阅读说明：本技术 硫化物固体电解质 (Sulfide solid electrolyte ) 是由 寺井恒太 佐藤淳 宇都野太 于 2018-05-23 设计创作，主要内容包括：本发明的目的之一在于提供一种在电池制造时的加工性良好且离子传导率较高的硫化物固体电解质。本发明涉及一种硫化物固体电解质,包含锂、磷以及硫,在使用CuKα射线的粉末X射线衍射中,在2θ＝25.2±0.5deg具有衍射峰A,在2θ＝29.7±0.5deg具有衍射峰B,在固体<Sup>31</Sup>P-NMR测量中,将在60～120ppm的范围内观测到的峰进行峰分离而得的峰的至少一个峰的半宽值为500～800Hz。(An object of the present invention is to provide a sulfide solid electrolyte having good processability in battery production and high ionic conductivity. Hair brushDisclosed is a sulfide solid electrolyte containing lithium, phosphorus and sulfur, which has a diffraction peak A at 25.2 + -0.5 deg. in powder X-ray diffraction using CuKa radiation, a diffraction peak B at 29.7 + -0.5 deg. in 2 theta, and a solid electrolyte 31 In the P-NMR measurement, at least one peak obtained by peak separation of peaks observed in a range of 60 to 120ppm has a half-width value of 500 to 800 Hz.)

1. A sulfide solid electrolyte characterized in that,

comprising lithium, phosphorus and sulfur,

has a diffraction peak A at 25.2 + -0.5 deg. and a diffraction peak B at 29.7 + -0.5 deg. in powder X-ray diffraction using CuK alpha rays,

in the solid³¹In the P-NMR measurement, at least one peak obtained by peak separation of peaks observed in a range of 60 to 120ppm has a half-width value of 500 to 800 Hz.

2. The sulfide solid electrolyte according to claim 1, wherein the relative half-width value of the diffraction peak B with respect to Si is 1.3 or more and 3.0 or less.

3. A sulfide solid electrolyte characterized in that,

comprising lithium, phosphorus and sulfur,

has a diffraction peak A at 25.2 + -0.5 deg. and a diffraction peak B at 29.7 + -0.5 deg. in powder X-ray diffraction using CuK alpha rays,

the diffraction peak B has a relative half width value of 1.3 to 3.0 inclusive with respect to Si,

the relative peak intensity of the diffraction peak B to Si is 0.01 to 0.15.

4. The sulfide solid electrolyte according to any one of claims 1 to 3, wherein the sulfide solid electrolyte is a solid³¹In P-NMR measurement, it is observed that the area ratio of the peaks derived from the glass is 0% to 10% with respect to the total area of all peaks at 60 to 120 ppm.

5. The sulfide solid electrolyte according to any one of claims 1 to 4, further comprising a halogen.

6. The sulfide solid electrolyte according to claim 5, wherein a molar ratio a of the lithium to the phosphorus (Li/P), a molar ratio b of the sulfur to the phosphorus (S/P), and a molar ratio C of the halogen to the phosphorus (X/P) satisfy the following formulas (A) to (C),

5.0≤a≤7.5…(A)，

6.5≤a+c≤7.5…(B)，

0.5≤a-b≤1.5…(C)，

wherein b >0 and c >0 are satisfied.

7. The sulfide solid electrolyte according to claim 5, having a composition represented by the following formula (1),

Li_a(P_1-αM_α)S_bX_c(1)

wherein M is at least one element selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi, X is at least one element selected from the group consisting of F, Cl, Br and I, a to C satisfy the following formulas (A) to (C), α is 0. ltoreq. α.ltoreq.0.3,

5.0≤a≤7.5…(A)，

6.5≤a+c≤7.5…(B)，

0.5≤a-b≤1.5…(C)，

wherein b >0 and c >0 are satisfied.

8. The sulfide solid electrolyte according to any one of claims 5 to 7, comprising chlorine (Cl).

9. The sulfide solid electrolyte according to any one of claims 5 to 7, comprising chlorine (Cl) and bromine (Br).

10. An electrode composite material comprising the sulfide solid electrolyte according to any one of claims 1 to 9 and an active material.

11. A lithium ion battery comprising at least one of the sulfide solid electrolyte according to any one of claims 1 to 9 and the electrode composite material according to claim 10.

12. An electrode composite material produced from the sulfide solid electrolyte according to any one of claims 1 to 9.

13. A lithium ion battery produced from at least one of the sulfide solid electrolyte according to any one of claims 1 to 9, the electrode composite material according to claim 10, and the electrode composite material according to claim 12.

Technical Field

The present invention relates to a sulfide solid electrolyte.

Background

In recent years, as information-related devices such as computers, video cameras, and cellular phones, and communication devices have rapidly spread, the development of batteries used as power sources thereof has been attracting attention. Among such batteries, lithium ion batteries have attracted attention from the viewpoint of high energy density.

Since a lithium ion battery that is currently commercially available uses an electrolyte solution containing a flammable organic solvent, it is necessary to install a safety device for suppressing a temperature rise at the time of short circuit or to improve a structure and a material for preventing short circuit. In contrast, a lithium ion battery in which the electrolyte is changed to a solid electrolyte to completely solidify the battery is considered to be capable of simplifying a safety device and to be excellent in manufacturing cost and productivity because a combustible organic solvent is not used in the battery.

As a solid electrolyte used in a lithium ion battery, a sulfide solid electrolyte is known. Various structures are known as the crystal structure of the sulfide solid electrolyte, but from the viewpoint of expanding the use temperature range of the battery, a stable crystal structure in which the structure is hard to change over a wide temperature range is preferable. As such a sulfide solid electrolyte, for example, a sulfide solid electrolyte having an Argyrodite (Argyrodite) type crystal structure has been developed (for example, see patent documents 1 to 5).

