Glass, solid electrolyte, and oxide crystallized glass

Abstract

The present invention relates to a glass which has a CO2 content of less than 10% by weight in terms of oxides, and in which the total content of cations of one or more first elements selected from the group consisting of Si, B, P, Ge, As, Sb, Bi, Te, and V is 5% or more when expressed in terms of cation %.

Description

Glass, solid electrolytes, and oxide crystallized glass

[0001] This invention relates to glass. Furthermore, this invention relates to a solid electrolyte and oxide crystallized glass containing components derived from the above-mentioned glass.

[0002] Glass offers many advantages as a solid electrolyte material, including superior fluidity at low temperatures compared to crystalline materials, ease of manufacturing, and stability over a wide temperature range, which contributes to improved performance.

[0003] Glass used in lithium-ion secondary batteries requires high ionic conductivity to meet the demands for higher performance in these batteries. Furthermore, high ionic conductivity may also be required in other applications.

[0004] As a method for improving ionic conductivity, Patent Document 1 describes Li, a component that improves the ionic conductivity of glass. ＋ It is stated that it will increase.

[0005] Japanese Patent No. 6425450

[0006] However, when the present inventors examined the glass described in Patent Document 1, they found that there was room for improvement in its ionic conductivity. Furthermore, while glass is often used after sintering to achieve ionic conductivity, from the viewpoint of thermal stress, it was required to sinter at low temperatures.

[0007] The present invention aims to provide low-temperature sintered glass with high ionic conductivity.

[0008] The inventors of the present invention have diligently investigated the above problem and found that CO ３ ２－ We discovered that by including a predetermined proportion of [the substance], we could obtain a glass with high ionic conductivity that can be sintered at low temperatures, thus completing the present invention.

[0009] In other words, the present invention is as follows: [1] CO in terms of oxides ２A glass having a content of less than 10% by weight, wherein a total content of cations of one or more first elements selected from the group consisting of Si, B, P, Ge, As, Sb, Bi, Te, and V is 5% or more in terms of cation%. [2] The glass according to [1], which contains one or more alkali metal cations in an amount of more than 0.0% and 90% or less in terms of cation%. [3] B as a cation of the first element ３＋ and Si ４＋ is contained, Li as the alkali metal cation ＋ is contained, and the respective contents in terms of cation% are: B ３＋ is more than 0.0% and less than 50%, Si ４＋ is more than 0.0% and less than 50%, Li ＋ is 50% or more and 80% or less, and further contains O as an anion ２－ , the glass according to [2]. [4] The O ２－ and CO ３ ２－ has a total content of 70% or more and 100% or less in terms of anion%, the glass according to [3]. [5] B as a cation of the first element ３＋ and Si ４＋ is contained, and the respective contents in terms of cation% are: B ３＋ is more than 1.0% and 23% or less, and Si ４＋ is more than 5.0% and 20% or less, the glass according to any one of [1] to [4]. [6] Y ３＋ , La ３＋ , and Zr ４＋ further comprises one or more cations selected from the group consisting of: Y ３＋ , La ３＋ , and Zr ４＋ has a total content of more than 0% and 10% or less in terms of cation%, the glass according to any one of [1] to [5]. [7] The glass according to any one of [1] to [6], further comprising Cl as an anion － , wherein a content of Cl － is 0.0% or more and 4.0% or less in terms of anion%. [8] The glass has an ionic conductivity at 25°C of 2.0×10 －６Glass according to any of [1] to [7], having a concentration of S / cm or higher. [9] CO2 in terms of oxides ２ A glass according to any one of [1] to [8], wherein the content is 0.4% by weight or more and less than 10% by weight.

[10] A glass according to any one of [1] to [9], wherein the glass transition temperature is 800°C or lower.

[11] A glass according to any one of [1] to

[10] , wherein the first crystallization onset temperature is 300°C or higher.

[12] A glass according to any one of [1] to

[11] , wherein ((Tc-on)-Tg) is 20°C or more and 150°C or less, when the glass transition temperature is Tg and the first crystallization onset temperature is Tc-on.

[13] A glass according to any one of [1] to

[12] , wherein the ratio of the content of alkali metal cations to the content of the cations of the first element is 0.1 or more and 7 or less.

[14] Li as the alkali metal cation ＋ Including the cation content of the first element, ＋ A glass according to any one of [1] to

[13] , wherein the ratio of the content of is 0.1 or more and 7 or less.

