JP6256980B2 - Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material - Google Patents

Description

  The present invention relates to a sulfide solid electrolyte material having good ion conductivity.

  With the rapid spread of information-related equipment and communication equipment such as personal computers, video cameras, and mobile phones in recent years, development of batteries that are used as power sources has been regarded as important. Also in the automobile industry and the like, development of high-power and high-capacity batteries for electric vehicles or hybrid vehicles is being promoted. Currently, lithium batteries are attracting attention among various batteries from the viewpoint of high energy density.

  Since lithium batteries currently on the market use an electrolyte solution containing a flammable organic solvent, a safety device for preventing a temperature rise at the time of a short circuit and a structure for preventing a short circuit are required. In contrast, a lithium battery in which the electrolyte is changed to a solid electrolyte layer to make the battery completely solid does not use a flammable organic solvent in the battery, so the safety device can be simplified, and manufacturing costs and productivity can be reduced. It is considered excellent.

A sulfide solid electrolyte material is known as a solid electrolyte material used for an all solid lithium battery. For example, Non-Patent Document 1 discloses a sulfide solid electrolyte material obtained by performing mechanical milling on Li ₂ S and P ₂ S ₅ . In particular, in Non-Patent Document 1, an amorphous material is obtained in Li ₂ S: P ₂ S ₅ = 75: 25 (Li / P = 3), but Li ₂ S: P ₂ S ₅ = 80: At 20 (Li / P = 4), a Li ₂ S peak remains. Patent Document 1 discloses a sulfide-based solid electrolyte that is a Li-PS-based crystal. Patent Document 2 discloses a sulfide solid electrolyte material that substantially does not contain Li ₂ S and bridging sulfur.

JP 2013-030440 A JP 2010-199033 A

Akitoshi Hayashi et al., “Preparation of Li2S-P2S5 Amorphous Solid Electrolyte by Mechanical Milling”, Journal of the American Ceramic Society, Vol.84 / No.2, pp.477-479, 2001

  From the viewpoint of increasing the output of a battery, a solid electrolyte material having good ion conductivity is required. The present invention has been made in view of the above problems, and a main object of the present invention is to provide a sulfide solid electrolyte material having good ion conductivity.

  In order to solve the above-mentioned problems, the present invention contains Li element, P element and S element, and the ratio of Li to P element (Li / P) is larger than 3 and is amorphous. A sulfide solid electrolyte material is provided.

  According to the present invention, since the value of Li / P is large and amorphous, a sulfide solid electrolyte material having good ion conductivity can be obtained.

  In the said invention, it is preferable not to contain the metal element which belongs to 3rd group-16th group substantially.

In the above _invention, preferably contains a composition of _{Li 5x + 2y + 3 P 1} -x S 4 (0 ≦ x ≦ 0.2,0 <y <0.225).

In the above _invention, preferably contains a composition of _{Li 5x + 2y + 3 P 1} -x S 4 (0 ≦ x ≦ 0.2,0.175 ≦ y <0.225).

In the above _invention, Li 2 _S, it is preferable formed by using a raw material composition containing a P 2 _{S 5} and P.

  In the present invention, a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and an electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer In which at least one of the positive electrode active material layer, the negative electrode active material layer, and the electrolyte layer contains the sulfide solid electrolyte material described above.

  According to the present invention, a high-power battery can be obtained by using the above-described sulfide solid electrolyte material.

  Further, in the present invention, the sulfide solid electrolyte material manufacturing method described above, wherein a raw material composition containing a component of the sulfide solid electrolyte material is used, and an amorphous material is obtained by a melt quenching method. There is provided a method for producing a sulfide solid electrolyte material comprising a synthesis step of synthesizing a sulfide solid electrolyte material.

  According to the present invention, a sulfide solid electrolyte material having good ion conductivity can be obtained by performing amorphization by a melt quenching method using a predetermined raw material.

  The sulfide solid electrolyte material of the present invention has an effect that ion conductivity is good.