Disclosure of Invention

The sulfide solid electrolyte having a sigermorite-type crystal structure has high stability, and further, there is a sulfide solid electrolyte having high ionic conductivity. However, further improvements in processability, ion conductivity, and the like at the time of battery production are demanded.

An object of the present invention is to provide a sulfide solid electrolyte having good processability in battery production and high ionic conductivity.

As a result of intensive studies, the present inventors have found a sulfide solid electrolyte having characteristics different from those of a conventional sulfide solid electrolyte having a thiogermorite-type crystal structure. The sulfide solid electrolyte according to one embodiment of the present invention is a solid³¹In P-NMR measurement, a peak having a half width of 500 to 800Hz is observed. In addition, in the sulfide solid electrolyte according to an embodiment of the present invention, in the powder X-ray diffraction, the diffraction peak a is present at 25.2 ± 0.5 deg. and the diffraction peak B is present at 29.7 ± 0.5 deg. with respect to 2 θ, the relative half width value of the diffraction peak B with respect to Si is 1.3 or more and 3.0 or less, and the relative peak intensity of the diffraction peak B with respect to Si is 0.01 or more and 0.15 or less. The above characteristics have not been observed in conventional sulfide solid electrolytes.

The present inventors have found that the novel sulfide solid electrolyte having the above-described characteristics has high processability in battery production, and specifically, has high compactibility and high ionic conductivity.

According to an embodiment of the present invention, there is provided a sulfide solid electrolyte including lithium, phosphorus, and sulfur, having a diffraction peak a at 25.2 ± 0.5 deg. of 2 θ, a diffraction peak B at 29.7 ± 0.5 deg. of 2 θ, and a diffraction peak B at the solid in powder X-ray diffraction using CuK α rays³¹In P-NMR measurement, the range of 60 to 120ppm of the appearanceThe half-width value of at least one peak of the peaks obtained by peak separation of the measured peaks is 500-800 Hz.

Further, according to an embodiment of the present invention, there is provided a sulfide solid electrolyte containing lithium, phosphorus, and sulfur, and having a diffraction peak a at 25.2 ± 0.5 deg. and a diffraction peak B at 29.7 ± 0.5 deg. in powder X-ray diffraction using CuK α rays, the relative half width value of the diffraction peak B with respect to Si being 1.3 or more and 3.0 or less, and the relative peak intensity of the diffraction peak B with respect to Si being 0.01 or more and 0.15 or less.

According to one embodiment of the present invention, a sulfide solid electrolyte having good processability and high ionic conductivity in battery production can be provided.

Drawings

Fig. 1 is an X-ray diffraction (XRD) pattern of a standard sample (Si).

Fig. 2 is an XRD spectrum of the sulfide solid electrolyte of example 1.

FIG. 3 is a solid of a sulfide solid electrolyte of example 1³¹P-NMR spectrum.

FIG. 4 is a solid of a sulfide solid electrolyte of example 3³¹P-NMR spectrum.

Fig. 5 is an XRD spectrum of the sulfide solid electrolyte of comparative example 1.

FIG. 6 shows a sulfide solid electrolyte solid of comparative example 1³¹P-NMR spectrum.

FIG. 7 shows a sulfide solid electrolyte solid of comparative example 2³¹P-NMR spectrum.

Fig. 8 is an XRD spectrum of the sulfide solid electrolyte of example 7.

FIG. 9 shows the reduced two-volume distribution function of example 4 and comparative example 3.

FIG. 10 is that of FIG. 9

Enlarged view of (a).

FIG. 11 is that of FIG. 9

Enlarged view of (a).

Fig. 12 is a dark field image of TEM of the sulfide solid electrolyte of example 1.

Fig. 13 is a dark field image of TEM of the sulfide solid electrolyte of comparative example 1.

Detailed Description

[ first embodiment ]

The sulfide solid electrolyte of the first embodiment of the present invention contains lithium (Li), phosphorus (P), and sulfur (S) as constituent elements. The following elements 1 and 2 are satisfied.

Element 1

In powder X-ray diffraction using CuK α rays, the diffraction peak a was 25.2 ± 0.5 deg. at 2 θ, and the diffraction peak B was 29.7 ± 0.5 deg. at 2 θ.

Element 2

In the solid³¹In the P-NMR measurement, at least one peak obtained by peak separation of peaks observed in a range of 60 to 120ppm has a half-width value of 500 to 800 Hz.

In the present application, the description "○ to ○" indicating the range means "○ to ○".

Regarding the element 1, the diffraction peak a and the diffraction peak B are peaks derived from a digermorite-type crystal structure. In addition to the diffraction peaks a and B, the diffraction peaks of the digermorite-type crystal structure also appear at, for example, 15.3 ± 0.5deg, 17.7 ± 0.5deg, 31.1 ± 0.5deg, 44.9 ± 0.5deg, or 47.7 ± 0.5 deg. The sulfide solid electrolyte of the present invention may have these peaks.

When the central value is a, the position of the diffraction peak is determined to be a ± 0.5deg in the present application, but is preferably a ± 0.3 deg. For example, in the case of the diffraction peak having a 2 θ of 25.2 ± 0.5deg, the median a is 25.2deg, and preferably, it is within a range of 25.2 ± 0.3 deg. The same applies to the determination of the positions of all other diffraction peaks in the present application.

Regarding the element 2, the peak derived from the thiogermorite-type crystal structure and the peak derived from glass, which are contained in the sulfide solid electrolyteCan be in the solid state³¹Observed in the range of 60 to 120ppm in the P-NMR spectrum. Generally, the half-width value of the peak derived from the crystal is relatively narrow, and the half-width value of the peak derived from the glass is relatively wide. For example, in the measurement results of the examples and comparative examples of the present application, the half width value of the peak due to the crystal was 450Hz or less, whereas the half width value of the peak due to the glass was wider than 1000 Hz.

