Compounds and batteries comprising the same

Abstract

To provide a compound capable of being used as a binder having ion conductivity and a battery including the compound. One of the present invention is a compound including P and S as constituent elements, and having: a group bonded to the above P and including one or more elements selected from the group consisting of O, N, and halogen; and a disulfide bond.

Description

Technical Field

[0001] This invention relates to a compound and a battery containing the compound. Background Technology

[0002] All-solid-state batteries, such as all-solid-state lithium-ion batteries, typically consist of a positive electrode layer, a solid electrolyte layer (sometimes simply called the "electrolyte layer"), and a negative electrode layer. By incorporating binders into these layers, it is possible to fabricate the individual layers or their laminates into sheets.

[0003] Polymerization of PS4 on the surface of electrode active materials is disclosed in Non-Patent Documents 1 and 2. Furthermore, Non-Patent Document 3 discloses a chemical structural change in 70Li2S-30P2S5 caused by heat treatment.

[0004] Existing technical documents

[0005] Non-patent literature

[0006] Non-patent literature 1: Masato Sumita et al., “Possible Polymerization of PS4 at a Li3PS4 / FePO4 Interface with Reduction of the FePO4 Phase”, The Journal of Physical Chemistry C, April 24, 2017, Vol. 121, pp. 9698-9704.

[0007] Non-patent literature 2: Takashi Hakari et al., 10, “Structural and Electronic-State Changes of a Sulfide Solid Electrolyte during the Li Deinsertion-Insertion Processes”, Chemistry of Materials, May 3, 2017, Vol. 29, pp. 4768-4774.

[0008] Non-Patent Document 3: Yuichi Hasegawa, "Chemical Structure Analysis of Sulfide-Based Solid Electrolyte 70Li2S-30P2S5", [Online], February 1, 2018, Toray Research Center Inc., [Retrieved on July 9, 2019], URL <URL: https: / / www.toray-research.co.jp / technical-info / trcnews / pdf / 201802-01.pdf> Summary of the Invention

[0009] As the binder, polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), etc. can be considered. However, such binders have the following technical problems: If the addition amount is increased to obtain the adhesiveness between the materials constituting the layer (for example, electrode composite materials), the ionic conductivity decreases. Therefore, a compound having ionic conductivity and capable of functioning as a binder is desired.

[0010] One object of the present invention is to provide a compound that can be used as an ionic conductive binder and a battery containing the compound.

[0011] The inventors of the present invention conducted intensive studies and found that a compound containing phosphorus and sulfur as constituent elements and having a disulfide bond can be used as an ionic conductive binder, thereby completing the present invention.

[0012] According to the present invention, the following compounds, etc. can be provided.

[0013] 1. A compound, comprising P and S as constituent elements, and having:

[0014] A group bonded to the P and containing one or more elements selected from the group consisting of O, N, and halogen; and

[0015] A disulfide bond.

[0016] 2. The compound according to 1, wherein the group contains O.

[0017] 3. The compound according to 1 or 2, having a peak derived from a disulfide bond bonding two Ps in Raman spectroscopic analysis.

[0018] 4. The compound according to any one of 1 to 3, in 31 P-NMR measurement, having a peak derived from PS x O y structure (where 1 ≤ x and 0 < y).

[0019] 5. The compound according to 4, derived from the PS x O yThe peaks in the structure are derived from the PS3O structure.

[0020] 6. The compound described in any one of 1 to 5, comprising a structure represented by the following formula (1).

[0021]

Chemistry 1

[0022]

[0023] (In equation (1), X is any group.)

[0024] 7. The compound described in any one of 1 to 6, comprising a structure represented by formula (1) and a structure represented by formula (7).

[0025]

Chemistry 2

[0026]

[0027] (In equations (1) and (7), X is any group, and multiple Xs can be the same or different.)

[0028] 8. The compound described in any one of 1 to 7, comprising one or more elements selected from the group consisting of Li, Na, Mg and Al as constituent elements.

[0029] 9. The compound as described in any one of 1 to 8 is a compound obtained by adding an oxidizing agent to a raw material compound and then reacting the raw material compound with the oxidizing agent, wherein the raw material compound comprises P and S, and one or more elements selected from the group consisting of O, N and halogens as constituent elements.

[0030] 10. The compound described in any one of 1 to 9, comprising a disulfide bond formed by the following reaction formula (9).

[0031]

Transformation 3

[0032]

[0033] (In the formula, R is a group containing one or more elements selected from the group consisting of O, N, and halogens. X is a halogen.)

[0034] 11. The compound as described in 10, wherein X in the reaction formula (9) is iodine (I), fluorine (F), chlorine (Cl) or bromine (Br).

[0035] 12. A battery adhesive comprising any one of the compounds described in 1 to 11.

[0036] 13. The battery adhesive as described in 12, comprising halogen.

[0037] 14. The battery adhesive as described in 13, wherein the halogen is I or Br.

[0038] 15. A battery electrode composite material layer or electrolyte layer comprising the battery adhesive described in any one of 12 to 14.

[0039] 16. The electrode composite material layer or electrolyte layer for batteries as described in 15, further comprising a solid electrolyte.

[0040] 17. A battery sheet comprising one or more layers selected from the group consisting of a battery electrode composite material layer and an electrolyte layer as described in 15 or 16.

[0041] 18. A battery comprising the compound described in any one of 1 to 11.

[0042] 19. A method for manufacturing a compound, comprising:

[0043] An oxidizing agent is added to a raw material compound containing P and S, and one or more elements selected from the group consisting of O, N, and halogens as constituent elements; and

[0044] The raw material compound is reacted with the oxidant.

[0045] 20. A method for manufacturing a compound as described in 19, wherein the raw material compound comprises one or more constituent elements selected from the group consisting of Li, Na, Mg and Al.

[0046] 21. A method for producing the compound as described in 19 or 20, wherein the starting compound comprises PS x O y Structure (where 1≤x and 0) <y)。

[0047] 22. The method for manufacturing the compound as described in 21, wherein the PS x O y The structure is a PS3O structure.

[0048] 23. A method for producing a compound according to any one of claims 19 to 22, wherein the oxidant is a halogen monomer.

[0049] 24. The method for producing the compound as described in 23, wherein the halogen monomer is I2 or Br2.

[0050] 25. A method for producing a compound as described in any one of 19 to 24, wherein the raw material compound is reacted with the oxidant by means of one or more energies selected from the group consisting of physical energy, thermal energy and chemical energy.

[0051] 26. A method for producing a compound as described in any one of 19 to 24, wherein the starting compound is reacted with the oxidizing agent in a liquid.

[0052] According to the present invention, a compound and a battery comprising the compound can be provided, the compound being usable as an ion-conducting adhesive. Attached Figure Description

[0053] Figure 1 The Raman spectra are those of the compounds obtained in Manufacturing Example 1 and Examples 1-4.

[0054] Figure 2 The Raman spectra are those of the compounds obtained in Manufacturing Example 3 and Example 6.

[0055] Figure 3 The image shows the Raman spectrum of the compound obtained in Example 7.

[0056] Figure 4 This is a graph showing the results of powder X-ray analysis of the compounds obtained in Manufacturing Example 1 and Examples 1-4.

[0057] Figure 5 The solid of the compound obtained in Manufacturing Example 1 and Example 1 31 P-NMR spectrum.

[0058] Figure 6 The solid of the compound obtained in Examples 2-4 31 P-NMR spectrum.

[0059] Figure 7 The solid of the compound obtained in Example 5 31 P-NMR spectrum.

[0060] Figure 8 This is a graph showing the initial charge and discharge results of the batteries of Example 13 and Comparative Examples 6 and 7.

[0061] Figure 9 This is a graph showing the initial charge and discharge results of the battery in Example 14.

[0062] Figure 10 This is the Cole-Cole plot of the batteries in Example 13 and Comparative Examples 6 and 7.

[0063] Figure 11 This is the Cole-Cole plot of the battery in Example 14.

[0064] Figure 12 This is a graph showing the results of the cycle characteristics of the batteries of Example 13 and Comparative Examples 6 and 7.

[0065] Figure 13 This is a graph showing the results of the cycle characteristics of the battery in Example 14.

[0066] Figure 14 The Raman spectra are those of the compounds obtained in Examples 15 and 16.

[0067] Figure 15 This is a graph showing the XPS measurement results of Example 15.

[0068] Figure 16 This is a graph showing the XPS measurement results of Example 16. Detailed Implementation

[0069] The following describes in detail the compounds, battery adhesives, battery electrode composite material layers, electrolyte layers, battery sheets, batteries, and methods for manufacturing the compounds of the present invention.

[0070] In addition, in this specification, "x~y" refers to a numerical range of "above x and below y". The upper and lower limits of the numerical range can be combined arbitrarily.

[0071] Solutions obtained by combining two or more of the various solutions of the present invention described below are also solutions of the present invention.

[0072] <Compound α>

[0073] One embodiment of the compound of the present invention (also referred to as "compound α") contains P and S as constituent elements and has the following characteristics:

[0074] A group (also referred to as "group R") bonded to the P and comprising one or more elements selected from the group consisting of O, N, and halogens; and

[0075] Disulfide bonds.

[0076] Compound α exhibits ionic conductivity and is preferably used as an adhesive, such as a battery binder. Furthermore, compound α demonstrates excellent solubility. This can be attributed to the fact that even with high concentrations of compound α, branching of the molecular chains is suppressed, thus inhibiting the formation of a three-dimensional mesh structure that reduces solubility.

[0077] There are no particular limitations on the group R as long as it contains one or more elements selected from the group consisting of O, N, and halogens. Examples include -OM (where M is a metal element), halogens, =NH, -N=Y, and -N(Z). 1 )Z 2 etc. (Regarding Y, Z) 1 and Z 2 (To be discussed later). In -OM, M can be exemplified by, for example, Li, Na, Mg, Al, etc.

[0078] In one embodiment, the group R contains one or more elements selected from the group consisting of O and N.