It is a ternary diagram illustrating the composition range of the sulfide solid electrolyte material of the present invention. It is a schematic sectional drawing which shows an example of the battery of this invention. It is explanatory drawing which shows an example of the manufacturing method of the sulfide solid electrolyte material of this invention. It is a ternary figure which shows the composition of the sulfide solid electrolyte material obtained in Example 1 and Comparative Examples 1-4. 2 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Example 1. FIG. 2 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Comparative Example 1. 3 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Comparative Example 2. 4 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Comparative Example 3. 4 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Comparative Example 4. 6 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Comparative Example 5. 7 is an X-ray diffraction spectrum of a sulfide solid electrolyte material obtained in Comparative Example 6. It is a measurement result of Li ion conductivity of the sulfide solid electrolyte material obtained in Example 1 and Comparative Examples 1 and 2. It is a measurement result of Li ion conductivity of the sulfide solid electrolyte material obtained in Example 1 and Comparative Examples 3-6.

  Hereinafter, the sulfide solid electrolyte material, battery, and method for producing the sulfide solid electrolyte material of the present invention will be described in detail.

A. First, the sulfide solid electrolyte material of the present invention will be described. The sulfide solid electrolyte material of the present invention contains Li element, P element and S element, and the ratio of Li to the P element (Li / P) is larger than 3 and is amorphous. To do.

  According to the present invention, since the value of Li / P is large and amorphous, a sulfide solid electrolyte material having good ion conductivity can be obtained. When the value of Li / P is large, the Li content is relatively increased, so that the ionic conductivity is considered to be improved. In the present invention, “amorphous” means that no peak is observed in X-ray diffraction (XRD), that is, no periodicity as a crystal is observed. In addition, the sulfide solid electrolyte material of the present invention preferably has a so-called halo pattern observed in X-ray diffraction (XRD).

  The sulfide solid electrolyte material of the present invention contains Li element, P element and S element. The sulfide solid electrolyte material of the present invention may contain only Li element, P element and S element, or may contain other elements. A part of the Li element may be substituted with a monovalent or divalent metal element. It is considered that ion conductivity is improved by substituting a part of the Li element with another element. Examples of the monovalent or divalent metal element include at least one of Na, K, Mg, and Ca. The substitution amount of the metal element can be determined, for example, by XRD Rietveld analysis and ICP emission spectroscopy.

  Further, a part of the S element may be substituted with the O element. The ratio of O element to the total of S element and O element (O / (S + O)) is, for example, preferably 0.1% or more, and more preferably 0.5% or more. The substitution amount ratio of the O element is, for example, preferably 50% or less, and more preferably 34% or less.

  In the present invention, the ratio of Li to P element (Li / P) is usually greater than 3. Among them, the value of Li / P is, for example, preferably 3.1 or more, more preferably 3.2 or more, and further preferably 3.5 or more. This is because when the value of Li / P is large, ion conductivity can be improved. On the other hand, the value of Li / P is, for example, 7 or less, and preferably 5 or less. This is because if the value of Li / P is too large, amorphous may not be obtained.

Moreover, it is preferable that the sulfide solid electrolyte material of the present invention mainly contains PS ₄ ^3- structure. The ratio of PS ₄ ^3- structure to the total anion structure is preferably 60 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, and particularly preferably 90 mol% or more. preferable. Note that the ratio of the PS ₄ ^3- structure can be determined by Raman spectroscopy, NMR, XPS, or the like. Since the ratio can be determined with high accuracy, it is particularly preferable to use NMR.

  It is preferable that the sulfide solid electrolyte material of the present invention does not substantially contain a metal element belonging to Group 3 to Group 16. This is because these metal elements can cause a reduction in the reduction resistance of the sulfide solid electrolyte material. Therefore, reduction resistance can be improved by substantially not using these metal elements. Here, the metal element belonging to Group 3 to Group 16 refers to a metal element belonging to Group 3 to Group 12 and a metal element belonging to Group 13 to Group 16. Further, the metal element belonging to Group 13 refers to aluminum and an element having an atomic number larger than that of aluminum, and the metal element belonging to Group 14 refers to silicon and an element having an atomic number larger than that of silicon. Good, a metal element belonging to Group 15 means arsenic and an element having an atomic number larger than that of arsenic, and a metal element belonging to Group 16 means an element having an atomic number larger than that of tellurium and tellurium. Say.