On the other hand, in the sulfide solid electrolyte of the present embodiment, 1 or more peaks having a half-width value of 500 to 800Hz are observed. In this embodiment, the half-width value of the peak having the largest peak area ratio is preferably 500 to 800 Hz. In addition, the area ratio of the peak with the half width value of 500 to 800Hz is preferably 20 to 100%, more preferably 40 to 100%, more preferably 60 to 100%, further preferably 70 to 100%, and particularly preferably 75 to 100%.

The sulfide solid electrolyte according to the present embodiment is defined by the above element 1 to include a geigrite-type crystal structure. However, element 2 shows a form in which the conventional germanite-type crystal structure is different from the germanite-type crystal structure of the present embodiment. It is presumed that the value having the half-width value within the above range indicates that the digermorite-type crystal structure of the present embodiment is a distorted structure in which the positions of atoms in the conventional crystal structure are slightly shifted. Since the structure is twisted, plastic deformation is likely to occur due to stress, and the workability is considered to be good.

In the present embodiment, it is preferable that the polymer is a solid³¹The area ratio of a peak derived from glass to the total area of all peaks at 60 to 120ppm observed in P-NMR measurement is 0% to 10%. Thereby, the ion conductivity of the sulfide solid electrolyte is further improved. The area ratio is more preferably 8% or less, and particularly preferably 5% or less.

In general, glass has a softer structure than crystal, and therefore, when glass is contained in a large amount, processability in the production of a battery is improved (see japanese patent application laid-open No. 2008-103203). However, the ion conductivity of the glass is low compared to the digermorite-type crystal structure. Therefore, the ion conductivity is lowered when glass is included. In the present invention, workability is improved by making crystal morphology different from that of the conventional one, not by including a large amount of glass. Has a thiogermorite type crystal structure, thereby having high ion conductivity.

From solids³¹Determination of peaks obtained by P-NMR measurement, half-width value and area ratio of each peak were determined by subjecting solid to nonlinear least squares method³¹The signal observed at 60 to 120ppm in the P-NMR spectrum is separated into peaks, and the half-width value of each peak is measured and calculated.

By means of solids³¹The chemical shift of the sulfide solid electrolyte measured by P-NMR varies depending on the arrangement state of atoms, the coordination number and coordination state of surrounding atoms, and the like. Further, since chemical shifts of crystals and glasses included in the sulfide solid electrolyte are not averaged due to molecular motion, spectra corresponding to all of these structures are observed.

The Geranite-type crystal structure contains PS in the crystal₄ ^3-Structure but due to differences in symmetry of the crystal, or PS₄ ^3-Differences in coordination states of atoms around the structure, passing solid in respective crystals³¹The chemical shift positions of the peaks obtained by P-NMR measurement were different. On the other hand, as the glass, PS is reported₄ ^3-Structure, P₂S₇ ^4-Structure and P₂S₆ ^4-The chemical shifts of these chemical structures are observed at positions different from the chemical shift positions of the peaks of the crystals, or the half-widths are significantly different in the glasses having the structures.

By utilizing the above difference, in the sulfide solid electrolyte, the solid can be formed³¹The P-NMR spectrum was separated into a peak due to the crystal and a peak due to the glass, and the respective amounts were quantified. The details are described in the embodiments described later. Each peak area represents the amount of phosphorus present when the ambient environment is the same.

[ second embodiment ]

A sulfide solid electrolyte according to another embodiment of the present invention contains lithium, phosphorus, and sulfur as constituent elements. The present invention is characterized by satisfying the following elements 1 and 3.

Element 1

In powder X-ray diffraction using CuK α rays, the diffraction peak a was 25.2 ± 0.5 deg. at 2 θ, and the diffraction peak B was 29.7 ± 0.5 deg. at 2 θ.

Element 3

The relative half width value of the diffraction peak B to Si is 1.3 to 3.0, and the relative peak intensity of the diffraction peak B to Si is 0.01 to 0.15.

The element 1 is the same as in the first embodiment.

Element 3 defines that the relative half-width value of a typical diffraction peak (diffraction peak B) of the sigermorite-type crystal structure is broad with respect to Si, and the relative peak intensity is strong. It is known that the half width of the diffraction peak is related to the grain size, and the half width becomes wider as the grain size becomes smaller (scherrer equation). On the other hand, a strong peak intensity indicates that the sulfide solid electrolyte contains a large amount of the digermorite-type crystal structure. Here, when the sulfide solid electrolyte is in a glass state, the half-width value is extremely large, and the diffraction peak is broadened. However, in this case, since the amount of the crystal present is small, the diffraction peak intensity strain derived from the crystal is small. In this embodiment, the half-width value of the diffraction peak derived from the digermorite-type crystal structure is large, and the intensity is large. That is, it shows a crystal structure containing a large amount of digermorite having a smaller crystal grain size ratio than the conventional one. Since a large number of interfaces between crystal grains exist, when stress is applied, the interfaces are plastically deformed as slip surfaces, and thus the workability is considered to be good.

The relative half-width value of the diffraction peak B with respect to Si is preferably 1.5 to 2.8, more preferably 1.6 to 2.5, further preferably 1.8 to 2.4, and particularly preferably 2.0 to 2.4. The relative peak intensity of the diffraction peak B with respect to Si is preferably 0.02 to 0.12, more preferably 0.04 to 0.1, further preferably 0.04 to 0.08, and particularly preferably 0.05 to 0.07.

