Patent Grant
10541443
This application is a national phase application of International Application No. PCT/JP2016/070331, filed Jul. 8, 2016, and claims the priority of Japanese Application No. 2015-138029, filed Jul. 9, 2015, the content of both of which is incorporated herein by reference.
The present invention relates to a lithium solid electrolyte with favorable ion conductivity and to a lithium battery including the solid electrolyte.
With the rapid spread of information-related and communication apparatuses such as personal computers, video cameras, and mobile phones in recent years, the development of batteries utilized as power supplies for the apparatuses has been regarded as important. The development of high-output and high-capacity batteries for electric or hybrid vehicles has also been pursued in the automobile industry and the like. Among the various batteries, lithium batteries currently attract attention from the viewpoint of having high energy densities.
In currently commercially available lithium batteries, electrolytic solutions including flammable organic solvents are used, and therefore it is preferable to attach safety devices that inhibit temperature from increasing in the event of a short circuit and to improve structures and materials for preventing a short circuit. In contrast, all-solid-state lithium batteries in which solid electrolyte layers are used instead of electrolytic solutions are considered to allow the simplification of safety devices and to be excellent in production cost and productivity because any flammable organic solvent is not used in the batteries.
Sulfide solid electrolyte materials are known as solid electrolyte materials used in all-solid-state lithium batteries. For example, Non Patent Literature 1 discloses a Li ion conductor (sulfide solid electrolyte material) having a composition of Li(4-x)Ge(1-x)PxS4. Patent Literature 1 discloses an LiGePS-based sulfide solid electrolyte material having a high ratio of crystal phase having a specific peak in X-ray diffraction measurement. In addition, Non Patent Literature 2 discloses an LiGePS-based sulfide solid electrolyte material.
A solid electrolyte material with favorable ion conductivity is demanded from the viewpoint of the higher output of a battery. The present invention was made in view of the above-described problems, with an object of providing a sulfide solid electrolyte material with favorable Li ion conductivity.
Non Patent Literature 1 and Patent Literature 1 examine a composition of Li(4-x)Ge(1-x)PxS4. Non Patent Literature 2 examines Li10GeP2S12 (LGPS) which exhibits a high ion conductivity of 12 mS cm−1 equivalent to the ion conductivity of an electrolytic solution and which is a system found in a composition of Li3.35Ge0.35P0.65S4. The sulfide solid electrolyte materials, which are solid-solution systems of Li4GeS4 and Li3PS4, include compositions with relatively high Li contents. An object of the present invention is to provide a sulfide solid electrolyte material that includes a composition in which the content of Li is less than those in the conventional technologies and that has favorable Li ion conductivity.
Still another object of the present invention is to provide a lithium battery including the sulfide solid electrolyte material.
The following solutions to the problems described above are provided by the present invention.
[1] A solid electrolyte including a sulfide-based solid electrolyte represented by a composition formula: (Li2S)x(MS2)y(P2S5)2, wherein
M is at least one selected from the group consisting of Ge, Sb, Si, Sn, B, Al, Ga, In, Zr, V, and Nb; and
0.53≤x≤0.74, 0.13≤y≤0.37, 0.04≤z≤0.15, and x+y+z=1 are satisfied.
[2] The solid electrolyte according to [1], wherein at least some of the sulfide-based solid electrolytes include characteristic peaks at at least diffraction angles (2θ) in the vicinities of 15.9°, 18.3°, 25.9°, 30.4°, 31.8°, 40.3°, 41.3°, 45.5°, and 48.4° in powder X-ray diffractometry with a Cu-Kα ray having an X-ray wavelength of 1.5418 Å.
[3] A lithium battery including the solid electrolyte according to [1] or [2].
According to the present invention, the sulfide solid electrolyte material is provided that includes a composition in which the content of Li is lower than those in conventional technologies and any halogen element with low stability is not included, and that has favorable Li ion conductivity and excellent electrochemical stability. In addition, the sulfide solid electrolyte material includes an argyrodite type structure which is stable at room temperature. There is also provided the lithium battery including the sulfide solid electrolyte material.
A sulfide solid electrolyte material of the present invention and a lithium battery including the sulfide solid electrolyte material will be described in detail below. However, the present invention is not limited to embodiments described below.