  In the present invention, “substantially free of metal elements belonging to Group 3 to Group 16” means the molar ratio of the metal element to the P element (number of moles of the metal element / number of moles of the P element). ) Is 0.1 or less. Among these, the molar ratio is preferably 0.08 or less, and more preferably 0.05 or less. This is because the reduction resistance can be further improved. The proportion of the metal element can be confirmed by ICP emission spectroscopy. By obtaining the mass distribution by ICP emission spectroscopy and dividing by the atomic weight, the number of moles (molar fraction) of each element can be obtained. The fact that the sulfide solid electrolyte material has Li element, P element and S element can be confirmed by X-ray photoelectron spectroscopy.

The composition of the sulfide solid electrolyte material of the present invention is not particularly limited. Among these, a sulfide solid electrolyte material of the present invention _preferably contains a composition of _{Li 5x + 2y + 3 P 1} -x S 4 (0 ≦ x ≦ 0.2,0 <y <0.225). In particular, a sulfide solid electrolyte material having high reduction resistance can be obtained by having an ionic conductor having a composition of Li _{5x + 2y + 3} P _1-x S ₄ as a main component. In addition, the metal element belonging to Group 3 to Group 16 may be included, for example, in a trace amount (a quantity not substantially contained).

More precisely, the above composition can also be expressed as Li _{5x + 2y + 3} P ^(III) _y P ^(V) _1-xy S ₄ . P ^(III) and P ^(V) are trivalent and pentavalent phosphorus, respectively. Further, the composition is a composition which deviates from the tie line of Li ₂ S and _P 2 _{S 5,} for example, _Li 2 _S, a composition obtained by using a P 2 _{S 5} and P. The above composition is assumed to be a pseudo ternary system of Li ₂ S, Li ₅ PS ₄ (ortho composition using trivalent phosphorus) and Li ₃ PS ₄ (ortho composition using pentavalent phosphorus). It has been decided. That is,
_{x (Li 8 S 4) ·} yLi 5 P (III) S 4 · (1-x-y) Li 3 P (V) S 4
→ Li _{5x + 2y + 3} P ^(III) _y P ^(V) _1-xy S ₄
In the above composition, the range of 0 ≦ x ≦ 0.2 and 0 <y <0.225 corresponds to the region A in FIG. A range of 0 ≦ x ≦ 0.2 and 0.175 ≦ y <0.225 corresponds to the region B in FIG.

Moreover, the sulfide solid electrolyte material of the present invention may include a composition of Li _{5x + 3} P _1-x S ₄ (0.1 ≦ x ≦ 0.2). In particular, by having an ionic conductor having a composition of Li _{5x + 3} P _1-x S ₄ as a main component, a sulfide solid electrolyte material having high reduction resistance can be obtained. In addition, the metal element belonging to Group 3 to Group 16 may be included, for example, in a trace amount (a quantity not substantially contained). Further, the composition is a composition of the tie line of Li ₂ S and _P 2 _{S 5.}

The sulfide solid electrolyte material of the present invention preferably has high ionic conductivity, and the ionic conductivity of the sulfide solid electrolyte material at 25 ° C. is preferably 1.0 × 10 ⁻⁴ S / cm or more. Further, the shape of the sulfide solid electrolyte material of the present invention is not particularly limited, and examples thereof include a powder form. Furthermore, the average particle diameter of the powdered sulfide solid electrolyte material is preferably in the range of 0.1 μm to 50 μm, for example.

Since the sulfide solid electrolyte material of the present invention has good ionic conductivity, it can be used for any application that requires ionic conductivity. Especially, it is preferable that the sulfide solid electrolyte material of this invention is what is used for a battery. This is because it can greatly contribute to the high output of the battery. The method for producing the sulfide solid electrolyte material of the present invention will be described in detail in “C. Method for producing sulfide solid electrolyte material” described later. In particular, the sulfide solid electrolyte material of the present invention is preferably formed using a raw material composition containing Li ₂ S, P ₂ S ₅ and P.