[15] A solid electrolyte containing a component derived from the glass according to any one of [1] to

[14] .

[16] An oxide crystallized glass having the glass according to any one of [1] to

[14] as the base glass.

[0010] According to the present invention, it is possible to provide low-temperature sintered glass with high ionic conductivity.

[0011] Figure 1 shows an example of a TG curve obtained from TG-MS measurement. Figure 2 is a schematic cross-sectional view of an all-solid-state lithium-ion secondary battery having a solid electrolyte according to this embodiment. Figure 3 is a schematic cross-sectional view showing an example of the configuration of a multilayer ceramic capacitor. Figure 4 is a schematic cross-sectional view showing an example of the configuration of a ceramic multilayer substrate.

[0012] Embodiments of the present invention will be described in detail below. The following descriptions of constituent elements may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, weight-based ratios, etc., are synonymous with mass-based ratios, etc. In this specification, the "~" indicating a numerical range is used to mean that the numbers written before and after it are included as the lower and upper limits.

[0013] In this specification, "CO2 on an oxide basis" ２ "Content" refers to the amount of CO2 contained in the glass. ３ ２－ This value is calculated as an oxide and expressed as a weight fraction. CO2 contained in glass. ３ ２－ CO is used as the composition of the preparation. ３ ２－ In addition to using materials containing CO2, the glass manufacturing process involves the production of CO2 through chemical reactions. ２ This also includes cases where it remains in the glass.

[0014] In this specification, "cation %" refers to a unit that expresses the molar content of each cation component relative to the total molar content of all cation components contained in the glass, after separating the glass into cation components and anionic components, as a percentage. In this specification, when the content of cation components is expressed in percentage, it means cation % unless otherwise specified. The content of each cation component contained in the glass is determined from the results of inductively coupled plasma atomic emission spectroscopy (ICP-AES) of the obtained glass. For example, an Agilent 5800 ICP-AES can be used for inductively coupled plasma atomic emission spectroscopy.

[0015] In this specification, "anion %" refers to a unit that expresses the molar content of each anionic component as a percentage of the total molar content of all anionic components contained in the glass, after separating the constituent components of the glass into cationic and anionic components. In this specification, when the content of anionic components is expressed in percentage, it means anion % unless otherwise specified. ２－ The content of anionic components other than O is determined from the results of inductively coupled plasma emission spectroscopy, quartz tube combustion ion chromatography, thermogravimetric-mass spectrometry (TG-MS), etc. Specifically, first, the content of O in the sample is determined by the above method. ２－ Determine the molar amounts of anionic components other than the one mentioned above. Also, determine the molar amounts of each cationic component in the sample using the method described above. Here, calculate the molar amount of oxygen atoms contained in the glass, assuming the most stable oxide of each cationic component contained in the glass under standard conditions. From the above molar amount of oxygen atoms, the above O ２－ The molar amount obtained by subtracting the content of anionic components other than O in the measurement sample is O ２－ This is the molar amount. The O in the measurement sample calculated above ２－ The molar amount of and the amount of O in the sample being measured ２－ The sum of the molar amounts of other anionic components and the amount of O in the measured sample ２－ The ratio of molar amounts is expressed in anion %. ２－ The content shall be as follows. Furthermore, the ratio of the molar amount of each anionic component in the sample to the above total value shall be expressed in anion %. ２－ The content of each anion other than the specified one shall be used. For the quartz tube combustion ion chromatography method, for example, a Dionex ICS-2100 manufactured by Thermo Fisher Scientific, Inc. can be used.

[0016] In this specification, "mol%" refers to a unit that expresses the molar amount of each component of glass as a percentage of the total molar amount of all components.

[0017] In this specification, "not containing or substantially not containing" cationic components means that they are not contained except for unavoidable impurities contained in the raw materials, etc., or unavoidable impurities that may be introduced during the manufacturing process; in other words, they are not intentionally included. Specifically, for example, the content of cationic components in the glass relative to the total molar amount is preferably 0.3% or less (e.g., 0.0 to 0.3%), more preferably 0.2% or less (e.g., 0.0 to 0.2%), even more preferably 0.1% or less (e.g., 0.0 to 0.1%), and particularly preferably 0.01% or less (e.g., 0.0 to 0.01%).