[0079] Preferably, the group R contains O. Furthermore, it is also preferred that the group R contains N.

[0080] The group R can be a single bond or a multiple bond (e.g., a double bond or a triple bond) relative to P in compound α.

[0081] In one embodiment, the O, N, or halogen contained in group R is directly bonded (e.g., covalently bonded) to the P contained in compound α.

[0082] Compound α can have more than one group R. When there are two or more groups R, the two or more groups R can be the same or different from each other.

[0083] In one embodiment, compound α exhibits a peak in Raman spectrophotometry originating from a disulfide bonded to two P atoms.

[0084] In one embodiment, compound α, in Raman spectrophotometry, has a Raman shift of 425 cm⁻¹. -1 Above 500cm -1 The following, preferably 440cm -1 Above 490cm -1 The following, or more preferably, is 460cm -1 Above 480cm -1 The following range has a peak (hereinafter also referred to as "peak A").

[0085] Peak A originates from the disulfide bond (SS) of two P atoms in compound α.

[0086] The presence of a disulfide bond (SS) in compound α can be used to identify it by the presence of peak A.

[0087] In one embodiment, compound α, in Raman spectrophotometry, has a Raman shift of 370 cm⁻¹. -1 Above and below 425cm -1 The preferred size is 380cm. -1 Above 423cm -1 The following, or more preferably, is 390cm -1 Above 420cm -1 The following range has a peak (hereinafter also referred to as "peak B").

[0088] Peak B originates from PS (described later). x O y Symmetrical scaling of the PS key in the structure and / or PS4 structure.

[0089] Raman spectroscopic analysis of compound α was carried out by the method described in the examples. At this time, it is crucial to measure after treating compound α with toluene. This is to remove monomeric sulfur that may be mixed in compound α. Monomeric sulfur has a peak at a position that may overlap with peak A. Therefore, by removing monomeric sulfur, peak A derived from compound α can be measured well. The toluene treatment is carried out according to the procedure described in the examples.

[0090] In one embodiment, compound α has a peak derived from PS 31 in the x P-NMR measurement y structure (where 1 ≤ x and 0 < y).

[0091] For PS x O y structure, there is no particular limitation.

[0092] In one embodiment, the PS x O y structure is one or more selected from the group consisting of PS3O structure, PS2O2 structure, and PSO3 structure, and P2S6O structure (PS3O 1 / 2 structure), P2S5O2 structure (PS 5 / 2 O), P2S4O3 structure (PS2O 3 / 2 structure), P2S3O4 structure (PS 3 / 2 O2 structure), and P2S2O7 structure (PSO 7 / 2 structure) may exist as similar structures.

[0093] In one embodiment, the PS x O y structure is PS3O structure.

[0094] In addition, P-NMR measurement can be carried out by the method described in the examples. 31

[0095] In one embodiment, compound α contains one or more structures selected from the group consisting of the structures represented by the following general formulas (1) to (5). Thus, the effects of the present invention can be exerted better.

[0096]

Chemical formula 4

[0097]

[0098] In formulas (1) to (3), X is an arbitrary group, for example, the above-mentioned metal element M. In formula (4), Y is an arbitrary group, for example, ═PS2. In formula (5), Z 1 and Z 2These can be any group, and they can be the same as or different from each other, for example, -PS3.

[0099] The preferred compound α comprises a structure represented by formula (1). This allows for a better application of the invention.

[0100] In one embodiment, compound α comprises a structure represented by the following formula (6). This allows for a better application of the effects of the invention.

[0101]

Transformation 5

[0102]

[0103] In equation (6), X is any group, such as the metal element M mentioned above. The two Xs can be the same or different.

[0104] In one embodiment, compound α collectively comprises a structure represented by formula (1) and a structure represented by formula (7) below.

[0105]

Transformation 6

[0106]

[0107] In formula (7), X is any group, such as the metal element M mentioned above.

[0108] Here, in compound α, the structure represented by formula (1) can be included as the structure represented by formula (6). Furthermore, compound α can include both the structure represented by formula (1) and the structure represented by formula (7). In this case, the multiple Xs can be the same or different.

[0109] In one embodiment, the structure represented by formula (1) is included as a repeating unit in compound α. In another embodiment, when compound α includes the structure represented by formula (7), the structure represented by formula (7) is included as a repeating unit in compound α.

[0110] In addition, NMR and Raman measurements can confirm that compound α contains the structures represented by formulas (1) to (7).

[0111] In one embodiment, compound α comprises one or more elements selected from the group consisting of Li, Na, Mg, and Al as constitutive elements. In one embodiment, these constitutive elements are bonded to S in compound α via ionic bonds. Furthermore, when compound α contains O, these constitutive elements are bonded to O via ionic bonds to form an example of the aforementioned group R, namely -OM.

[0112] <Battery Adhesive>

[0113] A battery adhesive (hereinafter referred to as battery adhesive (A)) according to one embodiment of the present invention comprises the above-described compound α. Battery adhesive (A) may further comprise a halogen. The halogen may be derived from an oxidant or the like used in the manufacture of compound α.

[0114] Halogens can be one or more selected from the group consisting of I, F, Cl, and Br. Halogens can also be I or Br.

[0115] The form of the halogen is not particularly limited, and can be one or more selected from the group consisting of salts and halogen monomers, wherein the salt is a salt of one or more elements selected from the group consisting of Li, Na, Mg, and Al with a halogen. Examples of salts include LiI, NaI, MgI2, AlI3, LiBr, NaBr, MgBr2, and AlBr3. Among these, LiI and LiBr are preferred from the viewpoint of ionic conductivity. Examples of halogen monomers include I2, F2, Cl2, and Br2. Among these, I2 and Br2 are preferred from the viewpoint of reducing corrosion when remaining in the binder (A).

[0116] In one embodiment, by including halogens in the battery adhesive (A) in the manner described above as salts, higher ionic conductivity can be achieved.

[0117] In one embodiment, the battery adhesive (A) further comprises one or more selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid and their salts.

[0118] The content of compound α in the battery adhesive (A) is not particularly limited. For example, from the viewpoint of the binding force of active materials and solid electrolytes described later, when the total mass of the battery adhesive (A) is set to 100% by mass, the content of compound α is 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.8% by mass or more, or 99.9% by mass or more.

[0119] The content of halogen-containing substances (halogen monomers and halogen compounds; however, halogen compounds belonging to compound α are not included in the halogen-containing substances) in the battery adhesive (A) is not particularly limited. For example, from the viewpoint of the conductivity of ions as carriers and the binding force of active materials and solid electrolytes, when the total mass of the battery adhesive (A) is set as 100% by mass, the content of the halogen-containing substances can be 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, 5% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.1% by mass or less, 0.05% by mass or less, or 0.01% by mass or less.

[0120] There is no particular limitation on the total content of orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid and their salts in the battery adhesive (A).

[0121] In addition, the battery adhesive (A) is substantially 100% by mass of compound α, or can be compound α and one or more selected from the group consisting of halogen-containing substances, or selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphorous acid and their salts.

[0122] The battery adhesive (A) can be used in various types of batteries. Examples of batteries include rechargeable batteries such as lithium-ion batteries. Furthermore, the battery can be an all-solid-state battery. In such batteries, the "adhesive" can be incorporated into any element, for example, into one or more layers selected from the group consisting of battery electrode composite material layers and electrolyte layers, thereby exerting adhesive properties (adhesive force) to bond other components contained in that element (e.g., the layer) together and maintain their integrity.

[0123] Existing battery electrode composite material layers (such as the positive or negative electrodes described later) are difficult to adapt to the expansion and contraction (volume change) of the electrode active materials during charging and discharging, easily leading to capacity degradation and other problems. The electrolyte layer adjacent to the battery electrode composite material layer may also be affected by the volume changes of the battery electrode composite material layer, resulting in degradation. In contrast, by using a battery adhesive (A), the battery electrode composite material layer or electrolyte layer can absorb volume changes through the flexibility of the battery adhesive (A), preventing capacity degradation. As a result, the battery can exhibit excellent cycle characteristics. Furthermore, since the battery adhesive (A) itself has ionic conductivity, even if the amount of battery adhesive (A) added is increased to improve the adhesion between the constituent materials (e.g., electrode composite materials), the decrease in ionic conductivity can be suppressed, allowing the battery to perform well. Moreover, in one embodiment, since the battery adhesive (A) has superior heat resistance compared to conventional organic adhesives or polymeric solid electrolytes (e.g., polyethylene oxide), the operating temperature range of the battery can be expanded.

[0124] <Electrode composite material layer or electrolyte layer for batteries>

[0125] The battery electrode composite material layer or electrolyte layer of one embodiment of the present invention includes the above-mentioned battery adhesive (A).

[0126] In one embodiment, the battery adhesive (A) is either non-uniformly distributed or uniformly distributed (dispersed) within the battery electrode composite material layer or electrolyte layer. In another embodiment, the battery adhesive (A) is uniformly distributed (dispersed) within the layer, thereby better maintaining the integrity of the layer.

[0127] The preferred electrode composite material layer or electrolyte layer for the battery also includes a solid electrolyte (hereinafter referred to as solid electrolyte (B)). Furthermore, the term "solid electrolyte (B)" as used herein does not include the battery binder (A). The solid electrolyte (B) is not particularly limited; for example, oxide solid electrolytes and sulfide solid electrolytes can be used. Among these, sulfide solid electrolytes are preferred, and specifically, sulfide solid electrolytes having the following crystal structures can be cited as examples: argillium sulfide-germanium sulfide crystal structure, Li3PS4 crystal structure, Li4P2S6 crystal structure, and Li7P3S6 crystal structure. 11 Crystal structure, Li 4-x Ge 1-x P x S4 type sulfide crystalline lithium superionic conductor thio-LISICON Region II crystal structure, and Li 4-x Ge 1-x P xCrystal structures similar to those of thio-LISICON Region II (hereinafter sometimes simply referred to as the RII-type crystal structure) of the S4 type lithium superionic conductor, etc.