B. Battery Next, the battery of the present invention will be described. FIG. 2 is a schematic cross-sectional view showing an example of the battery of the present invention. The battery 10 in FIG. 2 was formed between the positive electrode active material layer 1 containing the positive electrode active material, the negative electrode active material layer 2 containing the negative electrode active material, and the positive electrode active material layer 1 and the negative electrode active material layer 2. An electrolyte layer 3, a positive electrode current collector 4 for collecting current of the positive electrode active material layer 1, a negative electrode current collector 5 for collecting current of the negative electrode active material layer 2, and a battery case 6 for housing these members. I have it. In the present invention, at least one of the positive electrode active material layer 1, the negative electrode active material layer 2, and the electrolyte layer 3 contains the sulfide solid electrolyte material described in the above-mentioned “A. Sulfide solid electrolyte material”. And

According to the present invention, a high-power battery can be obtained by using the above-described sulfide solid electrolyte material.
Hereinafter, the battery of this invention is demonstrated for every structure.

1. Negative electrode active material layer The negative electrode active material layer in the present invention is a layer containing at least a negative electrode active material, and may contain at least one of a solid electrolyte material, a conductive material and a binder, if necessary. good. In particular, in the present invention, the negative electrode active material layer preferably contains a solid electrolyte material, and the solid electrolyte material is the sulfide solid electrolyte material described above. This is because the sulfide solid electrolyte material has high reduction resistance. The ratio of the sulfide solid electrolyte material contained in the negative electrode active material layer varies depending on the type of the battery. For example, it is in the range of 0.1% by volume to 80% by volume, and in particular, 1% by volume to 60% by volume. It is preferable to be within the range, particularly within the range of 10% by volume to 50% by volume. Examples of the negative electrode 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), highly oriented graphite (HOPG), hard carbon, and soft carbon.

  The negative electrode active material layer may further contain a conductive material. By adding a conductive material, the conductivity of the negative electrode active material layer can be improved. Examples of the conductive material include acetylene black, ketjen black, and carbon fiber. The negative electrode active material layer may contain a binder. Examples of the type of binder include fluorine-containing binders such as polyvinylidene fluoride (PVDF). Moreover, it is preferable that the thickness of a negative electrode active material layer exists in the range of 0.1 micrometer-1000 micrometers, for example.

2. Electrolyte layer The electrolyte layer in this invention is a layer formed between a positive electrode active material layer and a negative electrode active material layer. The electrolyte layer is not particularly limited as long as it is a layer capable of conducting ions, but is preferably a solid electrolyte layer made of a solid electrolyte material. This is because a battery with higher safety can be obtained as compared with a battery using an electrolytic solution. Furthermore, in this invention, it is preferable that a solid electrolyte layer contains the sulfide solid electrolyte material mentioned above. The ratio of the sulfide solid electrolyte material contained in the solid electrolyte layer is, for example, preferably in the range of 10% to 100% by volume, and more preferably in the range of 50% to 100% by volume. The thickness of the solid electrolyte layer is, for example, preferably in the range of 0.1 μm to 1000 μm, and more preferably in the range of 0.1 μm to 300 μm. Moreover, as a formation method of a solid electrolyte layer, the method of compression-molding a solid electrolyte material etc. can be mentioned, for example.

Further, the electrolyte layer in the present invention may be a layer composed of an electrolytic solution. When the electrolytic solution is used, it is necessary to further consider safety compared to the case where the solid electrolyte layer is used, but a battery with higher output can be obtained. In this case, usually, at least one of the positive electrode active material layer and the negative electrode active material layer contains the above-described sulfide solid electrolyte material. The electrolytic solution usually contains a lithium salt and an organic solvent (nonaqueous solvent). Examples of the lithium salt include inorganic lithium salts such as LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , and LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiC An organic lithium salt such as (CF ₃ SO ₂ ) ₃ can be used. Examples of the organic solvent include ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), butylene carbonate (BC), and the like.