[0018] In this specification, "absent or substantially absent" of anionic components means that they are not contained except for unavoidable impurities contained in the raw materials, etc., or unavoidable impurities that may be introduced during the manufacturing process; in other words, they are not intentionally included. Specifically, for example, the content of anionic components in the glass relative to the total molar amount of all anionic components is preferably 0.3% or less (e.g., 0.0 to 0.3%), more preferably 0.2% or less (e.g., 0.0 to 0.2%), even more preferably 0.1% or less (e.g., 0.0 to 0.1%), and particularly preferably 0.01% or less (e.g., 0 to 0.01%).

[0019] <Glass> In this specification, "glass" refers to a material in which no diffraction peaks originating from crystals are observed in the X-ray diffraction chart obtained by X-ray diffraction. The absence of diffraction peaks originating from crystals in the X-ray diffraction chart means that only a halo pattern is observed. Furthermore, "glass" is defined as a material in which a glass transition temperature can be confirmed by differential thermal analysis (DTA). However, even if some diffraction peaks originating from crystals are observed, the material is defined as "glass" as long as it contains amorphous material.

[0020] The glass according to this embodiment has CO2 equivalent in oxide terms. ２The content is less than 10% by weight, and it contains at least 5% of one or more primary element cations, expressed as cation percentage. In this specification, "primary element" refers to an element that is considered capable of forming a network structure (continuous three-dimensional mesh structure) of glass and is a component that contributes to the stability of glass. Specifically, examples include silicon (Si), boron (B), phosphorus (P), germanium (Ge), arsenic (As), antimony (Sb), bismuth (Bi), tellurium (Te), and vanadium (V). Primary element cations are Si ４＋ , B ３＋ , P ５＋ , Ge ４＋ As ３＋ As ５＋ Sb ３＋ Sb ５＋ , Bi ３＋ Te ４＋ Te ６＋ , V ３＋ , V ４＋ , and V ５＋ These are some examples.

[0021] The mechanism by which the glass according to this embodiment increases ionic conductivity is not entirely clear, but the inventors speculate as follows.

[0022] CO in glass ２ As the content decreases, isolated SiO forms in the glass. ４ The proportion of tetrahedral structures increases, and the number of cross-linked oxygen atoms decreases. As a result, the mobility of alkali metal cations and other elements that affect ionic conductivity increases, which is thought to lead to higher ionic conductivity. Furthermore, since ionic conductivity is also affected by the concentration of alkali metal cations, CO ２ It is thought that a decrease in content leads to an increase in alkali metal cation concentration and thus higher ionic conductivity. Isolated SiO ４ A tetrahedron is a SiO ４ Other SiO in the tetrahedral structure ４ SiO2 has zero bridging oxygen atoms shared with the tetrahedron. ４ This shows a tetrahedron.

[0023] CO2 oxide equivalent in the glass according to the present embodiment ２The content is less than 10% by weight, preferably 8% by weight or less, and more preferably 5% by weight or less. It is often 0.1% by weight or more, preferably 0.3% by weight or more, more preferably 0.4% by weight or more, even more preferably 1% by weight or more, and particularly preferably 2% by weight or more.

[0024] CO2 contained in the glass according to this embodiment ２ The method for measuring the content is not particularly limited, but examples include thermogravimetric-mass spectrometry (TG-MS) and thermogravimetric-differential thermal analysis (TG-DTA).

[0025] More specifically, CO ２ The content can be determined by the following method. First, glass is crushed and passed through a sieve of an appropriate mesh to produce glass powder. This glass powder is packed into a cell and TG-MS measurement is performed. TG can be measured using, for example, STA 449 F3 (manufactured by Jupiter NETZSCH), and MS can be measured using JMS Q1500GC (manufactured by JEOL). Ionization can be performed by the electron ionization method. Then, the sample is heated in a nitrogen atmosphere at a constant heating rate, and the weight change is measured and the gas generated during heating is analyzed while the sample is held at a constant temperature for a certain period of time after heating. Figure 1 shows an example of a TG curve obtained from TG-MS measurement. As shown in Figure 1, the weight loss from the start of measurement is calculated, and CO ２ The content can be determined.

[0026] MS measurement results show that the TIC (Total Ion Chromatogram) and the ion profile at m / z=44 are in close agreement, and the mass spectrum is CO ２ This closely matches the results, indicating that the weight loss in TG measurements is mainly due to CO2. ２ It can be assumed that this is the cause of the occurrence.