As a result of intensive examination, the present inventor found that a solid electrolyte including a sulfide-based solid electrolyte represented by a composition formula: (Li2S)x(MS2)y(P2S5)z, in which M is at least one selected from the group consisting of Ge, Sb, Si, Sn, B, Al, Ga, In, Zr, V, and Nb, and 0.53≤x≤0.74, 0.13≤y≤0.37, 0.04≤z≤0.15, and x+y+z=1 are satisfied, has a high ion conductivity, and arrived at the present invention.
(Sulfide-Based Solid Electrolyte)
The sulfide-based solid electrolyte of the present invention will be described with reference to the ternary composition diagram of an Li2S-MS2-P2S5 of ” in
” indicate the compositions of comparative examples described later, and the points “
” indicate the compositions of the sulfide-based solid electrolytes described in the above Citation List and the like. A chain line connecting Li4GeS4 and Li3PS4 is a line of a Li4GeS4—Li3PS4 solid-solution system, and the compositions of the conventionally reported sulfide-based solid electrolytes are located above the line and proved to have a relatively high Li content.
The sulfide-based solid electrolyte of the present invention includes a composition represented by (Li2S)x(MS2)y(P2S5)z, in which M is at least one selected from the group consisting of Ge, Sb, Si, Sn, B, Al, Ga, In, Zr, V, and Nb, and 0.53≤x≤0.74, 0.13≤y≤0.37, 0.04≤z≤0.15, and x+y+z=1 are satisfied. When the composition of the solid electrolyte is within the above range, the solid electrolyte having an excellent ion conductivity can be obtained.
In the ternary composition diagram of the Li2S-MS2-P2S5 system of
M included in the composition is at least one selected from the group consisting of Ge, Sb, Si, Sn, B, Al, Ga, In, Zr, V, and Nb. The actual adoption of Ge has been reported as a conventional technology. According to the present invention, however, M is not limited to Ge. Because Ge is relatively expensive, the possible selection of the elements other than Ge is advantageous in terms of cost. Further, the composition of the present invention includes no halogen element. Since halogen elements have low stability, the inclusion of no halogen element results in improvement in the stability of the solid electrolyte of the present invention.
The solid electrolyte in the composition range includes an argyrodite type phase at a high rate. The argyrodite type phase is a phase observed in a high ion-conductive Li7PS6 known as a conventional technology. While not wishing to be bound by any particular theory, the inclusion of the argyrodite type phase at a high rate into the solid electrolyte is considered to contribute to the high ion conductivity of the solid electrolyte.
The argyrodite type phase exhibits characteristic peaks in X-ray diffraction measurement.
More specifically, at least some of the sulfide solid electrolyte materials of the present invention include characteristic peaks at at least diffraction angles (2θ) in the vicinities of 15.9°, 18.3°, 25.9°, 30.4°, 31.8°, 40.3°, 41.3°, 45.5°, and 48.4° in powder X-ray diffractometry with a Cu-Kα ray having an X-ray wavelength of 1.5418 Å. At least some of the sulfide solid electrolyte materials of the present invention include an argyrodite type phase at a high rate, as judged by the diffraction angles (2θ) of the characteristic peaks. An argyrodite type phase observed in Li7PS6 known as a conventional technology was confirmed at 210° C. or more, whereas an argyrodite type crystal structure observed in the sulfide solid electrolyte material of the present invention was confirmed at room temperature. In other words, the argyrodite type phase observed in the present invention is stable at room temperature.
A method of producing the solid electrolyte of the present invention will be described. A method of producing the solid electrolyte material of the present invention includes: a raw material composition preparation step of grinding, mixing, and molding a Li element, an M element (M is at least one selected from the group consisting of Ge, Sb, Si, Sn, B, Al, Ga, In, Zr, V, and Nb), a P element, and a S element to prepare a raw material composition; and a heating step of heating the raw material composition, thereby obtaining a solid electrolyte material.
Mechanical milling may be used for the grinding and the mixing. The mechanical milling is a method of grinding a sample while applying mechanical energy thereto. Examples of such mechanical milling include vibration mill, ball mill, turbo mill, mechano-fusion, and disk mill. Especially, vibration mill and ball mill are preferred. The conditions of vibration mill as one example are not particularly limited if the conditions enable a physical object to be ground and mixed. The vibrational amplitude of vibration mill is preferably, for example, within a range of 5 mm to 15 mm, especially, within a range of 6 mm to 10 mm. The vibration frequency of vibration mill is preferably, for example, within a range of 500 rpm to 2000 rpm, especially, within a range of 1000 rpm to 1800 rpm. The filling rate of a sample in vibration mill is preferably, for example, within a range of 1% by volume to 80% by volume, especially, within a range of 5% by volume to 60% by volume, particularly, within a range of 10% by volume to 50% by volume. A vibrator (for example, a vibrator made of alumina) is preferably used for vibration mill.