[0128] In addition, the solid electrolyte (B) may or may not contain a compound obtained by substituting all groups R in compound α with -SM (where M is a metal element, referring to the description of compound α) (also referred to as "compound α'"). Furthermore, the solid electrolyte (B) may or may not contain an organic binder.

[0129] Examples of the battery electrode composite material layer include, for example, a positive electrode, a negative electrode, etc.

[0130] When the battery electrode composite material layer is a positive electrode, the positive electrode can further contain a positive electrode active material. The positive electrode active material is a substance capable of intercalating and deintercalating lithium ions, and substances known as positive electrode active materials in the battery field can be used.

[0131] Examples of the positive electrode active material include, for example, metal oxides, sulfides, etc. Sulfides include metal sulfides and non-metal sulfides.

[0132] The metal oxide is, for example, a transition metal oxide. Specifically, examples include V2O5, V6O 13 , LiCoO2, LiNiO2, LiMnO2, LiMn2O4, Li(Ni a Co b Mn c )O2 (where 0 < a < 1, 0 < b < 1, 0 < c < 1, a + b + c = 1), LiNi 1-Y Co Y O2, LiCo 1-Y Mn Y O2, LiNi 1-Y Mn Y O2 (where 0 ≤ Y < 1), Li(Ni a Co b Mn c )O4 (0 < a < 2, 0 < b < 2, 0 < c < 2, a + b + c = 2), LiMn 2-Z Ni Z O4, LiMn 2-Z Co Z O4 (where 0 < Z < 2), LiCoPO4, LiFePO4, CuO, Li(Ni a Co b Al c )O2 (where 0 < a < 1, 0 < b < 1, 0 < c < 1, a + b + c = 1), etc.

[0133] Examples of metal sulfides include titanium sulfide (TiS2), molybdenum sulfide (MoS2), iron sulfide (FeS, FeS2), copper sulfide (CuS), and nickel sulfide (Ni3S2).

[0134] In addition, examples of metal oxides include bismuth oxide (Bi2O3) and bismuth lead oxide (Bi2Pb2O5).

[0135] Examples of non-metallic sulfides include organic disulfides and carbon disulfides.

[0136] In addition, niobium selenide (NbSe3), metallic indium, and sulfur can also be used as positive electrode active materials.

[0137] When the electrode composite material layer for batteries is the negative electrode, the negative electrode can further contain negative electrode active material.

[0138] The negative electrode active material can be any of the materials commonly used in lithium-ion secondary batteries, such as: carbon materials like graphite, natural graphite, artificial graphite, hard carbon, and soft carbon; composite metal oxides like polyphenylene conductive polymers and lithium titanate; and compounds that form alloys with lithium, such as silicon, silicon alloys, silicon composite oxides, tin, and tin alloys. Preferably, the negative electrode active material includes one or more materials selected from the group consisting of Si (silicon, silicon alloys, silicon-graphite composites, silicon composite oxides, etc.) and Sn (tin, tin alloys).

[0139] One or both of the positive and negative electrodes may contain conductive additives. When the electronic conductivity of the active material is low, it is preferable to add conductive additives. This improves the rate performance of the battery.

[0140] Specific examples of conductive additives include carbon materials, substances containing at least one element selected from the group consisting of nickel, copper, aluminum, indium, silver, cobalt, magnesium, lithium, chromium, gold, ruthenium, platinum, beryllium, iridium, molybdenum, niobium, osmium, rhodium, tungsten, and zinc, more preferably carbon monomers with high conductivity, carbon materials other than carbon monomers; and metal monomers, mixtures, or compounds containing nickel, copper, silver, cobalt, magnesium, lithium, ruthenium, gold, platinum, niobium, osmium, or rhodium.

[0141] In addition, specific examples of carbon materials include Ketjen black, acetylene black, Denka black, thermal cracking carbon black, channel black, etc.; graphite, carbon fiber, activated carbon, etc. These can be used alone or in combination of two or more. Among them, acetylene black and Ketjen black, with their high electronic conductivity, are preferred.

[0142] The electrolyte layer may contain a battery binder (A) and a solid electrolyte (B) other than the battery binder (A) as any component.

[0143] The composition of the positive electrode is not particularly limited. For example, the positive electrode active material can be in the following mass ratio: solid electrolyte (B): battery binder (A): conductive additive = 50-99: 0-30: 1-30: 0-30.

[0144] The positive electrode contains 30% or more by mass, 50% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 98% or more by mass, or 99% or more by mass, which can be used as positive electrode active material, solid electrolyte (B), battery binder (A) and conductive additive.

[0145] The composition of the negative electrode is not particularly limited. For example, the negative electrode active material can be in the following mass ratio: solid electrolyte (B): battery binder (A): conductive additive = 40-99: 0-30: 1-30: 0-30.

[0146] The negative electrode contains 30% or more by mass, 50% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 98% or more by mass, or 99% or more by mass, which can be used as negative electrode active material, solid electrolyte (B), battery binder (A) and conductive additive.

[0147] The composition of the electrolyte layer is not particularly limited; for example, it can be a solid electrolyte (B) : battery binder (A) ratio of 99.9 : 0.1 to 0 : 100 by mass.

[0148] When the mass ratio of the solid electrolyte (B) is 0, the battery binder (A) can also function as a solid electrolyte.

[0149] The electrolyte layer can be 30% or more by mass, 50% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 98% or more by mass, 99% or more by mass, or 99.9% or more by mass to be a solid electrolyte (B) and a battery binder (A).

[0150] The method for forming the layer containing compound α, such as the method for forming the layers constituting the battery as described above, is not particularly limited; for example, a coating method can be used. In the coating method, a coating liquid obtained by dissolving or dispersing the components contained in each layer in a solvent can be used. As the solvent contained in the coating liquid, chain-like, cyclic, or aromatic ethers (e.g., dimethyl ether, dibutyl ether, tetrahydrofuran, anisole, etc.), esters (e.g., ethyl acetate, ethyl propionate, etc.), alcohols (e.g., methanol, ethanol, etc.), amines (e.g., tributylamine, etc.), amides (e.g., N-methylformamide, etc.), lactams (e.g., N-methyl-2-pyrrolidone, etc.), hydrazine, acetonitrile, etc. can be used. After coating, the solvent is dried, thereby forming a layer (the dried coating film). From the viewpoint of easy drying of the solvent, anisole is preferred. The drying method is not particularly limited; for example, one or more methods selected from the group consisting of heating drying, air drying, and reduced pressure drying (including vacuum drying) can be used.

[0151] The compound α in this scheme has excellent solubility, improved dispersibility and stretchability, and is preferably suitable for the coating method described above. It can be used with various solvents with high versatility and can improve the adhesion of the formed layer.

[0152] The component to which the coating solution is applied is not particularly limited. The formed layer can be used in the battery along with the component, or the formed layer can be peeled off from the component and used in the battery. In one embodiment, the coating solution for forming the positive electrode is applied to the positive electrode current collector. In one embodiment, the coating solution for forming the negative electrode is applied to the negative electrode current collector. In one embodiment, the coating solution for forming the electrolyte layer is applied to either the positive or negative electrode. In one embodiment, after the coating solution for forming the electrolyte layer is applied to an easily peelable component, the formed layer is peeled off from the easily peelable component and disposed between the positive and negative electrodes.

[0153] It is preferable to stamp the dried coating (layer). Stamping simply involves pressing and compressing the layer. For example, stamping can be performed to reduce the porosity of the layer. The stamping apparatus is not particularly limited; for example, a roller press or a uniaxial press can be used. The stamping temperature is not particularly limited; it can be around room temperature (23°C), or a temperature lower or higher than room temperature. By performing stamping, the battery binder (A) contained in the layer is appropriately deformed due to its flexibility, promoting the formation of interfaces between the electrode composite materials contained in the layer. As a result, the battery characteristics are further improved.

[0154] Each layer can be stamped, or multiple layers (such as "battery sheet" as described later) can be pressed in the stacking direction to perform stamping.

[0155] <Battery Sheets>

[0156] One embodiment of the present invention provides a battery sheet comprising one or more layers selected from the group consisting of the aforementioned electrode composite material layer and electrolyte layer. By including compound α or a battery adhesive (A) in the battery sheet, excellent flexibility is achieved, preventing breakage or peeling from the current collector.

[0157] <Battery>

[0158] The battery of one embodiment of the present invention comprises the above-described compound α.

[0159] In one embodiment, the battery is an all-solid-state battery.

[0160] In one embodiment, the all-solid-state battery comprises a stack comprising, in sequence, a positive current collector, a positive electrode, an electrolyte layer, a negative electrode, and a negative current collector. The current collector can be a plate-like or foil-like material made of copper, magnesium, stainless steel, titanium, iron, cobalt, nickel, zinc, aluminum, germanium, indium, lithium, or alloys thereof.

[0161] In the battery, it is preferred to have one or more layers containing compound α, selected from the group consisting of a positive electrode, an electrolyte layer and a negative electrode.

[0162] The above description (and the examples described later) mainly focuses on the use of compound α in batteries, but is not limited to this. Due to the excellent flexibility and ionic conductivity of compound α, it can be widely used in various applications.

[0163] <Method for manufacturing compound α>

[0164] One aspect of the present invention provides a method for manufacturing compound α, comprising: adding an oxidizing agent to a raw material compound containing P, S, and O as constituent elements; and reacting the raw material compound with the oxidizing agent.

[0165] By reacting the above-mentioned raw material compound with an oxidizing agent, the above-mentioned compound α can be obtained as a product.

[0166] In one embodiment, compound α is a compound obtained by adding an oxidant to a raw material compound and then reacting the raw material compound with the oxidant, wherein the raw material compound contains P and S, and one or more elements selected from the group consisting of O, N and halogens as constituent elements.

[0167] The raw material compound (hereinafter referred to as "raw material compound (C)") contains P and S, and one or more elements selected from the group consisting of O, N and halogens as constituent elements.

[0168] The raw material compound (C) preferably contains one or more elements selected from the group consisting of Li, Na, Mg and Al as constituent elements.