[0027] Furthermore, TG-DTA measurements show CO ２The content can be determined by the following method. Glass powder prepared in the same manner as the TG-MS measurement described above is packed into a cell and measured. TG-DTA measurement can be performed using, for example, a differential thermal analyzer (Rigaku Corporation, product name: Themo plus EVO2 Sample Observation TG-DTA). The sample is heated in a nitrogen atmosphere at a constant heating rate, and after heating, the weight change is measured and differential heat is analyzed while it is held at a constant temperature for a certain period of time. The same curve as the TG-MS measurement can be obtained with TG-DTA measurement. As shown in Figure 1, the weight loss from the start of measurement is calculated, and CO ２ The content can be determined.

[0028] The glass transition temperature (Tg) and the first crystallization onset temperature (Tc-on) can be determined in the aforementioned TG-DTA measurement by using the inflection point of the DTA curve showing the exothermic-endothermic amounts, the intersection of the peak and the baseline, etc. Both Tg and Tc-on are temperatures specific to the composition of the glass.

[0029] More specifically, Tg can be determined by the following method. First, the linear portion on the low-temperature side before the glass transition and the linear portion on the high-temperature side after the glass transition are set as baselines. Tg can be identified as the intersection of the low-temperature baseline and the high-temperature baseline, or as the inflection point of the DTA curve.

[0030] (Cationic Components) The cationic components contained in the glass according to this embodiment are not particularly limited, but contain a total of 5% or more of cations of one or more first elements selected from the group consisting of Si, B, P, Ge, As, Sb, Bi, Te, and V, expressed in cation percentage. The content of the cations of one or more first elements is preferably 10% or more, and preferably 20% or more, expressed in cation percentage. Furthermore, there is no particular upper limit, but it may be, for example, 30% or less, or 25% or less. Below, the cations of first elements, alkali metal cations, and other cationic components contained in the glass according to one embodiment of the glass according to this embodiment will be described.

[0031] The cation of the first element contained in the glass according to this embodiment is Si ４＋ Or B３＋ any one of the above is preferable, and Si ４＋ and B ３＋ it is more preferable to include both.

[0032] In the glass according to the present embodiment, when Si is contained as a cation of the first element ４＋ , the content is not particularly limited. From the viewpoint of improving ionic conductivity by increasing the mobility of alkali metal cations and the like, a content exceeding 0.0% and less than 50% is preferable. In a preferred embodiment from the viewpoint that the glass according to the present embodiment is more easily vitrified, Si ４＋ the content of is more than 0.0%, may be more than 0.3%, may be 1.0% or more, preferably 2.5% or more, more preferably 5.0% or more, further preferably more than 5.0%, still further preferably 6.0% or more, and particularly preferably 7.0% or more. Further, in the above embodiment, Si ４＋ the content of is preferably 20% or less, more preferably 10.0% or less, further preferably 9.0% or less, and particularly preferably 8.0% or less.

[0033] In the glass according to the present embodiment, when B is contained as a cation of the first element ３＋ , the content is not particularly limited. From the viewpoint of improving ionic conductivity by increasing the mobility of alkali metal cations and the like, a content exceeding 0.0% and less than 50% is preferable. In one embodiment, B ３＋ the content of is preferably more than 1.0%, preferably 10.0% or more, more preferably 11.0% or more, and further preferably 12.0% or more. Further, in the above embodiment, B ３＋ the content of is preferably 23% or less, more preferably 18.5% or less, and further preferably 16.0% or less.

[0034] In the glass according to the present embodiment, the total content of Si ４＋ and B ３＋ from the viewpoint of glass stability, is preferably 10.0% or more, more preferably 20.0% or more, further preferably 25.0% or more, and most preferably 29.0% or more. Further, Si ４＋ and B ３＋The total content is preferably 36.0% or less, more preferably 35.0% or less, and even more preferably 30.0% or less.

[0035] In the glass according to the present embodiment, as cations of the first element, P ５＋ , Ge ４＋ , As ３＋ , As ５＋ , Sb ３＋ , Sb ５＋ , Bi ３＋ , Te ４＋ , Te ６＋ , V ３＋ , V ４＋ , and V ５＋ may contain one or more cations selected from the group consisting of, and the content is not particularly limited, but is preferably more than 0% and 10% or less for each, respectively.

