefor is that the minute solid electrolyte material may be obtained and Li ion conductivity may be improved.
In the above-mentioned present invention, the solid electrolyte material preferably has a thickness of 200 nm to 5 μm.
In the above-mentioned present invention, the “a” and the “b” are preferably 0.
Further, the present invention provides a lithium battery comprising a cathode active material layer containing a cathode active material, an anode active material layer containing an anode active material, and a solid electrolyte layer formed between the above-mentioned cathode active material layer and the above-mentioned anode active material layer, characterized in that the above-mentioned solid electrolyte layer contains the above-mentioned solid electrolyte material.
According to the present invention, the use of the above-mentioned solid electrolyte material allows a high-output lithium battery.
Further, the present invention provides a method of producing a solid electrolyte material, comprising steps of: preparing a raw material, in which the raw material is made of Li, La, Ti, M1 (M1 being at least one selected from the group consisting of Sr, Na, Nd, Pr, Sm, Gd, Dy, Y, Eu, Tb, and Ba), and M2 (M2 being at least one selected from the group consisting of Mg, W, Mn, Al, Ge, Ru, Nb, Ta, Co, Zr, Hf, Fe, Cr, and Ga); and forming a thin film, in which the solid electrolyte material is formed using the raw material to a substrate by a reactive deposition method using oxygen, and the solid electrolyte material is represented by a general formula: Lix(La1-aM1a)y(Ti1-bM2b)zOδ, in which “x”, “y”, and “z” satisfy relations of x+y+z=1, 0.652≦x/(x+y+z)≦0.753, and 0.167≦y/(y+z)≦0.232; “a” is 0≦a≦1; “b” is 0≦b≦1; “δ” is 0.8≦δ≦1.2.
According to the present invention, the use of the reactive deposition method allows a minute thin film to be formed, and a solid electrolyte material having excellent Li ion conductivity may be obtained by the above-mentioned general formula.
In the above-mentioned present invention, the above-mentioned solid electrolyte material is preferably amorphous. The reason therefor is to allow resistance increase in the grain boundary to be prevented.
In the above-mentioned present invention, the solid electrolyte material preferably has a thickness of 200 nm to 5 μm. The reason therefor is that the minute solid electrolyte material may be obtained and Li ion conductivity may be improved.
In the above-mentioned present invention, the solid electrolyte material is preferably formed in the thin film forming step by the reactive deposition method using an oxygen plasma.
In the above-mentioned present invention, the substrate is preferably a member containing a cathode active material layer or an anode active material layer. The reason therefor is to be useful for producing a lithium battery.
The present invention produces the effect such as to allow a solid electrolyte material having excellent Li ion conductivity.
A solid electrolyte material, a lithium battery and a method of producing a solid electrolyte material of the present invention are hereinafter described in detail.
A solid electrolyte material of the present invention is first described. A solid electrolyte material of the present invention is represented by a general formula: Lix(La1-aM1a)y(Ti1-bM2b)zOδ, characterized in that “x”, “y”, and “z” satisfy relations of x+y+z=1, 0.652≦x/(x+y+z)≦0.753, and 0.167≦y/(y+z)≦0.232; “a” is 0≦a≦1; “b” is 0≦‘b≦1; “δ” is 0.8≦δ≦1.2; “M1” is at least one selected from the group consisting of Sr, Na, Nd, Pr, Sm, Gd, Dy, Y, Eu, Tb, and Ba; and “M2” is at least one selected from the group consisting of Mg, W, Mn, Al, Ge, Ru, Nb, Ta, Co, Zr, Hf, Fe, Cr, and Ga.
A solid electrolyte material having excellent Li ion conductivity may be obtained for the reason that the present invention has the above-mentioned general formula. It has been conventionally known that a solid electrolyte material having a perovskite type structure, such as La2/3-xLi3xTiO3, has high Li ion conductivity. However, with regard to a compound such as La2/3-xLi3xTiO3, the problem is that lithium content in the compound is so low that carrier concentration for contributing to Li ion conduction is low and consequently sufficient Li ion conductivity may not be obtained. On the other hand, the problem is that a compound having high lithium content (such as Li3N) is unstable in the atmosphere while having high Li ion conductivity. On the contrary, the solid electrolyte material of the present invention has the advantages such as to have high lithium content and be stable in the atmosphere.