3. Positive electrode active material layer The positive electrode active material layer in the present invention is a layer containing at least a positive electrode active material, and may contain at least one of a solid electrolyte material, a conductive material and a binder, if necessary. good. In particular, in the present invention, the positive electrode active material layer preferably contains a solid electrolyte material, and the solid electrolyte material is preferably the sulfide solid electrolyte material described above. The ratio of the sulfide solid electrolyte material contained in the positive electrode active material layer varies depending on the type of the battery. It is preferable to be within the range, particularly within the range of 10% by volume to 50% by volume. As the positive electrode active material, for example, LiCoO ₂ , LiMnO ₂ , Li ₂ NiMn ₃ O ₈ , LiVO ₂ , LiCrO ₂ , LiFePO ₄ , LiCoPO ₄ , LiNiO ₂ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ etc. can be mentioned. Note that the conductive material and the binder used in the positive electrode active material layer are the same as those in the negative electrode active material layer described above. Moreover, it is preferable that the thickness of a positive electrode active material layer exists in the range of 0.1 micrometer-1000 micrometers, for example.

4). Other Configurations The battery of the present invention has at least the negative electrode active material layer, the electrolyte layer, and the positive electrode active material layer described above. Furthermore, it usually has a positive electrode current collector for collecting current of the positive electrode active material layer and a negative electrode current collector for collecting current of the negative electrode active material layer. Examples of the material for the positive electrode current collector include SUS, aluminum, nickel, iron, titanium, and carbon. On the other hand, examples of the material for the negative electrode current collector include SUS, copper, nickel, and carbon. In addition, the thickness and shape of the positive electrode current collector and the negative electrode current collector are preferably appropriately selected according to the use of the battery. Moreover, the battery case of a general battery can be used for the battery case used for this invention. Examples of the battery case include a SUS battery case.

5. Battery The battery of the present invention may be a primary battery or a secondary battery, but among them, a secondary battery is preferable. This is because it can be repeatedly charged and discharged and is useful, for example, as an in-vehicle battery. Examples of the shape of the battery of the present invention include a coin type, a laminate type, a cylindrical type, and a square type. Moreover, the manufacturing method of the battery of this invention will not be specifically limited if it is a method which can obtain the battery mentioned above, The method similar to the manufacturing method of a general battery can be used. For example, when the battery of the present invention is an all-solid battery, as an example of the manufacturing method thereof, a material constituting the positive electrode active material layer, a material constituting the solid electrolyte layer, and a material constituting the negative electrode active material layer are sequentially provided. Examples of the method include producing a power generation element by pressing, housing the power generation element inside the battery case, and caulking the battery case.

C. Next, a method for producing a sulfide solid electrolyte material of the present invention will be described. FIG. 3 is an explanatory view showing an example of a method for producing a sulfide solid electrolyte material of the present invention. In the method for producing a sulfide solid electrolyte material in FIG. 3, first, a raw material composition is prepared by mixing Li ₂ S, P ₂ S ₅ , and P. At this time, in order to prevent the raw material composition from being deteriorated by moisture in the air, it is preferable to prepare the raw material composition in an inert gas atmosphere. Next, an amorphous sulfide solid electrolyte material is obtained by a melt quenching method using the raw material composition.

  According to the present invention, a sulfide solid electrolyte material having good ion conductivity can be obtained by performing amorphization by a melt quenching method using a predetermined raw material.

In particular, when the raw material composition contains simple phosphorus, a slurry-like compound may be obtained when an attempt is made to be amorphous by mechanical milling. On the other hand, in the present invention, since the melt quenching method of quenching the melt is used, not the slurry compound but the target sulfide solid electrolyte material can be obtained.
Hereafter, the manufacturing method of the sulfide solid electrolyte material of this invention is demonstrated for every process.

1. Synthesis Step The synthesis step in the present invention will be described. The synthesizing step in the present invention is a step of synthesizing an amorphous sulfide solid electrolyte material by a melt quenching method using a raw material composition containing the components of the sulfide solid electrolyte material.

The raw material composition in the present invention contains at least Li element, P element and S element, and may contain other elements such as O element. Examples of the compound containing Li element include a sulfide of Li and an oxide of Li. Specific examples of the sulfide of Li include Li ₂ S. Specific examples of the oxide of Li include Li ₂ O. Examples of the compound containing P element include P alone, P oxide, P sulfide, and the like. Specific examples of P sulfide include P ₂ S ₅ . Specific examples of the P oxide include P ₂ O ₅ . The compound containing S element is not particularly limited, and may be a simple substance or a sulfide. Examples of the sulfide include a sulfide containing the above-described element.