[0036] In addition, the glass according to the present embodiment preferably contains alkali metal cations. As used herein, the term "alkali metal cation" refers to a cation of an alkali metal, which is a component that improves the ionic conductivity of glass and tends to lower the glass transition point (Tg). Specifically, Li ＋ , Na ＋ , K ＋ , Rb ＋ , Cs ＋ and Fr ＋ can be mentioned. Here, the glass according to the present embodiment preferably contains alkali metal cations in an amount of more than 0.0% and 90% or less, more preferably 50% or more and 80% or less, and even more preferably 70% or more and 78% or less, expressed in cation%.

[0037] In the glass according to the present embodiment, as the alkali metal cation, Li ＋ is preferably contained, and the content is not particularly limited. Li ＋If it contains, the content is preferably 50% to 80%. Furthermore, in terms of increasing ionic conductivity, it is preferable that it exceeds 67.0%, more preferably 69.0% or more, even more preferably 71.0% or more, particularly preferably 73.0% or more, especially preferably 74.0% or more, and most preferably 75.0% or more. Furthermore, in terms of improving the stability of the glass, it is preferable that it is 79.0% or less, more preferably 78.0% or less, and even more preferably 77.0% or less.

[0038] In the glass according to this embodiment, Na ＋ _K ＋ , Rb ＋ , Cs ＋ and Fr ＋ If it contains, the content is not particularly limited. In terms of easily suppressing crystallization of the glass, it is preferable that it be 0% or more, more preferably 0.01% or more, and still preferable 0.1% or more, respectively. Also, in terms of easily suppressing the decrease in ionic conductivity, it is preferable that it be 30% or less, more preferably 10.0% or less, and still preferable 5.0% or less.

[0039] Furthermore, in the glass according to this embodiment, Y ３＋ , Zr ４＋ , and, La ３＋ Preferably, the content of each is further one or more cations selected from the group consisting of Y. ３＋ , Zr ４＋ , and, La ３＋ The total content is preferably more than 0% and 10% or less in terms of cation percentage. ３＋ , Zr ４＋ , and, La ３＋ The total content of is more preferably 0.1% or more, may exceed 0.3%, even more preferably 0.4% or more, particularly preferably 0.6% or more, especially preferably 0.8% or more, and most preferably 1.0% or more, in terms of suppressing crystallization of the glass. Also, in terms of making it easier to maintain the amorphous state of the glass, Y ３＋ , Zr ４＋ , and, La ３＋The total content is more preferably 8.0% or less, even more preferably 7.0% or less, particularly preferably 6.0% or less, and especially preferably 5.0% or less.

[0040] Y ３＋ If it includes Y ３＋ The content of is preferably 0.1% or more, more preferably 0.2% or more, may exceed 0.3%, even more preferably 0.5% or more, particularly preferably 0.8% or more, and especially preferably 1.0% or more. Furthermore, in the glass according to this embodiment, Y ３＋ If it includes Y ３＋ The content of is preferably 5.0% or less, more preferably 4.0% or less, even more preferably 3.0% or less, and particularly preferably 2.0% or less.

[0041] Zr ４＋ If it includes Zr ４＋ The content of is preferably 0.1% or more, may exceed 0.3%, more preferably 0.5% or more, and even more preferably 1.0% or more. Furthermore, in the glass according to this embodiment, Zr ４＋ If it includes Zr ４＋ The content of is preferably 7.0% or less, more preferably 5.0% or less, even more preferably 4.0% or less, particularly preferably 3.0% or less, and especially preferably less than 2.0%. In addition, in a preferred embodiment of the glass according to this embodiment, Zr ４＋ It may not include or substantially not include.

[0042] La ３＋ If it includes La ３＋ The content of is preferably 0.1% or more, may exceed 0.3%, more preferably 0.5% or more, even more preferably 1.0% or more, particularly preferably 1.5% or more, and especially preferably 2.0% or more. Furthermore, in the glass according to this embodiment, La ３＋ If it includes, La ３＋ The content of is preferably 6.0% or less, more preferably 5.0% or less, even more preferably 4.0% or less, particularly preferably 3.0% or less, and especially preferably 2.5% or less. In addition, in a preferred embodiment of the glass according to this embodiment, La ３＋It may not include or substantially not include.