A solid electrolyte material of the present invention is represented by a general formula: Lix(La1-aM1a)y(Ti1-bM2b)zOδ. In the above-mentioned general formula, “x”, “y”, and “z” satisfy relations of 0.652≦x/(x+y+z)≦0.753, and 0.167≦y/(y+z)≦0.232.
Further, in the above-mentioned general formula, “a” is 0≦a≦1, and is preferably 0≦a≦0.5. Similarly, in the above-mentioned general formula, “b” is 0≦b≦1, and is preferably 0≦b≦0.5. In the present invention, “a” or “b” may be 0, and “a” and “b” may be 0.
Further, in the above-mentioned general formula, “δ” is 0.8≦δ≦1.2. In consideration of valences of metallic elements included in the above-mentioned general formula, the value of δ may be specified by the electroneutrality principle; yet, oxygen deficiency and oxygen excess may be actually caused. Thus, in the present invention, the range of δ is prescribed at 0.8≦δ≦1.2 in consideration of oxygen deficiency and oxygen excess.
Further, in the above-mentioned general formula, “M1” is a metal capable of being located at the same site as that of La in a crystal structure; specifically, at least one selected from the group consisting of Sr, Na, Nd, Pr, Sm, Gd, Dy, Y, Eu, Tb, and Ba.
Further, in the above-mentioned general formula, “M2” is a metal capable of being located at the same site as that of Ti in a crystal structure; specifically, at least one selected from the group consisting of Mg, W, Mn, Al, Ge, Ru, Nb, Ta, Co, Zr, Hf, Fe, Cr, and Ga.
A solid electrolyte material of the present invention may be amorphous or crystalline. The case of being amorphous has the advantage that resistance increase in a grain boundary may be prevented. On the other hand, the case of being crystalline has the advantage that Li ion conductivity in a crystal grain is high. In addition, in the present invention, the use of the after-mentioned reactive deposition method allows crystal grains to be favorably joined to each other and allows resistance increase in a grain boundary to be restrained even in the case of being crystalline.
Further, a solid electrolyte material of the present invention may be bulky or in thin film form, and is preferably in thin film form. The reason therefor is that the use of the after-mentioned reactive deposition method allows a minute solid electrolyte material to be obtained and allows Li ion conductivity to be improved.
The size of a solid electrolyte material of the present invention is not particularly limited. Above all, in the case where a solid electrolyte material of the present invention is in thin film form, the thickness of the thin film is preferably 200 nm or more, more preferably 500 nm or more, and far more preferably 800 nm or more. On the other hand, the thickness of the thin film is preferably 5 μm or less, more preferably 3 μm or less, and far more preferably 2 μm or less.
A solid electrolyte material of the present invention may be used for optional uses in which Li ion conductivity is required. Examples of the uses of the solid electrolyte material include batteries such as a lithium battery and sensors such as a gas sensor. A method of producing a solid electrolyte material of the present invention is described in detail in the after-mentioned ‘C. Method of producing solid electrolyte material’. A solid electrolyte material in a bulk body may be produced by using a method such as a mechanical milling method and a solid phase method.
Next, a lithium battery of the present invention is described. A lithium battery of the present invention is a lithium battery comprising a cathode active material layer containing a cathode active material, an anode active material layer containing an anode active material, and a solid electrolyte layer formed between the above-mentioned cathode active material layer and the above-mentioned anode active material layer, characterized in that the above-mentioned solid electrolyte layer contains the above-mentioned solid electrolyte material.
According to the present invention, the use of the above-mentioned solid electrolyte material allows a high-output lithium battery.
A lithium battery of the present invention is hereinafter described in each constitution.