The relative half-width value of the diffraction peak B with respect to Si and the relative peak intensity with respect to Si are ratios between Si as a standard sample and the measured value of the diffraction peak at which 2 θ of Si becomes 28.6 ± 0.5 deg. In order to correct the variation in the measured value of the diffraction peak B due to the difference in the measuring apparatus or the like, a relative value to the standard sample is used. Details of the measurement method are shown in the examples.

Can be calculated by calculating the reduced two-body distribution function of the emission XRD or neutron diffraction [ G (r)]It was confirmed that the sulfide solid electrolyte of the present embodiment had crystallinity and a small crystal grain size. G (r) can also be evaluated

The above is relative to the atomic dependencies over medium and long distances. In g (r), when the sulfide solid electrolyte of the present embodiment is compared with a sulfide solid electrolyte produced by a conventional method (the crystal grain size is large), the periodicity of both is equivalent in a short distance range of less than 5nm, but the periodicity is different in a long distance range of 5 to 10 nm. This fact shows that the sulfide solid electrolyte of the present embodiment has the same crystal structure in the distance range of less than 5nm, but does not have the same periodic structure when the distance is 5nm or more, that is, the crystal grain size of the sulfide solid electrolyte of the present embodiment is about less than 5 nm.

Further, it can also be confirmed by observation with a Transmission Electron Microscope (TEM) that the crystal grains of the sulfide solid electrolyte of the present embodiment are composed of small-sized particles. In addition, sulfide samples are fragile by strong electron beams such as TEM, and therefore need to be cooled at low temperatures. Further, the presence of fine crystal grains in the particles and the particle diameter thereof can be confirmed by observation in a dark field image including a point of electron beam diffraction.

The sulfide solid electrolytes according to the first and second embodiments (hereinafter collectively referred to as the sulfide solid electrolytes of the present invention) have a characteristic of being excellent in compactibility. Conventional sulfide solid electrolytes having a crystal structure of a stable phase such as a digermorite-type crystal structure or an LGPS-type crystal structure need to be heat-treated at a high temperature (for example, 550 ℃) during production. In general, crystallization is promoted by heat treatment at high temperature, and the degree of crystallization increases. It is considered that a higher ionic conductivity is exhibited by increasing the amount of crystals contained in the sulfide solid electrolyte. However, on the other hand, the sulfide solid electrolyte may become hard due to, for example, the interface between crystal grains becoming strong. If the sulfide solid electrolyte is hard, various problems occur in manufacturing the battery. For example, when sulfide solid electrolyte particles are pressed to be in close contact with each other to form a solid electrolyte layer (compacting), the particles are less likely to be deformed, and therefore the contact area between the particles is small, and the formation of an ion path may become insufficient. In addition, when the electrode layer is formed, the active material particles used may be destroyed when mixed with the sulfide solid electrolyte particles.

Since the sulfide solid electrolyte of the present invention has a crystal form different from that of the conventional one, it is presumed that the hardness of the sulfide solid electrolyte particles is lowered. As a result, the density at the time of compacting becomes higher (the compacting property is improved) compared with the conventional sulfide solid electrolyte.

In addition, the crystal structure of the Geranite type is provided, so that the ion conductivity is higher.

In the first embodiment, the relative half-width value of the diffraction peak B with respect to Si is preferably 1.3 to 3.0, more preferably 1.5 to 2.8, more preferably 1.6 to 2.5, further preferably 1.8 to 2.4, and particularly preferably 2.0 to 2.3. The relative peak intensity of the diffraction peak B with respect to Si is preferably 0.01 to 0.15, more preferably 0.02 to 0.12, even more preferably 0.04 to 0.1, even more preferably 0.04 to 0.08, and particularly preferably 0.05 to 0.07.

In addition, in the second embodiment, in the solid³¹The area ratio of a peak derived from glass to the total area of all peaks at 60 to 120ppm observed in P-NMR measurement is 0% to 10%. The area ratio is more preferably 8% or less, and particularly preferably 5% or less.

In the sulfide solid electrolyte according to an embodiment of the present invention, in addition to Li, P, and S, halogen may be contained as a constituent element. Examples of halogen include F, Cl, Br and I. In the present embodiment, Cl or Br is preferably contained, and Cl and Br are particularly preferably contained.

Further, elements such As Si, Ge, Sn, Pb, B, Al, Ga, As, Sb, and Bi may be contained. Furthermore, chalcogens (oxygen (O), selenium (Se), tellurium (Te), and the like) may also be included.

In the sulfide solid electrolyte according to one embodiment of the present invention, the molar ratio a (Li/P) of lithium to phosphorus, the molar ratio b (S/P) of sulfur to phosphorus, and the molar ratio C (X/P) of halogen to phosphorus preferably satisfy the following formulas (a) to (C),

5.0≤a≤7.5…(A)

6.5≤a+c≤7.5…(B)

0.5≤a-b≤1.5…(C)。

(wherein b >0 and c >0 are satisfied.)

In the case where the sulfide solid electrolyte contains one or more elements M selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb, and Bi, the molar ratio of each element in the above (a) to (C) is the molar ratio relative to the total of the element M and phosphorus. For example, the molar ratio a (Li/P) of lithium to phosphorus is Li/(P + M).

When the molar ratio of F or Cl in the whole halogen is the largest, the above formula (A) is preferably 5.0. ltoreq. a.ltoreq.6.5, and particularly preferably 5.2. ltoreq. a.ltoreq.6.0. When the molar ratio of Br is at a maximum, the above formula (A) is preferably 5.2. ltoreq. a.ltoreq.6.8, and particularly preferably 5.3. ltoreq. a.ltoreq.6.6. When the molar ratio of I is the largest, the above formula (A) is preferably 5.5. ltoreq. a.ltoreq.7.2, and particularly preferably 5.5. ltoreq. a.ltoreq.7.0.