The heating temperature in the heating step can be adjusted as appropriate depending on a starting material, and is preferably within a range of about 500° C. to 900° C. The heating time includes heating-up time and retention time, each time of which is preferably adjusted as appropriate so as to obtain a desired solid electrolyte material. Each may be allowed to be, for example, within a range of 30 minutes to 10 hours. Further, when cooling is performed to room temperature after the heating, natural cooling may be adopted or annealing may be performed so as to obtain a desired solid electrolyte material.
It is preferable to operate the series of steps under an inert gas atmosphere such as argon in order to prevent the raw material composition and the obtained solid electrolyte material from degrading due to moisture in air.
The sulfide solid electrolyte material of the present invention preferably has a high ion conductivity, and the ion conductivity of the sulfide solid electrolyte material at 25° C. is preferably 7.5×10−6 S/cm or more, and more preferably 1.0×10−5 S/cm or more. The form of the sulfide solid electrolyte material of the present invention is not particularly limited, but examples thereof include a powder form. Further, the average particle diameter of the sulfide solid electrolyte material in a powder form is preferably, for example, within a range of 0.1 μm to 50 μm.
The sulfide solid electrolyte material of the present invention has a high ion conductivity and can be therefore used in an optional application in need of ion conductivity. Especially, the sulfide solid electrolyte material of the present invention is preferably used in a battery, because the sulfide solid electrolyte material can greatly contribute to the higher output of the battery.
The lithium battery of the present invention will be described with reference to
The present invention will be described in more detail below with reference to examples. The following examples are not intended to limit the present invention.
(Production of Li2S-MS2 (GeS2)—P2S5-Based Sample)
In a glove box under an argon atmosphere, Li2S, MS2 (GeS2), and P2S5 as starting materials were weighed to produce a mixed sample by using a vibration mill. The sample was put in a pelleter, and a pressure of 20 MPa was applied to the pelleter by using a uniaxial pressing machine, to mold a pellet having a diameter of 13 mm. The pellet was vacuum-encapsulated in a quartz tube coated with carbon. The temperature of the quartz tube in which the pellet was put was raised to 700° C. for 6 hours (at a temperature-raising rate of 1.89° C./min). Then, the quartz tube was retained for 8 hours and thereafter naturally cooled. The compositions of the synthesized samples are listed in Table 1. Referring to the ternary composition diagram of the Li2S-MS2 (GeS2)—P2S5 system of ” indicate the compositions of examples, the points “
” indicate the compositions of comparative examples, and the points “
” indicate the compositions of the sulfide-based solid
electrolytes described in the above Citation List and the like.
(Powder X-Ray Diffraction Measurement)
Powder X-ray diffraction measurement was performed using powder X-ray diffractometers Ulima-IV (manufactured by Rigaku Corporation) and Smart Lab (manufactured by Rigaku Corporation) in order to identify crystals included in the produced samples. A Cu-Kα ray having an X-ray wavelength of 1.5418 Å was used in the powder X-ray diffraction measurement. The powder X-ray diffraction measurement was performed at diffraction angles (2θ) in a range of 10 to 100°.
(Measurement of Conductivity)
The ground sample was put in a cell for ordinary temperature, and a pressure of 5 MPa was then applied to the cell for ordinary temperature to produce a pellet. A gold powder was dispersed on both surfaces of the pellet, and a pressure of 15 MPa was applied to the pellet to form electrodes on both surfaces of the pellet and to produce a test sample. An impedance gain phase analyzer Solatron 1260 (manufactured by Solartron) was used in measurement of the conductivity of the test sample. An alternating-current impedance was measured under conditions of a measurement range of 1 Hz to 10 MHz, a measurement temperature of 25° C., an alternating voltage of 50 to 100 mV, and an integration time of 2 seconds, to measure the conductivity of the sample.