A solid electrolyte layer in the present invention is first described. A solid electrolyte layer in the present invention contains the above-mentioned solid electrolyte material. The range of the thickness of the solid electrolyte layer is preferably the same as the range of the thickness of the above-mentioned solid electrolyte material.
Next, a cathode active material layer in the present invention is described. A cathode active material layer in the present invention is a layer containing at least a cathode active material, and may contain at least one of a conductive material, a solid electrolyte material and a binder, as required. Examples of the cathode active material include LiCoO2, LiMnO2, Li2NiMn3O8, LiVO2, LiCrO2, LiFePO4, LiCoPO4, LiNiO2 and LiNi1/3Co1/3Mn1/3O2.
A cathode active material layer in the present invention may further contain a conductive material. The addition of the conductive material allows the conductivity of the cathode active material layer to be improved. Examples of the conductive material include acetylene black, Ketjen Black and carbon fiber. Further, the cathode active material layer may further contain a solid electrolyte material. The addition of the solid electrolyte material allows Li ion conductivity of the cathode active material layer to be improved. Examples of the solid electrolyte material include an oxide solid electrolyte material and a sulfide solid electrolyte material. Further, the cathode active material layer may further contain a binder. Examples of the binder include a fluorine-containing binder such as polytetrafluoroethylene (PTFE). The thickness of the cathode active material layer is preferably within a range of 0.1 μm to 1000 μm, for example.
Next, an anode active material layer in the present invention is described. An anode active material layer in the present invention is a layer containing at least an anode active material, and may contain at least one of a conductive material, a solid electrolyte material and a binder, as required. Examples of the anode active material include a metal active material and a carbon active material. Examples of the metal active material include In, Al, Si, and Sn. On the other hand, examples of the carbon active material include mesocarbon microbeads (MCMB), high orientation property graphite (HOPG), hard carbon and soft carbon.
A conductive material, a solid electrolyte material and a binder used for the anode active material layer are the same as in the case of the above-mentioned cathode active material layer. The thickness of the anode active material layer is preferably within a range of 0.1 μm to 1000 μm, for example.
A lithium battery of the present invention comprises at least the above-mentioned solid electrolyte layer, cathode active material layer and anode active material layer, ordinarily further comprises a cathode current collector for performing current collecting of the cathode active material layer and an anode current collector for performing current collecting of the anode active material layer. Examples of a material for the cathode current collector include SUS, aluminum, nickel, iron, titanium and carbon, and preferably SUS among them. On the other hand, examples of a material for the anode current collector include SUS, copper, nickel and carbon, and preferably SUS among them. Factors such as the thickness and shape of the cathode current collector and the anode current collector are preferably selected properly depending on the uses of a lithium battery. A battery case of a general lithium battery may be used for a battery case used for the present invention. Examples of the battery case include a battery case made of SUS.
A lithium battery of the present invention may be a primary battery or a secondary battery, and preferably a secondary battery among them. The reason therefor is to be repeatedly chargeable and dischargeable and be useful as a car-mounted battery, for example. Examples of the shape of a lithium battery of the present invention include a coin shape, a laminate shape, a cylindrical shape and a rectangular shape. A method of producing a lithium battery of the present invention is not particularly limited as long as it is a method for allowing the above-mentioned lithium battery, and the same method as that of producing a general lithium battery may be used. Examples thereof include a method such that a material constituting a cathode active material layer, a material constituting a solid electrolyte layer and a material constituting an anode active material layer are sequentially pressed to thereby produce a power generating element and this power generating element is stored inside a battery case, which is crimped.