The above formula (B) is preferably 6.6. ltoreq. a + c. ltoreq.7.4, particularly preferably 6.7. ltoreq. a + c. ltoreq.7.3.

The above formula (C) is preferably 0.6. ltoreq. a-b. ltoreq.1.3, particularly preferably 0.7. ltoreq. a-b. ltoreq.1.3.

The sulfide solid electrolyte according to one embodiment of the present invention preferably has a composition represented by the following formula (1),

Li_a(P_1-αM_α)S_bX_c(1)。

(wherein M is at least one element selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, As, Sb and Bi, X is at least one element selected from the group consisting of F, Cl, Br and I, and a to C satisfy the following formulas (A) to (C). alpha.is 0. ltoreq. alpha.ltoreq.0.3.)

5.0≤a≤7.5…(A)

6.5≤a+c≤7.5…(B)

0.5≤a-b≤1.5…(C)。

(wherein b >0 and c >0 are satisfied.)

X in the formula (1) represents one or more elements (X) selected from the group consisting of F, Cl, Br and I₁、…、x_n: n is an integer of 1 to 4). X is preferably composed of one (X)₁) Or two (x)₁、x₂) The element is particularly preferably composed of two elements. The molar ratio of each element is not particularly limited.

α is preferably 0.

The above formula (B) is preferably 6.6. ltoreq. a + c. ltoreq.7.4, particularly preferably 6.7. ltoreq. a + c. ltoreq.7.3.

The above formula (C) is preferably 0.6. ltoreq. a-b. ltoreq.1.3, particularly preferably 0.7. ltoreq. a-b. ltoreq.1.3.

In the formula (1), when the molar ratio of F or Cl to the total X is the maximum, the above formula (A) is preferably 5.0. ltoreq. a.ltoreq.6.5, and particularly preferably 5.2. ltoreq. a.ltoreq.6.0. When the molar ratio of Br to the total X is the maximum, the above formula (A) is preferably 5.2. ltoreq. a.ltoreq.6.8, and particularly preferably 5.3. ltoreq. a.ltoreq.6.6. When the molar ratio of I to all X is the largest, the above formula (A) is preferably 5.5. ltoreq. a.ltoreq.7.2, and particularly preferably 5.5. ltoreq. a.ltoreq.7.0.

The molar ratio or composition of each element is not the molar ratio or composition in the raw material used for production, but the molar ratio or composition in the sulfide solid electrolyte as a product. The molar ratio of each element can be controlled by adjusting the content of each element in the raw material, for example.

In the present application, the molar ratio or composition of each element in the sulfide solid electrolyte can be measured by, for example, ICP emission spectrometry, ion chromatography, RBS method, AES method, fluorescent X-ray method. In the present application, the molar ratio or composition of each element in the sulfide solid electrolyte is measured by ICP emission spectrometry, except for special reasons such as difficulty in analysis. The measurement method of the ICP emission spectrometry is described in examples.

The sulfide solid electrolyte of the present invention can be produced, for example, by applying a stronger mechanical stress than conventional ones to a mixture of raw materials and reacting the mixture.

Here, "applying mechanical stress" means mechanically applying a shear force, an impact force, or the like. Examples of the method of applying mechanical stress include a pulverizer such as a planetary ball mill, a vibration mill, or a rotary mill, or a kneader. The raw materials may be pulverized and mixed by these apparatuses.

The conditions for the pulverization and mixing may be appropriately adjusted depending on the apparatus used and the like. For example, when a planetary ball mill is used as the pulverizer, the treatment may be performed for 0.5 to 100 hours at a rotation speed of several tens to several hundreds revolutions per minute. More specifically, in the case of the planetary ball mill (model P-7, manufactured by flight (flight) corporation) used in the examples of the present application, the rotation speed of the planetary ball mill is preferably 450rpm to 700rpm, more preferably 500rpm to 650 rpm. Conventionally, when the raw materials are pulverized and mixed (mechanically ground) by the above-mentioned apparatus, the rotation speed of the planetary ball mill is usually 350rpm to 400 rpm. In the present manufacturing method, the rotational speed is set to be very high compared to the conventional method, so that a strong impact force is applied to the raw material.

When zirconia balls are used as the balls for the pulverization means, the diameter of the balls is preferably 0.2 to 20 mm.

The temperature during mixing may be room temperature without any particular setting, and temperature control is not necessary, but crystallization may be promoted at a high temperature. The temperature during mixing is preferably 0 ℃ to 300 ℃ inclusive, and more preferably 20 ℃ to 250 ℃ inclusive.

In the prior art (for example, patent document 2 and the like), the raw material powder is pulverized and mixed to such an extent that the crystallinity of the raw material powder can be maintained, and then, heat treatment is performed at a high temperature to form a thiogermorite-type crystal structure. Further, in patent document 1, the raw material is heated at 550 ℃ for 6 days to thereby form a thiogermorite-type crystal structure. On the other hand, in the above method, a sulfide solid electrolyte having a different crystal structure from that of the conventional one can be produced by applying a mechanical stress stronger than that of the conventional one to the raw material and reacting the raw material. In the present method, since it is not necessary to subject the raw material to heat treatment at a high temperature, there is no crystal growth caused by the heat treatment.

The raw material used is a combination of 2 or more compounds or monomers, and contains elements necessary for the sulfide solid electrolyte as a whole, i.e., elements such as lithium, phosphorus, sulfur, and an arbitrary halogen.

As the raw material containing lithium, for example, lithium sulfide (Li) can be cited₂S), lithium oxide (Li)₂O), lithium carbonate (Li)₂CO₃) And lithium compounds and lithium metal monomers. Among these, lithium compounds are preferable, and lithium sulfide is more preferable.