[0169] The raw material compound (C) preferably contains PS. x O y Structure (where 1≤x and 0) <y)。

[0170] In one implementation, PS x O y The structure can be selected from one or more structures composed of PS3O, PS2O2, and PSO3, and can also contain a P2S6O structure (PS3O). 1 / 2 (structure), P2S5O2 structure (PS) 5 / 2 O), P2S4O3 structure (PS2O) 3 / 2 (structure), P2S3O4 structure (PS) 3 / 2 O2 structure) and P2S2O7 structure (PSO 7 / 2 (Structure) as a similar structure.

[0171] In one implementation, PS x O y The structure is a PS3O structure.

[0172] Examples of raw material compounds (C) containing the PS3O structure include Li3PS3O, Na3PS3O, and Mg. 3 / 2 PS3O, etc.

[0173] Li3PS3O can be produced, for example, by reacting Li2O, Li2S and P2S5 in the presence of a dispersion medium using a mechanochemical method (mechanical grinding).

[0174] In one embodiment, compound α can be produced by reacting Li2O, Li2S, and P2S5 with an oxidant in the presence of a dispersion medium (e.g., n-heptane) using a mechanochemical method (mechanical grinding).

[0175] As a raw material compound (C), one type can be used alone, or two or more types can be used together.

[0176] Alternatively, a raw material compound (also called "raw material compound (C')") containing P and S as constituent elements and lacking O can be used together with the raw material compound (C). In this case, an oxidizing agent can be added to the mixture of raw material compound (C) and raw material compound (C') to react the raw material compound (C) and raw material compound (C') in the mixture with the oxidizing agent.

[0177] The raw material compound (C') preferably contains one or more elements selected from the group consisting of Li, Na, Mg and Al as constituent elements.

[0178] In one embodiment, the feedstock compound (C') comprises a PS4 structure.

[0179] Examples of starting material compounds (C') containing a PS4 structure include Li3PS4, Li4P2S7, Na3PS4, and Na4P2S7. Furthermore, the starting material compound (C) may contain two or more PS4 structures, as in Li4P2S7 and Na4P2S7. In the case where the starting material compound (C') contains two adjacent PS4 structures, these two PS4 structures may share one S atom.

[0180] Li3PS4 can be produced, for example, by reacting Li2S with P2S5 in the presence of a dispersion medium using a mechanochemical method (mechanical milling). Examples of dispersion media include n-heptane.

[0181] As a raw material compound (C'), one can be used alone or in combination with two or more.

[0182] In one embodiment, compound α can be produced by reacting a raw material compound (C) and a raw material compound (C') with an oxidant in the presence of a dispersion medium using a mechanochemical method (mechanical milling). Here, some or all of the raw material compound (C) can be replaced with a raw material of that raw material compound (C) (e.g., Li₂O, Li₂S, and P₂S₅). Similarly, some or all of the raw material compound (C') can be replaced with a raw material of that raw material compound (C') (e.g., Li₂S and P₂S₅).

[0183] In the above description, Na₂S, for example, can be used instead of Li₂S. Furthermore, Na₂O, for example, can be used instead of Li₂O. In mechanochemical methods, planetary ball mills, for example, can be used. As a dispersion medium, n-heptane, for example, can be used.

[0184] Examples of oxidizing agents include halogen monomers, oxygen or ozone, oxides (Fe₂O₃, MnO₂, Cu₂O, Ag₂O, etc.), oxyacid salts (chlorates, hypochlorites, iodates, bromates, chromates, permanganates, vanadates, bismuthates, etc.), peroxides (lithium peroxide, sodium peroxide, etc.), halide salts (AgI, CuI, PbI₂, AgBr, CuCl, etc.), cyanide salts (AgCN, etc.), thiocyanates (AgSCN, etc.), and sulfoxides (dimethyl sulfoxide, etc.). In one embodiment, from the viewpoint of improving ionic conductivity by utilizing the halide metal produced as a byproduct, the oxidizing agent is preferably a halogen monomer. The "halide metal" can be a salt of one or more elements selected from the group consisting of Li, Na, Mg, and Al derived from the raw material compound (C) and a halogen (e.g., lithium halide if the raw material compound (C) contains Li).

[0185] Examples of halogen monomers include I2, F2, Cl2, and Br2. From the viewpoint of obtaining higher ionic conductivity, I2 and Br2 are preferred halogen monomers.

[0186] As an oxidizing agent, it can be used alone or in combination with multiple agents.

[0187] To date, the inventors have discovered that the above-mentioned compound α' can be obtained by reacting a starting compound (C') (e.g., Li3PS4) with an oxidant (e.g., I2). This reaction can be represented by the following reaction formula (8).

[0188]

Transformation 7

[0189]

[0190] Crosslinking of disulfide bonds in PSSP is formed through a reaction represented by reaction formula (8). In particular, by elongating this crosslinking (the PSS chain formed by repeating repeating units composed of PSS), it exhibits good properties as an adhesive. Compound α' thus obtained is incorporated into a solid electrolyte, thereby enabling the fabrication of a separate solid electrolyte sheet. It has been confirmed that if this solid electrolyte sheet is disposed in positive and negative electrode materials, it functions as a battery.

[0191] Typically, battery binders are prepared by dispersing in a solvent to form a dispersion, and then a slurry consisting of active materials, solid electrolytes, and conductive additives is mixed into this dispersion before use. Therefore, solubility is one of the important physical properties for compounds used as battery binders. The compound α' mentioned above has three crosslinkable sulfur (S) single bonds in its PS4 structure. Therefore, if the PSS chain lengthens, although not shown in reaction formula (8), the disulfide bonds can branch and form a three-dimensional mesh structure. The three-dimensional mesh structure may be the reason for the reduced solubility relative to the solvent.

[0192] Therefore, the inventors further discovered that by using a starting compound (C) to replace part or all of the starting compound (C'), even if the PSS chain elongates, the branching of disulfide bonds (the formation of a three-dimensional mesh structure) can be suppressed, thereby enabling the production of compound α as a more linear, preferably straight-chain polymer. Such a reaction can be represented, for example, by the following reaction formula (9).

[0193]

Transformation 8

[0194]

[0195] (In the formula, R is a group containing one or more elements selected from the group consisting of O, N, and halogens (corresponding to the group R mentioned above). X is a halogen.)

[0196] In reaction formula (9), the starting compound (C) is shown as a substance obtained by replacing part of the sulfur (S) in the PS4 structure of the starting compound (C') with other groups R.

[0197] For example, when reacting a starting compound (C) (e.g., Li3PS3O) with an oxidant (e.g., I2), the group R is -OLi.

[0198] In one embodiment, compound α contains a disulfide bond formed by reaction (9).

[0199] In one embodiment, X in reaction formula (9) is iodine (I), fluorine (F), chlorine (Cl) or bromine (Br).

[0200] In one embodiment, X in reaction (9) is iodine (I).

[0201] In one embodiment, when the starting compound (C) is Li3PS3O and the oxidizing agent is a halogen monomer (X2), the reactions shown in the following reaction formulas (10) to (12) are carried out. In one embodiment, compound α has a P-S-S chain (a chain formed by repeating a repeating unit composed of P-S-S) (Reaction Formulas (10) and (11)). In one embodiment, the formation of branching (branching) accompanying the elongation of the P-S-S chain of compound α is prevented (Reaction Formula (12)). In one embodiment, two phosphorus elements and a disulfide bond bonding these two phosphorus elements form a P-S-S chain.

[0202]

Chemical Formula 9

[0203]

[0204] (In the formula, X is a halogen. n is an integer.)

[0205] In one embodiment, compound α contains a disulfide bond formed by any one of Reaction Formulas (10) to (12).

[0206] In one embodiment, X in Reaction Formulas (10) to (12) is iodine (I), fluorine (F), chlorine (Cl), or bromine (Br).

[0207] In one embodiment, X in Reaction Formulas (10) to (12) is iodine (I).

[0208] The molar ratio of Li3PS3O to I2 used in the reaction (Li3PS3O:I2) is not particularly limited, and for example, it can be 10:1 to 1:10, 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, 4:3 to 3:4, 5:4 to 4: five, or 8:7 to 7:8. The larger the proportion of I2, the longer the P-S-S chain can be extended.

[0209] In addition, the relationship of the above molar ratio is not limited to the case of reacting Li3PS3O with I2. For example, it can also be applied to the case of reacting a starting compound (C) containing a PS x O y structure (where 1≤x and 0<y) with a halogen monomer.

[0210] Furthermore, when the starting compound (C) and the starting compound (C') are used in combination, the relationship of the above molar ratio can be applied by replacing it with the molar ratio of the total of the starting compound (C) and the starting compound (C') to the halogen monomer.

[0211] Furthermore, when using raw materials (e.g., Li₂O, Li₂S, and P₂S₅) as raw material compound (C), the above molar ratio relationship can be applied based on the amount of raw material compound (C) generated when these raw materials react completely. Similarly, when using raw materials (e.g., Li₂S and P₂S₅) as raw material compound (C'), the above molar ratio relationship can also be applied based on the amount of raw material compound (C') generated when these raw materials react completely.

[0212] In the process of reacting the raw material compound (C) with an oxidant (reaction process), it is preferable to use one or more types of energy selected from the group consisting of physical energy, thermal energy and chemical energy to react the raw material compound (C) with the oxidant.

[0213] In the reaction process, it is preferable to use energy containing physical energy to react the raw material compound (C) with the oxidant. Physical energy can be supplied, for example, by using a mechanochemical method (mechanical grinding). In a mechanochemical method, for example, a planetary ball mill can be used.

[0214] In mechanochemical methods using planetary ball mills, there are no particular limitations on the processing conditions. For example, the rotation speed can be 100 rpm to 700 rpm, the processing time can be 1 hour to 100 hours, and the ball diameter can be 1 mm to 10 mm.