Next, a method of producing a solid electrolyte material of the present invention is described. A method of producing a solid electrolyte material of the present invention comprises steps of: preparing a raw material, in which the raw material is constituted of Li, La, Ti, M1 (M1 being at least one selected from the group consisting of Sr, Na, Nd, Pr, Sm, Gd, Dy, Y, Eu, Tb, and Ba), and M2 (M2 being at least one selected from the group consisting of Mg, W, Mn, Al, Ge, Ru, Nb, Ta, Co, Zr, Hf, Fe, Cr, and Ga); and forming a thin film, in which the solid electrolyte material is formed using the raw material to a substrate by a reactive deposition method using oxygen, and the solid electrolyte material is represented by a general formula: Lix(La1-aM1a)y(Ti1-bM2b)zOδ, in which “x”, “y”, and “z” satisfy relations of x+y+z=1, 0.652≦x/(x+y+z)≦0.753, and 0.167≦y/(y+z)≦0.232; “a” is 0≦a≦1; “b” is 0≦b≦1; “δ” is 0.8≦δ≦1.2.
According to the present invention, the use of the reactive deposition method allows a minute thin film to be formed, and a solid electrolyte material having excellent Li ion conductivity may be obtained by the above-mentioned general formula.
A method of producing a solid electrolyte material of the present invention is hereinafter described at each step.
The step of preparing a raw material in the present invention is first described. The step of preparing a raw material in the present invention is a step of preparing a raw material, in which the raw material is made of Li, La, Ti, M1 (M1 being at least one selected from the group consisting of Sr, Na, Nd, Pr, Sm, Gd, Dy, Y, Eu, Tb, and Ba), and M2 (M2 being at least one selected from the group consisting of Mg, W, Mn, Al, Ge, Ru, Nb, Ta, Co, Zr, Hf, Fe, Cr, and Ga).
In the present invention, simplex metals of Li, La, Ti, M1 and M2 are ordinarily prepared. These simplex metals have preferably high purity. The reason therefor is to allow a solid electrolyte material with fewer impurities. Further, ordinarily, M1 is not used in the case of obtaining a solid electrolyte material in which “a” in the above-mentioned general formula is 0, and M2 is not used in the case of obtaining a solid electrolyte material in which “b” in the above-mentioned general formula is 0.
Next, the step of forming a thin film in the present invention is described. The step of forming a thin film in the present invention is a step of forming the above-mentioned solid electrolyte material while using the above-mentioned raw material to a substrate by a reactive deposition method using oxygen.
In the present invention, the solid electrolyte material is formed by a reactive deposition method. In this method, the thin-film solid electrolyte material is formed by volatilizing the raw material to react the volatilized raw material with oxygen. Examples of a method of volatilizing the raw material include a resistance heating method and an electron beam method. Examples of a method of reacting the volatilized raw material with oxygen include a method of using oxygen plasma and a method of using oxygen gas. In addition, in the present invention, the reactive deposition is preferably performed in vacua, and is preferably performed specifically in a vacuum of 1×10−10 mBar or less. The reason therefor is that a minute thin film may be formed. The thickness of the solid electrolyte material may be controlled by deposition time.
Further, in the present invention, the thin-film solid electrolyte material is formed on the substrate. The substrate in the present invention is not particularly limited and preferably selected properly depending on the uses of the solid electrolyte material. For example, in the case of using the solid electrolyte material as a solid electrolyte layer of a lithium battery, a member having a cathode active material layer or an anode active material layer is preferably used as the substrate.
A solid electrolyte material obtained by the present invention is the same content as that described in the above-mentioned ‘A. Solid electrolyte material’; therefore, the description herein is omitted. The present invention may provide a solid electrolyte material characterized by being obtained by the above-mentioned method of producing a solid electrolyte material.
The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are exemplification, and any one that has substantially the same constitution as one that the technical idea described in the claim of the present invention and exerts similar effect is included in the technical scope of the present invention.
The present invention is described more specifically while showing Examples hereinafter.