Although the use of the above-mentioned lithium sulfide is not particularly limited, it is preferably high-purity lithium sulfide. For example, lithium sulfide can be produced by the methods described in Japanese patent application laid-open Nos. 7-330312, 9-283156, 2010-163356, and 2011-84438.

Specifically, lithium sulfide can be synthesized by reacting lithium hydroxide with hydrogen sulfide in a hydrocarbon organic solvent at 70 to 300 ℃ to produce lithium hydrosulfide, and then subjecting the reaction solution to a hydrogen sulfide removal treatment (jp 2010-163356 a).

Lithium sulfide can be synthesized by reacting lithium hydroxide with hydrogen sulfide in a water solvent at 10 to 100 ℃ to produce lithium hydrosulfide and then subjecting the reaction solution to a hydrogen sulfide removal treatment (jp 2011-84438 a).

Examples of the phosphorus-containing raw material include phosphorus trisulfide (P)₂S₃) Pentasulfide ofDiphosphorus (P)₂S₅) Phosphorus sulfide, sodium phosphate (Na) etc₃PO₄) And phosphorus compounds and phosphorus monomers. Among them, phosphorus sulfide is preferable, and phosphorus pentasulfide (P) is more preferable₂S₅). Phosphorus pentasulfide (P)₂S₅) The phosphorus compound and the phosphorus monomer may be used without any particular limitation as long as they are industrially produced and sold.

As the halogen-containing raw material, for example, a raw material containing a halogen compound represented by the following formula (2) is preferable.

M_l-X_m(2)

In formula (2), M represents sodium (Na), lithium (Li), boron (B), aluminum (Al), silicon (Si), phosphorus (P), sulfur (S), germanium (Ge), arsenic (As), selenium (Se), tin (Sn), antimony (Sb), tellurium (Te), lead (Pb), bismuth (Bi), or a combination of an oxygen element and a sulfur element with these elements, preferably Li or P, and particularly preferably lithium (Li).

X is a halogen element selected from F, Cl, Br and I.

In addition, l is an integer of 1 or 2, and m is an integer of 1 to 10. When m is an integer of 2 to 10, that is, when a plurality of xs are present, xs may be the same or different from each other. For example, SiBrCl described later₃Wherein m is 4 and X is composed of different elements such as Br and Cl.

Specific examples of the halogen compound represented by the formula (2) include sodium halides such as NaI, NaF, NaCl, and NaBr; lithium halides such as LiF, LiCl, LiBr, LiI, and the like; BCl₃、BBr₃、BI₃Boron halides, etc.; AlF₃、AlBr₃、AlI₃、AlCl₃And the like aluminum halides; SiF₄、SiCl₄、SiCl₃、Si₂Cl₆、SiBr₄、SiBrCl₃、SiBr₂Cl₂、SiI₄And the like silicon halides; PF (particle Filter)₃、PF₅、PCl₃、PCl₅、POCl₃、PBr₃、POBr₃、PI₃、P₂Cl₄、P₂I₄And the like phosphorus halides; SF₂、SF₄、SF₆、S₂F₁₀、SCl₂、S₂Cl₂、S₂Br₂And the like sulfur halides; GeF₄、GeCl₄、GeBr₄、GeI₄、GeF₂、GeCl₂、GeBr₂、GeI₂And the like germanium halides; AsF₃、AsCl₃、AsBr₃、AsI₃、AsF₅And the like arsenic halides; SeF₄、SeF₆、SeCl₂、SeCl₄、Se₂Br₂、SeBr₄And the like selenium halides; SnF₄、SnCl₄、SnBr₄、SnI₄、SnF₂、SnCl₂、SnBr₂、SnI₂And the like zinc halides; SbF₃、SbCl₃、SbBr₃、SbI₃、SbF₅、SbCl₅Antimony halides, etc.; TeF₄、Te₂F₁₀、TeF₆、TeCl₂、TeCl₄、TeBr₂、TeBr₄、TeI₄And (3) tellurium halides; PbF₄、PbCl₄、PbF₂、PbCl₂、PbBr₂、PbI₂Lead halides, etc.; BiF₃、BiCl₃、BiBr₃、BiI₃And bismuth halides, etc.

Among them, lithium halides such as lithium chloride (LiCl), lithium bromide (LiBr) and lithium iodide (LiI), and phosphorus pentachloride (PCl) can be preferably used₅) Phosphorus trichloride (PCl)₃) Phosphorus pentabromide (PBr)₅) Phosphorus tribromide (PBr)₃) And the like. Among them, lithium halides such as LiCl, LiBr and LiI, and PBr are preferable₃Lithium halides such as LiCl, LiBr, and LiI are more preferable, and LiCl and LiBr are particularly preferable.

The halogen compound may be used alone or in combination of two or more thereof.

In one embodiment of the present invention, the lithium compound, the phosphorus compound, and the halogen compound are contained, and preferably at least one of the lithium compound and the phosphorus compound contains a sulfur element, more preferably a combination of lithium sulfide, phosphorus sulfide, and lithium halide, and further preferably a combination of lithium sulfide, diphosphorus pentasulfide, and lithium halide.

For example, in the reaction of Li₂S、P₂S₅When LiCl or LiBr is used as a raw material of a sulfide solid electrolyte, the molar ratio of the charged raw material can be Li₂S∶P₂S₅The total ratio of LiCl to LiBr is 30-60: 10-25: 15-50.

For example, using Li₂S、P₂S₅When lithium halide (LiX) or elemental sulfur (S) is used as the raw material of the sulfide solid electrolyte of the present invention, the molar ratio of the charged raw materials can be Li₂S∶P₂S₅LiX and S are 45-70: 8-15: 20-40: more than 0 and less than or equal to 20. The sulfide solid electrolyte of the present invention can be obtained by applying a mechanical stress to these raw materials and reacting them.