[0215] In the reaction process, it is preferable to react the raw material compound (C) with the oxidant in a liquid. In this case, the raw material compound (C) can react with the oxidant in the presence of a dispersion medium. From the viewpoint of utilizing mechanical energy to improve reactivity, it is preferable to use a mechanochemical method (mechanical grinding) to react the raw material compound (C) with the oxidant in the presence of a dispersion medium.

[0216] Examples of dispersion media include, for example, aprotic liquids. Aprotic liquids are not particularly limited, and examples include: preferred chain or cyclic alkanes with 5 or more carbon atoms, such as n-heptane; aromatic hydrocarbons such as benzene, toluene, xylene, and anisole; chain or cyclic ethers such as dimethyl ether, dibutyl ether, and tetrahydrofuran; haloalkyl groups such as chloroform and dichloromethane; and esters such as ethyl propionate.

[0217] In one embodiment, when reacting the raw material compound (C) with the oxidant in a liquid, it is possible for one or both of the raw material compound (C) and the oxidant to react in a state of being mixed with a solvent.

[0218] As a solvent, a dispersion medium capable of dissolving one or both of the raw material compound (C) and the oxidant can be used, such as anisole, dibutyl ether, etc.

[0219] Even in such a solution, the reactant compound (C) can be reacted with an oxidant using one or more types of energy selected from the group consisting of physical energy, thermal energy, and chemical energy, such as stirring, grinding, and ultrasonic vibration. For example, when using thermal energy, the solution can be heated. There is no particular limitation on the heating temperature; for example, it can be 40–200°C, 50–120°C, or 60–100°C.

[0220] In the reaction process, compound α can be generated by oxidizing the raw material compound (C) with an oxidant.

[0221] The above explanation applies not only to the use of raw material compound (C) alone, but also to the use of raw material compound (C) in combination with raw material compound (C').

[0222] When compound α is generated by a reaction in a liquid, the liquid (dispersion medium or solvent) can be removed as needed. By removing the liquid, a solid (powder) of compound α can be obtained. There are no particular limitations on the method of liquid removal; for example, drying, solid-liquid separation, etc., or a combination of two or more of them, can be used.

[0223] In the case of solid-liquid separation, compound α can also be redeprecipitated. In this case, the liquid containing compound α can be added to a poor solvent (a solvent unsuitable for compound α) or a non-solvent (a solvent that does not dissolve compound α), and compound α can be recovered as a solid (solid phase). For example, a method of solid-liquid separation can be performed by adding n-heptane as a poor solvent to an anisole solution containing compound α. The solid-liquid separation method is not particularly limited; examples include evaporation, filtration, and centrifugation. Using solid-liquid separation can result in improved purity.

[0224] In one embodiment, LiI is generated as a byproduct along with the formation of compound α. This LiI may or may not be separated from compound α. As described above, by leaving LiI as a residue in the mixture, compound α can possess higher ionic conductivity.

[0225] Here, the crystal phase of LiI can be, for example, c-LiI (cubic) (ICSD 414244), h-LiI (hexagonal) (ICSD414242), etc. Generally, when a mechanochemical method (mechanical grinding) is used as a method to generate compound α, it is c-LiI (cubic), and when a method is used to carry out the reaction in a liquid (preferably in a solution), it is h-LiI (hexagonal).

[0226] Capable of being detected by powder X-ray diffraction or solid-state X-ray diffraction 7 Li-NMR measurements are used to determine the crystalline phase of LiI. In solid-state... 7In Li-NMR measurements, a peak originating from LiI (chemical shift -4.57 ppm) is identified as c-LiI, and a peak originating from LiI is identified as h-LiI when no peak originating from LiI is observed.

[0227] Example

[0228] The following describes embodiments of the present invention, but the present invention is not limited to the following embodiments.

[0229] 1. Preparation of compounds

[0230] (Manufacturing Example 1)

[0231] Li₂O (manufactured by a high-purity chemical company, 2N up powder), Li₂S (manufactured by FURUCHI Chemical Company, 3N powder, 200 mesh), and P₂S₅ (manufactured by Merck) were mixed in a molar ratio of Li₂O:Li₂S:P₂S₅ = 50:25:25 and reacted by mechanical milling under the following conditions. Then, the dispersion medium was removed by drying to obtain Li₃PS₃O (glass powder).

[0232] [Conditions for mechanical grinding]

[0233] Planetary ball mill: Made by Flying Company, Premium line PL-7

[0234] Sample mass: 3.6g

[0235] Method: Wet milling (dispersion medium: 11.7 mL n-heptane)

[0236] Ball: Material: ZrO2, Diameter: 5mm, Total Weight: 106g

[0237] Bottle: Made of ZrO2, capacity 80mL

[0238] Rotation: 500 rpm

[0239] Processing time: 20 hours

[0240] (Manufacturing Example 2)

[0241] Li₂S (manufactured by FRUCHI Chemical Co., Ltd., 200-mesh 3N powder) and P₂S₅ (manufactured by Merck) were mixed at a molar ratio of Li₂S:P₂S₅ = 3:1 and reacted by mechanical milling in the same manner as in Manufacturing Example 1. The dispersion medium was then removed by drying to obtain Li₃PS₄ (glass powder).

[0242] (Manufacturing Example 3)

[0243] Li₂O (manufactured by High Purity Chemical Company, 2N up powder), Li₂S (manufactured by FURUCHI Chemical Company, 3N powder, 200 mesh), and P₂S₅ (manufactured by Merck) were mixed in a molar ratio of Li₂O:Li₂S:P₂S₅ = 25:50:25 and reacted by mechanical milling in the same manner as in Manufacturing Example 1. The dispersion medium was then removed by drying to obtain Li₃PS. 7 / 2 O 1 / 2 (Glass powder).

[0244] (Example 1)

[0245] I2 (manufactured by a high-purity chemical company, 5N irregular grains; I2 pulverized by a mortar and pestle) was added to the Li3PS3O obtained in Manufacturing Example 1 at a molar ratio of Li3PS3O:I2 = 2:1, and the reaction (polysulfide) was carried out by mechanical grinding under the following conditions. Then, the dispersion medium was removed by drying to obtain the compound (powder; sometimes referred to as "Li3PS3O-I2(2:1)" based on the blending of raw materials).

[0246] [Conditions for mechanical grinding]

[0247] Planetary ball mill: Made by Flying Company, Premium line PL-7

[0248] Sample mass: 1g

[0249] Form: Wet grinding (n-heptane: 3 mL)

[0250] Ball: Material: ZrO2, Diameter: 5mm, Total Weight: 53g

[0251] Bottle: Made of ZrO2, capacity 45mL

[0252] Rotation: 500 rpm

[0253] Processing time: 20 hours

[0254] (Example 2)

[0255] Except for changing the molar ratio to Li3PS3O:I2 = 4:3, the compound was obtained in the same manner as in Example 1 (sometimes referred to as "Li3PS3O-I2(4:3)" based on the mixing of raw materials).

[0256] (Example 3)

[0257] Except for changing the molar ratio to Li3PS3O:I2 = 1:1, the compound was obtained in the same manner as in Example 1 (sometimes referred to as "Li3PS3O-I2(1:1)" based on the mixing of raw materials).

[0258] (Example 4)

[0259] Except for changing the molar ratio to Li3PS3O:I2 = 4:5, the compound was obtained in the same manner as in Example 1 (sometimes referred to as "Li3PS3O-I2(4:5)" based on the mixing of raw materials).

[0260] (Example 5)

[0261] The Li3PS3O and I2 obtained in Manufacturing Example 1 were added to anisole at a molar ratio of Li3PS3O:I2 = 1:1, and the reaction was carried out while stirring at 60°C for 3 days (polysulfide; liquid-phase synthesis). Then, the anisole was removed by drying to obtain the compound (sometimes referred to as "Li3PS3O-I2(1:1)Liq" based on the mixing of raw materials and the synthesis method (liquid phase; Liq).

[0262] (Example 6)

[0263] To the Li3PS obtained in manufacturing example 3 7 / 2 O 1 / 2 China and Israel Li3PS 7 / 2 O 1 / 2 I2 (high-purity chemical company, 5N irregular grains; I2 pulverized in a mortar and pestle) was added at a molar ratio of 1:1, and the reaction (polysulfide) was carried out by mechanical grinding in the same manner as in Example 1. The dispersion medium was then removed by drying to obtain the compound (powder; sometimes referred to as "Li3PS" based on the blending of the raw materials). 7 / 2 O 1 / 2 -I2(1:1)”).

[0264] (Example 7)

[0265] The Li3PS4 obtained in Manufacturing Example 2 and the Li3PS3O obtained in Manufacturing Example 1 were mixed in a molar ratio of Li3PS4:Li3PS3O = 50:50 to obtain a mixture. I2 was added to this mixture in a molar ratio of Li3PS4 + Li3PS3O:I2 = 1:1, and the reaction (polysulfide) was carried out by mechanical milling in the same manner as in Example 1. Then, the dispersion medium was removed by drying to obtain the compound (sometimes referred to as "Li3PS4-Li3PS3O(50 / 50)-I2(1:1)" based on the blending of raw materials).

[0266] (Comparative Examples 1-3)

[0267] Except that Li3PS4 obtained in Manufacturing Example 2 was used instead of Li3PS3O obtained in Manufacturing Example 1, the compounds were obtained in the same manner as in Examples 1 to 3. Sometimes, based on the blending of raw materials, the compound obtained in Comparative Example 1 is referred to as Li3PS4-I2(2:1), the compound obtained in Comparative Example 2 is referred to as Li3PS4-I2(4:3), and the compound obtained in Comparative Example 3 is referred to as Li3PS4-I2(1:1).

[0268] evaluate

[0269] (1) Raman spectrophotometry

[0270] The compound (Li3PS3O) obtained in Manufacturing Example 1 and the compound (Li3PS) obtained in Manufacturing Example 3 7 / 2 O 1 / 2 After the compounds obtained in Examples 1 to 4, 6 and 7 were treated with toluene as described below, micro Raman spectrophotometry was performed using a laser Raman spectrophotometer (LabRAM HR Evolution LabSpec 6, manufactured by Horiba Corporation).