Lithium metal (ribbon, a purity of 99.9%, manufactured by Sigma-Aldrich Co. LLC.), lanthanum metal (a purity of 99.9%, manufactured by Sigma-Aldrich Co. LLC.), and titanium metal (slug, a purity of 99.98%, manufactured by Alfa Aesar) were first prepared as a raw material. Next, the lithium metal was put in a 40-cm3 crucible made of pyrolytic boron nitride (PBN) and placed in a chamber. Next, the lanthanum metal and the titanium metal were each put in a 40-cm3 crucible made of pyrolytic graphite and placed in the chamber in the same manner. An Si/SiO2/Ti/Pt laminated body (manufactured by NOVA Electronic Materials, LLC.) was used as a substrate, a deposition area was determined at 0.785 cm2 (equivalent to φ 10 mm), and a distance from the raw material to the substrate was determined at 500 mm. Next, the inside of the chamber was subject to a high vacuum of 1×10−10 mBar or less.
Thereafter, resistance heating (Knudsen Cells) was performed for the crucible in which the lithium metal was put to volatilize the lithium, and simultaneously electron beam irradiation was performed for the crucible in which the lanthanum metal was put and the crucible in which the titanium metal was put to volatilize the lanthanum metal and the titanium metal. Oxygen plasma was caused in the chamber by using an oxygen plasma generator (manufactured by Oxford Applied Research Ltd., RF source, HD25™) and reacted with the volatilized raw material to thereby obtain a thin-film solid electrolyte material on the substrate. The substrate was not heated during the deposition.
The thickness of the obtained solid electrolyte material was 390 nm. When XRD measurement (using CuKa) was performed for the obtained solid electrolyte material, it was confirmed that the solid electrolyte material was amorphous. When ICP analysis (inductively coupled plasma analysis) was performed for the obtained solid electrolyte material, a result of Li:La:Ti=65.2:7.0:27.8 was obtained.
A thin-film solid electrolyte material was obtained in each case in the same manner as in Example 1 except for properly adjusting the amount of the metals volatilized from the crucible with a shutter. The composition of the solid electrolyte materials obtained in each of Examples 2 to 6 and Comparative Examples 1 and 2 at a ratio of Li:La:Ti was as shown in the following Table 1.
Li ion conductivity of the solid electrolyte materials obtained in each of Examples 1 to 6 and Comparative Examples 1 and 2 was evaluated. Platinum was first deposited on the surface of the solid electrolyte material formed on the substrate to produce a symmetrical cell of Pt/solid electrolyte material/Pt. Next, an alternating current impedance method was performed at a temperature of 25° C. to calculate Li ion conductivity. The results are shown in Table 1 and
As shown in Table 1, Examples 1 to 6 and Comparative Examples 1 and 2 were all fixed in the vicinity of La/(La+Ti)=0.20. Further, as shown in
A thin-film solid electrolyte material was obtained in each case in the same manner as in Example 1 except for properly adjusting the amount of the metals volatilized from the crucible with a shutter. The composition of the solid electrolyte materials obtained in each of Examples 7 to 9 and Comparative Examples 3 and 4 at a ratio of Li:La:Ti was as shown in the following Table 2.
Li ion conductivity of the solid electrolyte materials obtained in each of Examples 5, 7 to 9 and Comparative Examples 3 and 4 was evaluated. The evaluation method is the same as the above. The results are shown in Table 2 and
As shown in Table 2, Examples 5, 7 to 9 and Comparative Examples 3 and 4 were all fixed in the vicinity of Li/(Li+La+Ti)=0.75. Further, as shown in
A thin-film solid electrolyte material was obtained in each case in the same manner as in Example 1 except for properly adjusting the amount of the metals volatilized from the crucible with a shutter. The compositions of the solid electrolyte materials obtained in Examples 10 to 15 and Comparative Examples 5 to 11 at a ratio of Li:La:Ti were as shown in the following Table 3.
Li ion conductivity of the solid electrolyte materials obtained in each of Examples 10 to 15 and Comparative Examples 5 to 11 was evaluated. The evaluation method is the same as the above. The results are shown in Table 3.
As shown in Table 3, Li ion conductivity was remarkably high in Examples 10 to 15 as compared with Comparative Examples 5 to 11. In addition, when the result of Table 3 was shown in a ternary view, as shown in
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2010/056606 | 4/13/2010 | WO | 00 | 12/6/2012 |