The sulfide solid electrolyte of the present invention can be used for a solid electrolyte layer, a positive electrode, a negative electrode, and the like of a lithium ion secondary battery and the like.

[ electrode composite Material ]

An electrode composite material according to an embodiment of the present invention includes the sulfide solid electrolyte according to the present invention and an active material. Alternatively, it is produced from the sulfide solid electrolyte of the present invention. When the negative electrode active material is used as the active material, the negative electrode composite material is obtained. On the other hand, the use of a positive electrode active material results in a positive electrode composite material.

Negative electrode composite material

An anode composite material is obtained by blending an anode active material to the sulfide solid electrolyte of the present invention.

As the negative electrode active material, for example, a carbon material, a metal material, or the like can be used. A composite body composed of 2 or more of these materials can also be used. In addition, a negative electrode active material developed in the future can be used.

Preferably, the negative electrode active material has electron conductivity.

Examples of the carbon material include graphite (e.g., artificial graphite), graphitic carbon fiber, resin-fired carbon, thermally decomposed vapor-grown carbon, coke, mesocarbon microbeads (MCMB), furfuryl alcohol resin-fired carbon, polyacene, pitch-based carbon fiber, vapor-grown carbon fiber, natural graphite, and non-graphitizable carbon.

Examples of the metal material include a metal simple substance, an alloy, and a metal compound. Examples of the metal monomer include metal silicon, metal tin, metal lithium, metal indium, and metal aluminum. Examples of the alloy include alloys containing at least one of silicon, tin, lithium, indium, and aluminum. As the metal compound, a metal oxide can be cited. Examples of the metal oxide include silicon oxide, tin oxide, and aluminum oxide.

The blending ratio of the negative electrode active material to the solid electrolyte is preferably 95 wt% to 5 wt% to 95 wt%, more preferably 90 wt% to 10 wt% to 90 wt%, and still more preferably 85 wt% to 15 wt% to 85 wt%.

When the content of the negative electrode active material in the negative electrode composite material is too small, the capacitance decreases. In addition, when the negative electrode active material has electron conductivity and contains no or only a small amount of a conductive auxiliary agent, it is considered that the electron conductivity (electron conduction path) in the negative electrode is decreased to lower the rate capability, or the utilization rate of the negative electrode active material is decreased to lower the capacity. On the other hand, if the content of the negative electrode active material in the negative electrode composite is too large, it is considered that ion conductivity (ion conduction path) in the negative electrode is lowered to lower the rate capability, or the utilization rate of the negative electrode active material is lowered to lower the capacity.

The negative electrode composite material can also contain a conductive aid.

Preferably, the conductive aid is added when the electron conductivity of the negative electrode active material is low. The conductive assistant is only required to have conductivity, and the electron conductivity thereof is preferably 1 × 10³S/cm or more, more preferably 1X 10⁵And more than S/cm.

Specific examples of the conductive auxiliary agent include those containing at least one element selected from the group consisting of a carbon material, nickel, copper, aluminum, indium, silver, cobalt, magnesium, lithium, chromium, gold, ruthenium, platinum, beryllium, iridium, molybdenum, niobium, osmium, rhodium, tungsten, and zinc, and more preferably a carbon monomer having high conductivity, and a carbon material other than the carbon monomer; a metal monomer, mixture or compound comprising nickel, copper, silver, cobalt, magnesium, lithium, ruthenium, gold, platinum, niobium, osmium or rhodium.

Specific examples of the carbon material include carbon black such as ketjen black, acetylene black, superconducting acetylene black (DenkaBlack), thermal black, and channel black; graphite, carbon fiber, activated carbon, and the like, and they may be used alone or in combination of 2 or more. Among them, acetylene black having high electron conductivity, superconducting acetylene black, and ketjen black are preferable.

When the negative electrode composite material contains the conductive additive, the content of the conductive additive in the composite material is preferably 1-40% by mass, and more preferably 2-20% by mass. If the content of the conductive additive is too small, it is considered that the electron conductivity of the negative electrode is lowered to lower the rate capability, or the utilization rate of the negative electrode active material is lowered to lower the capacity. On the other hand, if the content of the conductive auxiliary agent is too large, the amount of the negative electrode active material and/or the amount of the solid electrolyte decreases. It is estimated that the capacitance decreases when the amount of the negative electrode active material decreases. Further, it is considered that when the amount of the solid electrolyte is decreased, the ion conductivity of the negative electrode may be decreased to lower the rate capability, or the utilization rate of the negative electrode active material may be decreased to lower the capacity.

A binder may be further included to tightly bind the negative electrode active material and the solid electrolyte to each other.

As the adhesive, a fluorine-containing resin such as Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), or fluororubber, a thermoplastic resin such as polypropylene or polyethylene, ethylene-propylene-diene rubber (EPDM), sulfonated EPDM, or Natural Butyl Rubber (NBR) may be used alone or as a mixture of 2 or more kinds. In addition, a cellulose-based or Styrene Butadiene Rubber (SBR) aqueous dispersion or the like can be used as the aqueous binder.

The negative electrode composite material can be produced by mixing the solid electrolyte, the negative electrode active material, and any of the conductive additives and/or binders.

The mixing method is not particularly limited, and for example, dry mixing using a mortar, a ball mill, a bead mill, a jet mill, a planetary ball mill, a vibration ball mill, a sand mill, a chopper can be applied; and wet mixing in which the raw materials are dispersed in an organic solvent, mixed using a mortar, ball mill, bead mill, planetary ball mill, vibration ball mill, sand mill, or thin film rotary mixer (Filmix), and then the solvent is removed. Among them, wet mixing is preferable so as not to destroy the negative electrode active material particles.

Positive electrode composite material

By blending a positive electrode active material into the solid electrolyte of the present invention, a positive electrode composite material can be obtained.