[0271] [Steps for toluene treatment]

[0272] a. Collect 1g of the compound into a vial, add 10mL of toluene (manufactured by Fujifilm and Koichi Chemical Co., Ltd., ultra-dehydrated), stir and let stand.

[0273] b. After removing the supernatant, add 10 mL of toluene to the solid component (precipitate), stir and let stand.

[0274] c. Repeat step b above once.

[0275] d. After removing the supernatant, the solid component (precipitate) is dried under vacuum at 60°C for 10 hours to obtain the compound treated with toluene.

[0276] The Raman spectra obtained by micro Raman spectrophotometry are shown in... Figure 1 (Compounds from Manufacturing Examples 1 and Examples 1-4) Figure 2 (The compounds of Manufacturing Example 3 and Example 6) and Figure 3 In (the compound of Example 7).

[0277] according to Figures 1-3 For the compounds in Examples 1-4, 6, and 7, a Raman shift of 477 cm⁻¹ for the disulfide (SS) bond originating from the PSS chain was confirmed. -1 The nearby peak (peak A mentioned above).

[0278] Furthermore, specifically, according to Figure 1It can be seen that with the increase of I2 as a raw material, the peak originating from the PS bond (peak B above) shifts to the lower wavenumber side (from a Raman shift of 422 cm⁻¹). -1 Towards 392cm -1 (Displacement). It is inferred that the PS bonds elongate due to the formation of PSS chains in the product.

[0279] (2) Powder X-ray analysis (XRD)

[0280] XRD was performed on the compound (Li3PS3O) obtained by manufacturing Example 1 and the compounds obtained in Examples 1-4. Figure 4 The results are shown. Figure 4 In the figure, peaks caused by LiI are labeled.

[0281] according to Figure 4 It is known that the compound (Li3PS3O-I2(2:1)) of Example 1, including the compound and LiI produced as a byproduct of the reaction (polysulfide), is amorphous. On the other hand, in Examples 2 to 4 (Li3PS3O-I2(4:3), (1:1), and (4:5)) in which the amount of I2 mixed as a raw material was increased compared to Example 1, the precipitation of c-LiI (cubic crystal) was confirmed.

[0282] (3) 31 P-NMR measurements

[0283] Solid-state processing was performed using the following apparatus and conditions on the compound (Li3PS3O) obtained in Manufacturing Example 1 and the compounds obtained in Examples 1-5. 31 P-NMR measurements.

[0284] Device: ECZ400R device (manufactured by JEOL Ltd.)

[0285] Observation kernel: 31 P

[0286] Observation frequency: 161.944MHz

[0287] Temperature measured: room temperature

[0288] Pulse sequence: Single pulse (using a 90° pulse)

[0289] 90° pulse width: 3.2μs

[0290] Waiting time from FID measurement until the next pulse is applied: 300s

[0291] Magic horn rotation speed: 11kHz

[0292] Total number of times: 64

[0293] Measurement range: 250ppm to -150ppm

[0294] In solid 31 In P-NMR spectroscopy measurements, (NH4)2HPO4 (chemical shift 1.0 ppm) was used as an external reference for chemical shift.

[0295] Will pass through solid 31 Solid obtained by P-NMR measurement 31 P-NMR spectra show that Figure 5 (The compounds of Manufacturing Example 1 and Example 1) Figure 6 (Compounds from Examples 2-4) and Figure 7 In (the compound of Example 5).

[0296] (4) Solubility

[0297] <Stillness Test>

[0298] The compound obtained in Example 3 (Li3PS3O-I2(1:1)) was added to anisole to prepare an anisole solution containing 20% ​​by mass of the compound. The anisole solution was allowed to stand at room temperature (20°C) for 1 hour, and then visually inspected for any precipitate. No precipitate was found.

[0299] In addition, the same standing test was performed on a 30% by mass anisole solution of the compound (Li3PS4-Li3PS3O(50 / 50)-I2(1:1)) obtained in Example 7, and no precipitate was found.

[0300] Furthermore, the compounds obtained in Examples 3, 6-7, and Comparative Example 3 were added to anisole to prepare anisole solutions containing 30% by mass of the compound. The anisole solutions were heated at 60°C for 30 minutes, allowed to cool (standing time: 1 hour), and their condition was evaluated. The results showed that Examples 6 and 3 exhibited slight turbidity and contained insoluble components, while Examples 3 and 7 showed uniform dissolution without turbidity. In addition, Example 7 yielded a highly fluid solution, allowing for further increases in solution concentration.

[0301] Centrifugation test

[0302] The compound obtained in Example 7 (Li3PS4-Li3PS3O(50 / 50)-I2(1:1)) was added to anisole to prepare an anisole solution containing 30% by mass of the compound. The anisole solution was centrifuged at 4000 rpm for 15 minutes, and the presence or absence of precipitate was visually observed. No precipitate was found.

[0303] The results of these experiments show that compound α has excellent solubility.

[0304] (5) Ionic conductivity

[0305] The compounds obtained in Manufacturing Examples 1, 2, Examples 1-3, 7 and Comparative Examples 1-3 were respectively added to a cylindrical container and clamped by cylindrical SUS shafts inserted from both ends of the container, thereby being stamped at room temperature (23°C) with a pressure of 333 MPa to form a disc-shaped powder molded body.

[0306] While maintaining the stamping state, the wires were connected to the powder molded body, and the ionic conductivity was measured. The measurement was performed using the Solartron 1470E Cell test system manufactured by Solartron Analytical.

[0307] The ionic conductivity was calculated based on the thickness of the powder body obtained by stamping. The results are shown in Table 1.

[0308] [Table 1]

[0309]

[0310] As shown in Table 1, the compounds of Examples 1-3 and 7 have high ionic conductivity, which is not much inferior to the compounds of Comparative Examples 1-3 (or the compounds of Manufacturing Examples 1 and 2).

[0311] 2. Sheet manufacturing

[0312] (Example 8)

[0313] Prepare a slurry-like coating solution with the following composition.

[0314] [Composition of the coating solution]

[0315] Li3PS4 solid electrolyte (Li3PS4 obtained in Manufacturing Example 2): 95% by mass (0.76 g)

[0316] The compound obtained in Example 3 (Li3PS3O-I2(1:1)): 5% by mass (0.04 g)

[0317] Anisole: 76 parts by weight (0.61 mL) relative to the total amount of the above two components (total solid components) per 100 parts by weight.

[0318] Specifically, first, 0.50 mL of anisole was added to 0.04 g of the compound obtained in Example 3 to dissolve it. Then, 0.76 g of Li3PS4 solid electrolyte was added to the solution, and kneading was performed using a planetary stirring degassing device (MAZERUSTAR KK-250S manufactured by Kurashiki Textile Co., Ltd.) under the kneading conditions described below.

[0319] [Kneading Conditions]

[0320] Rotation speed: 1600 rpm

[0321] Revolution: 1600rpm

[0322] Processing time: 180 seconds × 3

[0323] Next, the sample was treated with an ultrasonic cleaner for 5 minutes, and then kneaded again under the same kneading conditions as above. Then, 0.11 mL of anisole was added to the sample, and kneading was carried out again under the same kneading conditions as above to obtain a slurry-like coating liquid (slurry solids concentration of 57% by mass).

[0324] The obtained coating solution was applied to a 5cm × 10cm aluminum foil to form a coating film. Then, the coating film was dried at 60°C for 10 hours to remove the solvent (anisole), thus producing a solid electrolyte sheet (battery sheet). (The same applies to Examples 9-12 and Comparative Examples 4 and 5 described later.) The thickness of this solid electrolyte sheet (excluding the dried coating film containing the aluminum foil) is 100-120 μm.

[0325] (Example 9)

[0326] The solid electrolyte sheet was manufactured in the same manner as in Example 8, except that the composition of the coating solution was changed as follows.

[0327] [Composition of the coating solution]

[0328] Li3PS4 solid electrolyte (Li3PS4 obtained in manufacturing example 2): 92% by mass (0.736 g)

[0329] The compound obtained in Example 3 (Li3PS3O-I2(1:1)): 8% by mass (0.064g)

[0330] Anisole: 73 parts by weight (0.59 mL) relative to the total amount of the above two components (total solid components) per 100 parts by weight.

[0331] (Example 10)

[0332] The solid electrolyte sheet was manufactured in the same manner as in Example 8, except that the composition of the coating solution was changed as follows.

[0333] [Composition of the coating solution]

[0334] Li3PS4 solid electrolyte (Li3PS4 obtained in Manufacturing Example 2): 95% by mass (0.76 g)

[0335] The compound obtained in Example 7 (Li3PS4-Li3PS3O(50 / 50)-I2(1:1)): 5% by mass (0.04 g)

[0336] Anisole: 62 parts by weight (0.50 mL) relative to the total amount of the above two components (total solid components) per 100 parts by weight.

[0337] (Example 11)

[0338] The solid electrolyte sheet was manufactured in the same manner as in Example 8, except that the composition of the coating solution was changed as follows.

[0339] [Composition of the coating solution]

[0340] Li3PS4 solid electrolyte (Li3PS4 obtained in Manufacturing Example 2): 90% by mass (0.72 g)

[0341] The compound obtained in Example 7 (Li3PS4-Li3PS3O(50 / 50)-I2(1:1)): 10% by mass (0.08 g)

[0342] Anisole: 71 parts by weight (0.57 mL) relative to the total amount of the above two components (total solid components) per 100 parts by weight.

[0343] (Example 12)

[0344] The solid electrolyte sheet was manufactured in the same manner as in Example 8, except that the composition of the coating solution was changed as follows.

[0345] [Composition of the coating solution]

[0346] Li3PS4 solid electrolyte (Li3PS4 obtained in Manufacturing Example 2): 95% by mass (0.76 g)

[0347] The compound (Li3PS) obtained in Example 6 7 / 2 O 1 / 2 -I2 (1:1): 5% by mass (0.04g)

[0348] Anisole: 62 parts by weight (0.50 mL) relative to the total amount of the above two components (total solid components) per 100 parts by weight.