  In the present invention, an amorphous sulfide solid electrolyte material is obtained by a melt quenching method. The melt quenching method is a method in which a raw material composition is heated to a molten state, and then amorphized by rapid cooling. Although the heating temperature of a raw material composition will not be specifically limited if it is the temperature which can make a raw material composition into a molten state, For example, it is 550 degreeC or more and it exists in the range of 700 to 1200 degreeC. Is preferred. Examples of the method for heating the raw material composition include a method using a firing furnace. On the other hand, the cooling rate at the time of rapid cooling is, for example, 500 ° C./min or more, and preferably 700 ° C./min or more. Further, it is preferable to cool to 100 ° C. or lower, particularly 50 ° C. or lower by rapid cooling. As a method for cooling the melt, a method of bringing a refrigerant into contact with the melt directly or indirectly is usually used. Specifically, a method of bringing a container containing the melt into contact with a liquid such as water, a method of bringing the melt into contact with a rotating metal roll, and the like can be mentioned.

  In addition, the raw material composition may be subjected to heat treatment (calcination) before performing the melt quenching method. This is because by using a solid that has been heat-treated in advance, a melt having high dispersibility can be obtained in the subsequent melt treatment. The temperature of heat processing is in the range of 200 to 800 degreeC, for example, and it is preferable to exist in the range of 500 to 700 degreeC. The heating time is, for example, in the range of 30 minutes to 20 hours, and preferably in the range of 2 hours to 10 hours. The heat treatment is preferably performed in an inert gas atmosphere or in vacuum from the viewpoint of preventing oxidation.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Example 1]
As starting materials, lithium sulfide (Li ₂ S, manufactured by Nippon Kagaku Kogyo Co., Ltd.), diphosphorus pentasulfide (P ₂ S ₅ , manufactured by Aldrich) and red phosphorus (P, manufactured by High Purity Chemical Laboratory) are shown. Weighed at the ratio shown in 1. The mixed raw material composition was placed in a carbon-coated quartz tube and vacuum sealed. The pressure of the vacuum sealed quartz tube was about 30 Pa. Next, the quartz tube was placed in a firing furnace, heated from room temperature to 550 ° C. over 6 hours, maintained at 550 ° C. for 8 hours, and then gradually cooled to room temperature. As a result, Sample A was obtained.

Next, the obtained powder of Sample A was pulverized using a vibration mill. TI-100 manufactured by CM Science Co., Ltd. was used for the vibration mill. Specifically, 2 g of the sample A obtained by the above method and an alumina vibrator (φ36.3 mm, height 48.9 mm) are placed in a 10 mL zirconia pot and treated at a rotational speed of 1440 rpm for 30 minutes. Went. Thereafter, the obtained powder was placed in a carbon-coated quartz tube and vacuum-sealed. The pressure of the vacuum sealed quartz tube was about 30 Pa. Next, the quartz tube was placed in a baking furnace, heated from room temperature to 950 ° C. over 2 hours, maintained at 950 ° C. for 1 hour, and then the quartz tube was put into ice water and rapidly cooled. Thereby, a sulfide solid electrolyte material having a composition of Li _3.75 P _0.93 S ₄ (x = 0.07, y = 0.2, Li / P = 4.03) was obtained.

[Comparative Examples 1-3]
A sulfide solid electrolyte material was obtained in the same manner as in Example 1 except that the ratio of the raw material composition was changed to the ratio shown in Table 1.

[Comparative Example 4]
Raw material compositions were obtained at the ratios shown in Table 1. The obtained raw material composition was placed in a zirconia pot (45 ml) together with zirconia balls (10 mmφ, 10 pieces), and the pot was completely sealed (argon atmosphere). This pot was attached to a planetary ball mill (P7 made by Fritsch), and mechanical milling was performed at a base plate rotation speed of 370 rpm for 40 hours. Thereby, a sulfide solid electrolyte material was obtained. In addition, the composition of the sulfide solid electrolyte material obtained in Example 1 and Comparative Examples 1 to 4 is shown in FIG.