The positive electrode active material is a material capable of intercalating and deintercalating lithium ions, and a material known as a positive electrode active material in the field of batteries can be used. Further, a positive electrode active material developed in the future can be used.

Examples of the positive electrode active material include metal oxides and sulfides. The sulfide includes metal sulfide and nonmetal sulfide.

The metal oxide is, for example, a transition metal oxide. Specifically, V can be exemplified₂O₅、V₆O₁₃、LiCoO₂、LiNiO₂、LiMnO₂、LiMn₂O₄、Li(Ni_aCo_bMn_c)O₂(Here, 0)<a<1、0<b<1、0<c<1、a+b+c＝1)、LiNi_1-YCo_YO₂、LiCo_1-YMn_YO₂、LiNi_1-YMn_YO₂(Here, 0. ltoreq. Y<1)、Li(Ni_aCo_bMn_c)O₄(0<a<2、0<b<2、0<c<2、a+b+c＝2)、LiMn_2-ZNi_ZO₄、LiMn_2-ZCo_ZO₄(Here, 0)<Z<2)、LiCoPO₄、LiFePO₄、CuO、Li(Ni_aCo_bAl_c)O₂(Here, 0)<a<1、0<b<1、0<c<1. a + b + c ═ 1), and the like.

The metal sulfide includes titanium sulfide (TiS)₂) Molybdenum sulfide (MoS)₂) Iron sulfide (FeS )₂) Copper sulfide (CuS) and nickel sulfide (Ni)₃S₂) And the like.

In addition, as the metal oxide, bismuth oxide (Bi) can be mentioned₂O₃) Lead acid bismuth (Bi)₂Pb₂O₅) And the like.

Examples of the nonmetallic sulfide include organic disulfide compounds and carbon sulfide compounds.

In addition to the above, niobium selenide (NbSe)₃) Metal indium and sulfur can also be used as the positive electrode active material.

The positive electrode composite material may also further include a conductive auxiliary agent.

The conductive additive is the same as that used for the cathode composite material.

The blending ratio of the solid electrolyte and the positive electrode active material in the positive electrode composite material, the content of the conductive auxiliary agent, and the method for producing the positive electrode composite material are the same as those in the case of the negative electrode composite material described above.

[ lithium ion Battery ]

A lithium ion battery according to an embodiment of the present invention includes at least one of the sulfide solid electrolyte and the electrode composite material of the present invention. Or is produced from at least one of the sulfide solid electrolyte and the electrode composite material of the present invention.

The lithium ion battery is not particularly limited in configuration, but generally has a structure in which a negative electrode layer, an electrolyte layer, and a positive electrode layer are stacked in this order. The layers of the lithium ion battery are explained below.

(1) Negative electrode layer

The negative electrode layer is preferably a layer made of the negative electrode composite material of the present invention.

Alternatively, the negative electrode layer is preferably a layer containing the negative electrode composite material of the present invention.

The thickness of the negative electrode layer is preferably 100nm to 5mm, more preferably 1 μm to 3mm, and still more preferably 5 μm to 1 mm.

The negative electrode layer can be produced by a known method, for example, by a coating method or an electrostatic method (electrostatic spraying method, electrostatic screen method, or the like).

(2) Electrolyte layer

The electrolyte layer is a layer containing a solid electrolyte or a layer made of a solid electrolyte. The solid electrolyte is not particularly limited, and is preferably the sulfide solid electrolyte of the present invention.

The electrolyte layer may be composed of only a solid electrolyte, or may further contain a binder. As the binder, the same binder as that of the negative electrode composite material of the present invention can be used.

The thickness of the electrolyte layer is preferably 0.001mm or more and 1mm or less.

The solid electrolyte of the electrolyte layer may be fused. The fusion means that a part of the solid electrolyte particles is dissolved and the dissolved part is integrated with other solid electrolyte particles. The electrolyte layer may be a solid electrolyte plate-like body, and the plate-like body also includes a case where a part or all of the solid electrolyte particles are dissolved to form a plate-like body.

The electrolyte layer can be produced by a known method, for example, by a coating method or an electrostatic method (electrostatic spraying method, electrostatic screen method, or the like).

(3) Positive electrode layer

The positive electrode layer is a layer containing a positive electrode active material, and preferably a layer containing or made of the positive electrode composite material of the present invention.

The thickness of the positive electrode layer is preferably 0.01mm to 10 mm.

The positive electrode layer can be produced by a known method, for example, by a coating method or an electrostatic method (electrostatic spraying method, electrostatic screen method, or the like).

(4) Current collector

Preferably, the lithium ion battery according to an embodiment of the present invention further includes a current collector. For example, the negative electrode current collector is provided on the opposite side of the negative electrode layer from the electrolyte layer side, and the positive electrode current collector is provided on the opposite side of the positive electrode layer from the electrolyte layer side.

As the current collector, a plate-like body or a foil-like body made of copper, magnesium, stainless steel, titanium, iron, cobalt, nickel, zinc, aluminum, germanium, indium, lithium, or an alloy thereof or the like can be used.

The lithium ion battery according to an embodiment of the present invention can be manufactured by bonding and joining the above members. As a method of joining, there is a method of laminating the respective members and pressing them, or a method of passing them between two rollers and pressing them (roll to roll).

The bonding surface may be bonded via an active material having ion conductivity or a bonding material that does not inhibit ion conductivity.

In the joining, the fusion may be performed by heating in a range in which the crystal structure of the solid electrolyte does not change.

The lithium ion battery according to an embodiment of the present invention can also be manufactured by sequentially forming the above-described members. The resin composition can be produced by a known method, for example, by a coating method or an electrostatic method (electrostatic spraying method, electrostatic screen method, or the like).