[0349] (Comparative Example 4)

[0350] The solid electrolyte sheet was manufactured in the same manner as in Example 8, except that the composition of the coating solution was changed as follows.

[0351] [Composition of the coating solution]

[0352] Li3PS4 solid electrolyte (Li3PS4 obtained in Manufacturing Example 2): 95% by mass (0.76 g)

[0353] The compound obtained in Comparative Example 3 (Li3PS4-I2(1:1)): 5% by mass (0.04 g)

[0354] Anisole: 87 parts by weight (0.70 mL) relative to the total amount of the above two components (total solid components) per 100 parts by weight.

[0355] (Comparative Example 5)

[0356] The solid electrolyte sheet was manufactured in the same manner as in Example 8, except that the composition of the coating solution was changed as follows.

[0357] [Composition of the coating solution]

[0358] Li3PS4 solid electrolyte (Li3PS4 obtained in Manufacturing Example 2): 95% by mass (0.76 g)

[0359] Styrene-butadiene thermoplastic elastomer (SBS) (JSR Corporation, “TR2000”): 5% by mass (0.04g)

[0360] Anisole: 82 parts by weight (0.66 mL) relative to the total amount of the above two components (total solid components) per 100 parts by weight.

[0361] evaluate

[0362] (1) Sheet winding characteristics

[0363] The solid electrolyte sheets obtained in Examples 8-12 and Comparative Examples 4 and 5 were each wound into cylinders with a diameter of 16 mm, and visually observed for any breakage or peeling from the aluminum foil. The results showed that no breakage or peeling from the aluminum foil was found in the solid electrolyte sheets obtained in Examples 8-12. Similarly, no breakage or peeling from the aluminum foil was found in the solid electrolyte sheets obtained in Comparative Examples 4 and 5.

[0364] (2) Ionic conductivity

[0365] The solid electrolyte sheets obtained in Examples 8-12 and Comparative Examples 4 and 5 were punched together with aluminum foil into circular plates, placed into a cylindrical container, and clamped by cylindrical SUS shafts inserted from both ends of the container, thereby being punched at room temperature (23°C) with a pressure of 333 MPa.

[0366] While maintaining the stamping state, the ionic conductivity was measured by connecting a wire to the solid electrolyte sheet. The measurement was performed using a Solartron Analytical Cell test system 1470E. The ionic conductivity calculated based on the thickness of the stamped solid electrolyte sheet is shown in Table 2.

[0367] [Table 2]

[0368]

[0369] 3. Battery manufacturing

[0370] (Example 13)

[0371] LiCoO2, Li3PS4 solid electrolyte (Li3PS4 obtained in Manufacturing Example 2), and acetylene black (AB) (manufactured by DENKA) were mixed at a mass ratio of LiCoO2:Li3PS4:AB = 70:30:5 to obtain a mixture (total mass 0.2 g). Additionally, a solution was prepared by dissolving 10 mg of the compound obtained in Example 3 (Li3PS3O-I2 (1:1)) in 0.1 mL of anisole, and the above mixture was added to this solution. The resulting composition was LiCoO2:Li3PS4:AB:Li3PS3O-I2 (1:1) = 70:30:5:5. This composition was kneaded, treated with an ultrasonic cleaner for 5 minutes, and then approximately 0.05 mL of anisole was added and kneaded again to obtain a slurry (solid content concentration of 59% by mass). The obtained slurry was coated onto a 5 × 10 cm Al foil to form a coating film. After drying the coating at 60°C for 10 hours, it was then vacuum dried at 160°C for 3 hours. The resulting sheet was then punched to obtain a positive electrode sheet with a diameter of 9.9 mm.

[0372] The Li3PS4 solid electrolyte (Li3PS4 obtained in Manufacturing Example 2) (80 mg) was placed in a cylindrical container with SUS shafts on both sides and pressed to form a solid electrolyte layer. Next, the positive electrode sheet obtained above was placed in the cylindrical container in an overlapping manner with the solid electrolyte layer. Then, In foil and Li foil were sequentially placed on the opposite side of the electrode sheet in the solid electrolyte layer inside the cylindrical container and stamped and stacked. The stack was then bound with a special fixture to produce a test battery (positive half-cell).

[0373] (Example 14)

[0374] The battery was made in the same manner as in Example 13, except that the compound obtained in Example 7 (Li3PS4-Li3PS3O(50 / 50)-I2(1:1)) was used instead of the compound obtained in Example 3.

[0375] (Comparative Example 6)

[0376] The battery was made in the same manner as in Example 13, except that the compound obtained in Comparative Example 3 (Li3PS4-I2(1:1)) was used instead of the compound obtained in Example 3.

[0377] (Comparative Example 7)

[0378] The battery was made in the same manner as in Example 13, except that a styrene-butadiene thermoplastic elastomer (SBS) (JSR Corporation's "TR2000") was used instead of the compound obtained in Example 3.

[0379] evaluate

[0380] (1) Initial charge-discharge characteristics (initial charge-discharge curve)

[0381] The initial charge-discharge curves (0.1C) measured for the batteries obtained in Examples 13 and 14 and Comparative Examples 6 and 7 are shown below. Figure 8 (Batteries of Example 13 and Comparative Examples 6 and 7) and Figure 9 (Battery of Example 14). Here, as the 1C rate (the current at which the total capacity of the battery is discharged for 1 hour), the battery of Example 13 is 0.25mA, the battery of Example 14 is 0.29mA, the battery of Comparative Example 6 is 0.39mA, and the battery of Comparative Example 7 is 0.32mA.

[0382] according to Figure 8 and Figure 9 It can be seen that the batteries in Examples 13 and 14 can be charged and discharged without obvious side reactions.

[0383] (2) AC impedance (after initial charging)

[0384] The AC impedance of the batteries obtained in Examples 13 and 14 and Comparative Examples 6 and 7 was measured using a Solartron 1470E Cell test system manufactured by Solartron Analytical, and the Cole-Cole plots were obtained. The results (Cole-Cole plots) are shown in... Figure 10 (Batteries of Example 13 and Comparative Examples 6 and 7) and Figure 11 (Battery of Example 14).

[0385] according to Figure 10 and Figure 11 It can be seen that the interface resistance of the batteries in Examples 13 and 14 is relatively small after charging.

[0386] (3) Cyclic characteristics

[0387] The results of the cycle characteristics measured for the batteries obtained in Examples 13 and 14 and Comparative Examples 6 and 7 are shown in the figure. Figure 12 (Batteries of Example 13 and Comparative Examples 6 and 7) and Figure 13 (Battery of Example 14).

[0388] according to Figure 12 and Figure 13 It can be seen that the batteries in Examples 13 and 14 have good cycle characteristics.

[0389] In the following experiments, solid electrolytes containing S as a constituent element and having P-N bonds were synthesized according to the methods described in "Solid State Ionics 304 (2017) 85-89" in Examples 4 and 5 below. Then, according to Examples 15 and 16 below, the solid electrolytes were reacted with iodine to synthesize compounds containing P and S as constituent elements and having groups containing N bonded to the P and disulfide bonds.

[0390] (Manufacturing Example 4)

[0391] Li2S (manufactured by FRUCHI Chemical Co., Ltd., 3N powder 200 mesh), P2S5 (manufactured by Merck Co., Ltd.), and Li3N (manufactured by Hiroshima Wako Co., Ltd.) were mixed in a molar ratio of Li2S:P2S5:Li3N = 60:25:10, and reacted by mechanical grinding under the following conditions to obtain 60Li2S-25P2S5-10Li3N (glass powder, referred to as "LPS-10N").

[0392] [Conditions for mechanical grinding]

[0393] Planetary ball mill: Flying Company, P7

[0394] Sample mass: 1.5g

[0395] Form: Dry grinding

[0396] Spheres: Material: ZrO2, Diameter: 10mm, Quantity: 10

[0397] Bottle: Made of ZrO2, capacity 45mL

[0398] Rotation: 510 rpm

[0399] Processing time: 45 hours

[0400] (Manufacturing Example 5)

[0401] Li2S (manufactured by Idemitsu Kosan Co., Ltd., 3N powder 200 mesh), P2S5 (manufactured by Merck Co., Ltd.) and Li3N (manufactured by Hiroshima Wako Co., Ltd.) were mixed in a molar ratio of Li2S:P2S5:Li3N = 45:25:20 and reacted by mechanical grinding in the same way as in Manufacturing Example 4 to obtain 45Li2S-25P2S5-20Li3N (glass powder, referred to as "LPS-20N").

[0402] (Example 15)

[0403] Except for adding I2 (manufactured by High Purity Chemical Company, 5N irregular grains; using I2 pulverized by a mortar) to the LPS-10N obtained in Manufacturing Example 4 at a molar ratio of LPS-10N:I2 = 1:1, the compound (called DSP-10N) was obtained in the same manner as in Example 1.

[0404] (Example 16)

[0405] Except for adding I2 (manufactured by High Purity Chemical Company, 5N irregular grains; using I2 pulverized by a mortar) to the LPS-20N obtained in Manufacturing Example 5 at a molar ratio of LPS-20N:I2 = 1:1, the compound (called DSP-20N) was obtained in the same manner as in Example 1.

[0406] evaluate

[0407] (1) Raman spectrophotometry

[0408] The compounds (DSP-10N and DSP-20N) obtained in Examples 15 and 16 were subjected to the same micro Raman spectrophotometric analysis as those obtained in Manufacturing Example 1.

[0409] exist Figure 14 The image shows the Raman spectra obtained by micro Raman spectroscopy.

[0410] according to Figure 14 For either of the compounds (DSP-10N and DSP-20N) obtained in Examples 15 and 16, a Raman shift of 475 cm⁻¹ for the disulfide (SS) bond originating from the PSS chain was confirmed. -1 The nearby peak (peak A mentioned above).