[Comparative Examples 5 and 6]
A sulfide solid electrolyte material was obtained in the same manner as in Example 1 except that the ratio of the raw material composition was changed to the ratio shown in Table 1.

[Evaluation]
(X-ray diffraction measurement)
Using the sulfide solid electrolyte material obtained in Example 1 and Comparative Examples 1 to 6, X-ray diffraction (XRD) measurement was performed. XRD measurement was performed on the powder sample under an inert atmosphere and using CuKα rays. The results are shown in FIGS. In FIG. 5, an unknown peak was observed at 2θ = 22 °, which is presumed to be carbon mixed during synthesis or measurement. Therefore, in Example 1, it is determined that an amorphous sulfide solid electrolyte material was obtained. On the other hand, as shown in FIGS. 6 and 7, in Comparative Examples 1 and 2, peaks derived from the crystal phase were observed.

(Li ion conductivity measurement)
Using the sulfide solid electrolyte material obtained in Example 1 and Comparative Examples 1 to 6, Li ion conductivity at 25 ° C. was measured. First, 200 mg of the sulfide solid electrolyte material was weighed, placed in a cylinder made by Macor, and pressed at a pressure of 4 ton / cm ² . Both ends of the obtained pellet were sandwiched between SUS pins, and restraint pressure was applied to the pellet by bolting to obtain an evaluation cell. With the evaluation cell kept at 25 ° C., Li ion conductivity was calculated by the AC impedance method. For the measurement, Solartron 1260 was used, and the applied voltage was 5 mV and the measurement frequency range was 0.01 to 1 MHz. The results are shown in FIGS.

  As shown in FIG. 12, Example 1 showed higher Li ion conductivity than Comparative Example 1 and Comparative Example 2. Moreover, it was suggested that Li ion conductivity becomes high at y = 0.2 vicinity. Moreover, in Comparative Example 1 and Comparative Example 2, a peak derived from the crystal phase was observed in XRD, but Li ion conductivity was higher in Example 1 in which no peak derived from the crystal phase was observed. Moreover, as shown in FIG. 13, Example 1 showed Li ion conductivity higher than Comparative Examples 3-6. From the result of FIG. 13, it was confirmed that the Li ion conductivity increases as the value of Li / P increases. Although the Li / P value (4.08) in Comparative Example 2 is larger than the Li / P value (4.03) in Example 1, as shown in FIG. The Li ion conductivity of was lower than the Li ion conductivity of Example 1. Based on this point, in the present invention, it is presumed that the Li ion conductivity was the highest by simultaneously satisfying the condition that the value of Li / P was large and the condition that it was amorphous.

DESCRIPTION OF SYMBOLS 1 ... Positive electrode active material layer 2 ... Negative electrode active material layer 3 ... Electrolyte layer 4 ... Positive electrode collector 5 ... Negative electrode collector 6 ... Battery case 10 ... Battery

Claims (6)

Containing Li element, P element and S element,
The ratio of Li to the P element (Li / P) is greater than 3,
No peak is observed in X-ray diffraction (XRD) measurement,
A sulfide solid electrolyte material comprising a composition of Li _{5x + 2y + 3} P _1-x S ₄ (0 ≦ x ≦ 0.2, 0 <y <0.225) .   The sulfide solid electrolyte material according to claim 1, wherein the Li / P is 3.5 or more.   The sulfide solid electrolyte material according to claim 1, wherein the y satisfies 0.175 ≦ y <0.225. A battery comprising a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and an electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer. And
At least one of the positive electrode active material layer, the negative electrode active material layer, and the electrolyte layer contains the sulfide solid electrolyte material according to any one of claims 1 to 3. battery. A method for producing a sulfide solid electrolyte material according to any one of claims 1 to 3 ,
A sulfide solid electrolyte comprising a synthesis step of synthesizing an amorphous sulfide solid electrolyte material by a melt quenching method using a raw material composition containing a component of the sulfide solid electrolyte material Material manufacturing method.   The raw material composition is Li ₂ S, P ₂ S ₅ The method for producing a sulfide solid electrolyte material according to claim 5, further comprising: and P.

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