(Measurement of Thermal Stability)
Differential calorimetry was performed using a differential type differential thermal balance Thermo Plus EVO II TG8120 (manufactured by Rigaku Corporation) in order to examine the thermal stability of the sample. Among the compositions of the Li2S-MS2 (GeS2)—P2S5 system in Table 1, Li1.75Ge0.75P0.25S3 (Example 2) of which the characteristic peaks of the argyrodite type phase were able to be distinctly discriminated as a result of X-ray diffraction measurement described later was adopted as a composition as a base. Conditions for obtaining a solid electrolyte material were set to the same conditions as the conditions in the production of the Li2S-MS2 (GeS2)—P2S5-based sample described above except that in the heating step, the temperature was raised to 870° C. or 530° C. for 3 hours, followed by retention for 3 hours. A sample was prepared for measuring thermal stability in a glove box under an argon atmosphere. In an SUS pan, 10 mg of the ground sample was put, and encapsulated at 10 MPa to produce a test sample. In an SUS pan, Al2O3 was put, and encapsulated at 10 MPa to produce a reference sample. Differential calorimetry was performed by raising the temperature of the test sample from room temperature to 900° C. at a temperature-raising rate of 5° C. to 20° C./min.
(Production of Li2S-MS2 ((Sn, Si)S2)—P2S5-Based Sample)
In the compositions of Table 1, Ge was used as an element M in the compositions. A sample was produced using Sn and Si instead of Ge as the element M. Among the compositions of the Li2S-MS2 (GeS2)—P2S5 system in Table 1, Li1.75Ge0.75P0.25S3 (Example 2) of which the characteristic peaks of the argyrodite type phase were able to be distinctly discriminated as a result of X-ray diffraction measurement described later was adopted as a composition as a base. A procedure of producing the sample was the same as described above except that Ge as a starting material was changed to Sn and Si. The contents of Sn and Si were adjusted so that β=0.2 or 0.3 is satisfied, and α is in a range of 0 to 0.4 in a composition formula: Li3.45−4α+β(Sn0.09+αSi0.36+β)P0.55−βS4. Referring to a ternary composition diagram of a Li2S-MS2 ((Sn, Si)S2)—P2S5 system of ” indicates a composition of α=0.4. The points “∇” indicate compositions on the line of β=0.3, and in particular, the point “
” indicates a composition of α=0.4. The point “*” indicates the composition of Li1.75Ge0.75P0.25S3 (Example 2).
[Evaluation]
(X-Ray Diffraction Measurement)
X-ray diffraction (XRD) measurement was performed using the sulfide solid electrolyte material obtained in Example 2. The results are illustrated in
Then, X-ray diffraction measurement (using a CuKα ray) was performed using the sulfide solid electrolyte materials obtained in Examples 1 to 4 and the samples for comparisons obtained in Comparative Examples 22 to 26. The results are illustrated in
In contrast, in the samples of Comparative Examples 22 to 26, any peaks of the argyrodite type phase and the LGPS phase were not observed, and many reflections that were able to belong to other known impurities were observed. The solid electrolyte material within the composition range of the present invention includes an argyrodite type phase, an LGPS phase, and/or an unknown phase, and the inclusion of the phases is considered to contribute to performance such as excellent ion conductivity.
(Measurement of Li Ion Conductivity)
Li ion conductivities at 25° C. were measured using the sulfide solid electrolyte materials obtained in Examples 1 to 4 and the samples for comparisons obtained in Comparative Examples 22 to 24. The results of the measured conductivities of the solid electrolytes are listed in Table 2.
The Li5GePS7 system (Example 1) exhibited the highest ion conductivity, 6.6×10−5 S cm−1, followed by the Li1.75Ge0.75P0.25S3 system (Example 2) exhibiting 2.1×10−5 S cm−1. In Example 1, the LGPS phase (Li3PS4) is considered to contribute to high ion conductivity. The Li4.1Ge2.6P0.7S9 system including an argyrodite phase (Example 4) exhibited an ion conductivity of 7.5×10−6 S cm−1. The Li4.1Ge2.6P0.7S9 system was considered to have the ion conductivity that was lower than the ion conductivity in Example 2 in which the argyrodite phase was obtained as an approximately single phase because the system included germanium sulfide with insulating properties as an impurity. The Li5.5Ge1.5P0.5S7 system (Example 3) exhibited an ion conductivity of 1.5×10−5 S cm−1. In Example 3, not only known substances but also plural unknown reflections were observed in the powder X-ray diffraction pattern, suggesting a complicated system; however, relatively high ion conductivity was exhibited. The compositions of Comparative Examples exhibited relatively low ionic conductivity (<10−7 S cm−1). This is considered to be because impurities included in the compositions of Comparative Examples were more than those in Examples.