[0411] (2) X-ray photoelectron spectroscopy (XPS)

[0412] XPS measurements were performed on the compounds (DSP-10N and DSP-20N) obtained in Examples 15 and 16 using the following apparatus and conditions.

[0413] Device: Versa Probe II (ULVAC-PHI)

[0414] condition:

[0415] • Excitation X-rays: Monochromatic AlKα 1486.6 eV

[0416] • X-ray diameter and power: 200μm diameter, 50W, 15KV (fixed at all points)

[0417] • Photoelectron detection angle: 45°

[0418] • Horizontal axis (binding energy): Performs electrostatic neutralization correction with CC set to 284.8 eV for all elements.

[0419] Measurements were performed both on the outermost surface of the sample and on the GCIB (Gas Cluster Ion Beam) sputtering surface. GCIB processing conditions were 10 kV, 30 nA, and 2 × 2 mm. 2 5 minutes.

[0420] • Data processing: 5-point smoothing process

[0421] exist Figure 15 The measurement results of Example 15 are shown in the figure. Figure 16 The measurement results of Example 16 are shown below. XPS measurements confirmed that N was present as a constituent element in both compounds (DSP-10N and DSP-20N) obtained in Examples 15 and 16. For example, according to the aforementioned literature "Solid State Ionics 304 (2017) 85-89", for the substance equivalent to LPS-10N (Manufacturing Example 4), a peak of N originating from the PN=P bond was observed at 396.9 eV, and a peak of N originating from the P2-NP bond was observed at 398.3 eV. In the compounds (DSP-10N and DSP-20N) obtained in Examples 15 and 16, some peak shifts due to multi-quantization were found, but peaks were observed near 396.8 eV and 398.3 eV (see reference). Figure 15 and 16 Furthermore, if the elemental composition ratio is determined, as shown in Table 3, it is confirmed that element N exists at approximately 5 mol%.

[0422] [Table 3]

[0423]

[0424] Based on the above results, it can be inferred that the compounds obtained in Examples 15 and 16 have structures represented by the following formulas (13) and (14).

[0425]

Chemistry 10

[0426]

[0427] In the foregoing, several embodiments and / or examples of the present invention have been described in detail. However, those skilled in the art can readily make various modifications to these embodiments and / or examples without substantially departing from the new insights and effects of the present invention. Therefore, these various modifications are included within the scope of the present invention.

[0428] All references to the literature recorded in this specification and the contents of the application which form the basis of the priority claim under the Paris Convention are incorporated herein by reference.

Claims

1. A compound, characterized in that, It contains P and S as constituent elements and has the following characteristics: Disulfide bonds; and The structure represented by equation (1) and the structure represented by equation (7) are as follows: 【Chemistry 12】 In equations (1) and (7), X is Li, Na, Mg or Al, and multiple Xs can be the same or different.

2. The compound according to claim 1, characterized in that, In Raman spectrophotometry, it has a peak originating from a disulfide bonded to two P atoms.

3. The compound according to claim 1 or 2, characterized in that, In Raman spectrophotometry, at a Raman shift of 425 cm⁻¹ -1 Above 500cm -1 The following ranges have peaks.

4. The compound according to any one of claims 1 to 3, characterized in that, In Raman spectrophotometry, at a Raman shift of 440 cm⁻¹ -1 Above 490cm -1 The following ranges have peaks.

5. The compound according to any one of claims 1 to 4, characterized in that, In Raman spectrophotometry, at a Raman shift of 460 cm⁻¹ -1 Above 480cm -1 The following ranges have peaks.

6. The compound according to any one of claims 1 to 5, characterized in that, In Raman spectroscopy analysis, it has properties derived from PS x O y Peaks of symmetrical stretching of PS bonds in the structure and / or PS4 structure.

7. The compound according to any one of claims 1 to 6, characterized in that, In Raman spectrophotometry, at a Raman shift of 370 cm⁻¹ -1 Above and below 425cm -1 The range has a peak.

8. The compound according to any one of claims 1 to 7, characterized in that, In Raman spectrophotometry, at a Raman shift of 380 cm⁻¹ -1 Above 423cm -1 The following ranges have peaks.

9. The compound according to any one of claims 1 to 8, characterized in that, In Raman spectrophotometry, at a Raman shift of 390 cm⁻¹ -1 Above 420cm -1 The following ranges have peaks.

10. The compound according to any one of claims 1 to 9, characterized in that, exist 31 P-NMR measurements have origins from PS x O y The peak of the structure, where 1≤x and 0 <y。 11. The compound according to claim 10, characterized in that, Derived from the PS x O y The peaks in the structure are derived from the PS3O structure.

12. The compound according to any one of claims 1 to 11, characterized in that, The structure represented by equation (1) is included as the structure represented by equation (6) below. 【Transformation 5】 In equation (6), X is Li, Na, Mg or Al, and the two Xs are the same or different from each other.

13. The compound according to any one of claims 1 to 12, characterized in that, It is a compound obtained by adding an oxidizing agent to a raw material compound and then reacting the raw material compound with the oxidizing agent. The raw material compound contains P, S, and one or more elements selected from the group consisting of Li, Na, Mg and Al as constituent elements.

14. The compound according to any one of claims 1 to 13, characterized in that, It contains disulfide bonds formed through the following reaction (9), 【Chemistry 13】 In the formula, R is a group containing one or more elements selected from the group consisting of O, N and halogens, and X is a halogen.

15. The compound according to claim 14, characterized in that, In the reaction formula (9), X is iodine (I), fluorine (F), chlorine (Cl) or bromine (Br).

16. A battery adhesive, characterized in that, It includes the compound described in any one of claims 1 to 15.

17. The battery adhesive as claimed in claim 16, characterized in that, It contains halogens.

18. The battery adhesive as claimed in claim 17, characterized in that, The halogen is in the form of a halogen monomer.

19. The battery adhesive as described in claim 17 or 18, characterized in that, The halogen is I or Br.

20. The battery adhesive as claimed in claim 17, characterized in that, The halogen is in the form of a salt, which is a salt of one or more elements selected from the group consisting of Li, Na, Mg and Al with the halogen.

21. The battery adhesive according to any one of claims 16 to 20, characterized in that, When the total mass of the battery adhesive is set to 100% by mass, the content of the compound in the battery adhesive is 50% by mass or more.

22. The battery adhesive according to any one of claims 16 to 21, characterized in that, When the total mass of the battery adhesive is set to 100% by mass, the content of the compound in the battery adhesive is 60% by mass or more.

23. A battery electrode composite material layer or electrolyte layer, characterized in that, The adhesive for batteries comprises any one of claims 16 to 22.

24. The electrode composite material layer or electrolyte layer for batteries as described in claim 23, characterized in that, It further includes solid electrolytes.

25. The electrode composite material layer or electrolyte layer for batteries as described in claim 24, characterized in that, The solid electrolyte has crystal structures ranging from argentite-germanium sulfide, Li3PS4, Li4P2S6, and Li7P3S. 11 Crystal structure, Li 4-x Ge 1-x P x S4 type sulfide crystalline lithium superionic conductor region type II crystal structure, and its relationship with Li 4-x Ge 1-x P x S4 type sulfide crystalline lithium superionic conductor is a sulfide solid electrolyte with a crystal structure similar to that of Region II.

26. A sheet for batteries, characterized in that, It includes one or more layers selected from the group consisting of a battery electrode composite material layer and an electrolyte layer as described in any one of claims 23 to 25.

27. A battery, characterized in that, It includes the compound described in any one of claims 1 to 15.

28. A method for manufacturing a compound, characterized in that, include: An oxidant is added to a mixture containing Li3PS4 and also containing Li3PS3O, Na3PS3O, and Mg. 3 / 2 The raw material compounds selected in PS3O; and The raw material compound is reacted with the oxidant. The raw material compound reacts with the oxidant using one or more types of energy selected from the group consisting of physical energy, thermal energy, and chemical energy.

29. The method for manufacturing the compound according to claim 28, characterized in that, Further add a raw material compound (C') containing P and S as constituent elements but without O.

30. The method for manufacturing the compound according to claim 29, characterized in that, The oxidant is added to a mixture of the raw material compound and the raw material compound (C') to cause the raw material compound, the raw material compound (C') and the oxidant to react.

31. The method for manufacturing the compound according to claim 29 or 30, characterized in that, The raw material compound (C') contains one or more elements selected from the group consisting of Li, Na, Mg and Al as constituent elements.

32. A method for producing the compound according to any one of claims 29 to 31, characterized in that, The raw material compound (C') contains a PS4 structure.

33. A method for producing the compound according to any one of claims 29 to 32, characterized in that, The starting material compound (C') comprises a compound selected from Li3PS4, Li4P2S7, Na3PS4 and Na4P2S7.

34. A method for producing the compound according to any one of claims 28 to 33, characterized in that, The oxidant is selected from one or more of the following: halogen monomers, oxygen, ozone, oxides, oxyacid salts, peroxides, halide salts, cyanide salts, thiocyanates, and sulfoxides.

35. The method for manufacturing the compound according to claim 28, characterized in that, The oxidant is a halogen monomer.

36. The method for manufacturing the compound according to claim 35, characterized in that, The halogen monomer is I2 or Br2.

37. The method for producing the compound according to claim 35 or 36, characterized in that, The molar ratio of the starting compound to the halogen monomer used in the reaction is 1:10 to 10:

1.

38. A method for producing the compound according to any one of claims 28 to 37, characterized in that, The raw material compound is reacted with the oxidant in a liquid.

39. The method for manufacturing the compound according to claim 38, characterized in that, The raw material compound is reacted with the oxidant in the presence of a dispersion medium.

40. The method for manufacturing the compound according to claim 39, characterized in that, The dispersion medium is a nonprotic liquid selected from n-heptane, benzene, toluene, xylene, anisole, dimethyl ether, dibutyl ether, tetrahydrofuran, chloroform, dichloromethane, and ethyl propionate.

41. A method for producing the compound according to any one of claims 38 to 40, characterized in that, The compound is obtained by removing the liquid using one or more methods selected from drying and solid-liquid separation.

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