(Measurement of Thermal Stability)
In Li1.75Ge0.75P0.25S3 synthesized at 700° C. (Example 2), the characteristic peaks of an argyrodite type phase were able to be distinctly discriminated as a result of the X-ray diffraction measurement. A solid electrolyte material was synthesized at a synthesis temperature of 870° C. while the composition ratio was maintained. The temperature of the obtained solid electrolyte material was raised from room temperature to 900° C., and the differential thermal analysis (DTA) of the solid electrolyte material was performed. As a result, an exothermic peak was observed in the vicinity of 500° C., and an endothermic peak was observed in the vicinity of 550° C. Since a change of a temperature-raising rate at 5 to 20° C./min resulted in a change in temperature at which the exothermic peak occurred but in no change in temperature at which the endothermic peak occurred, the exothermic peak and the endothermic peak were considered to result from the stabilization of the phase and the fusion of the sample, respectively. On the basis of the results, the argyrodite type phase is considered to be a metastable phase.
On the basis of the results of the differential thermal analysis, a solid electrolyte material was synthesized at 530° C. to attempt to obtain the stable phase of a system. Further, the result of an ion conductivity measured according to each synthesis condition (heating temperature) of the solid electrolyte material is listed in Table 3. The solid electrolyte material with the stable phase had ion conductivity superior to the ion conductivity of the solid electrolyte material with the metastable phase.
(Production of Li2S-MS2 ((Sn, Si)S2)—P2S5-Based Sample)
A solid electrolyte material was produced using Sn and Si as elements M in a composition. In a composition formula: Li3.45−4α+β(Sn0.09+αSi0.36+β)P0.55−βS4, β=0.2 or 0.3 is satisfied, and α is in a range of 0 to 0.4. Referring to the ternary composition diagram of the Li2S-MS2 ((Sn, Si)S2)—P2S5 system of ” indicates a composition of α=0.4. The points “∇” indicate compositions on the line of β=0.3, and in particular, the point “
” indicates a composition of α=0.4. The point “*” indicates the composition of Li1.75Ge0.75P0.25S3 (Example 2) as a base.
The X-ray diffraction and Li ion conductivity of the produced solid electrolyte material including Sn and Si were measured under the same conditions as the conditions described above. The results are illustrated in
The compositions of samples illustrated in
Li3.075(Sn0.735Si0.84)P0.525S6(corresponding to “” in
Li3.225(Sn0.735Si0.99)P0.375S6 (corresponding to “” in
Li1.75Ge0.75P0.25S3 (Example 2) as a base (corresponding to “*” in
Li7PS6 as a reference sample for an argyrodite phase.
It was confirmed based on the results of the X-ray diffraction measurement that the solid electrolyte materials including Sn and Si also included argyrodite phases. In addition, the argyrodite phases were formed in the solid electrolyte materials “” and “
” in which the contents of Li in the compositions were less than that in the Ge-based material “*” as the base. The ion conductivities of the solid electrolyte materials were confirmed to be equivalent to the ion conductivity of the Ge-based material.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2015-138029 | Jul 2015 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2016/070331 | 7/8/2016 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2017/007030 | 1/12/2017 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 6277524 | Kanno | Aug 2001 | B1 |
| 20060246355 | Min | Nov 2006 | A1 |
| 20130040208 | Kanno et al. | Feb 2013 | A1 |
| 20160197374 | Kato | Jul 2016 | A1 |
| Number | Date | Country |
|---|---|---|
| 2002-109955 | Apr 2002 | JP |
| 2013-211171 | Oct 2013 | JP |
| 2015-69696 | Apr 2015 | JP |
| WO2011118801 | Sep 2011 | WO |
| Entry |
|---|
| Ryoji Kanno et al., “Lithium Ionic Conductor Thio-LISICON The Li2S—GeS2—P2S5 System,” Journal of the Electrochemical Society, 148 (7) A742-A746 (2001). |
| Noriaki Kamaya et al., “A Lithium Superionic Conductor,” Nature Materials, vol. 10, Sep. 2011, Advanced online publication, Jul. 31, 2011, DOI:10.1038/NMAT3066 pp. 682-686. |
| Office Action issued in Japanese patent application No. 2015-138029 dated Jan. 8, 2019. |
| Office Action issued in Chinese Application No. 201680040131.X dated Sep. 3, 2019. |
| Number | Date | Country | |
|---|---|---|---|
| 20180205116 A1 | Jul 2018 | US |