[0043] The glass according to this embodiment may contain cationic components other than those mentioned above. For example, Mg ２＋ Ca ２＋ , Sr ２＋ Ba ２＋ Fe ２＋ Fe ３＋ , Sc ３＋ Ce ３＋ Ce ４＋ , Nd ２＋ , Nd ３＋ , Gd ３＋ , Dy ２＋ , Dy ３＋ Yb ２＋ Yb ３＋ Ti ４＋ , Nb ２＋ , Nb ３＋ , Nb ４＋ , Nb ５＋ Ta ５＋ , Cr ３＋ , W ６＋ Mn ２＋ Mn ３＋ Mn ４＋ Co ２＋ Co ３＋ Ni ２＋ Ni ３＋ ,Cd ２＋ , Zn ２＋ Al ３＋ Ga ３＋ In ３＋ Sn ２＋ , and Sn ４＋ It may contain one or more cationic components selected from the group consisting of the following:

[0044] (Anionic component) The anionic component contained in the glass according to this embodiment is not particularly limited, but O ２－ It is preferable to include O ２－ If it contains, the content is preferably 70.0% or more, more preferably 85.0% or more, even more preferably 90.0% or more, and particularly preferably 95.0% or more. ２－ The content is less than 100.0%, preferably 99.9% or less, and more preferably 99.7% or less.

[0045] Cl － O ２－ It has a lower electronegativity than Li ＋ Because it is difficult to trap Cl, the glass according to this embodiment is Cl － The presence of Cl tends to increase the ionic conductivity. In the glass according to this embodiment, Cl － If it contains Cl, the amount is not particularly limited. － The content of is preferably 0.0% to 9.5%. － The content of is preferably 0.5% or more, more preferably 1.0% or more, particularly preferably 1.4% or more, and may also be 2.0% or more, as it tends to increase ionic conductivity. － The content of is preferably 7.0% or less, more preferably 4.0% or less, even more preferably 3.5% or less, particularly preferably 3.0% or less, and may also be 1.5% or less, in terms of improving the stability of the glass. － It does not need to include or substantially not include Cl. － It may also contain one or more other types of halogen ions.

[0046] In the glass according to this embodiment, SO ４ ２－ The content is not particularly limited. A value of more than 0.0% and less than or equal to 10.0% is preferred because it facilitates a high vitrification rate. ４ ２－ The content is preferably 0.05% or more, more preferably 0.1% or more, even more preferably 0.3% or more in terms of improving the stability of the glass, and may be greater than 0.3%. Also, SO ４ ２－ The content is preferably 7.0% or less, more preferably 6.0% or less, even more preferably 5.0% or less, particularly preferably 4.0% or less, and especially preferably 3.0% or less, as this tends to increase ionic conductivity, and may also be 2.0% or less. In a preferred embodiment of the glass according to this embodiment, SO ４ ２－ It may not include or substantially not include.

[0047] The glass in this embodiment is CO ３ ２－ It contains. The content is preferably 25.0% or less, more preferably 20.0% or less, even more preferably 15.0% or less, and particularly preferably 10.0% or less. ３ ２－ The content is preferably more than 0.0%, more preferably 0.3% or more, may be more than 0.3%, even more preferably 0.5% or more, and particularly preferably 1.0% or more.

[0048] O ２－ and CO ３ ２－ The total content is preferably 70% or more, more preferably 80.0% or more, even more preferably 90.0% or more, and particularly preferably 95.0% or more. ２－ and CO ３ ２－ The total content is 100% or less, preferably 99.5% or less, and may be 99.0% or less.

[0049] The glass according to this embodiment may contain anionic components other than those described above. For example, the glass according to this embodiment may contain F － , I － , and, S ２－ It may further contain one or more anionic components selected from the group consisting of the following. In one embodiment of the glass according to this embodiment, O ２－ CO ３ ２－ SO ４ ２－ , and Cl － The total content of is preferably 90.0% or more, more preferably 95.0% or more, and even more preferably 99.0% or more. In the glass according to this embodiment, O ２－ CO ３ ２－ SO ４ ２－ , and Cl － The total content may be 100.0%. That is, the glass according to this embodiment is O ２－ CO ３ ２－ SO ４ ２－ , and Cl－ It is not necessary to substantially contain any other anionic components.

[0050] (Properties of the glass) The glass according to this embodiment has high ionic conductivity. The ionic conductivity of the glass according to this embodiment at 25°C is 1.0 × 10⁻⁶. －６ A ratio of S / cm or higher is preferred, and 2.0 × 10 －６ S / cm or higher is more preferable, and 3.0 × 10 －６ A ratio of S / cm or higher is even more preferable, and 4.0 × 10 －６ A value of S / cm or higher is most preferable. In this specification, the ionic conductivity of glass is measured by the AC impedance method. Specifically, the ionic conductivity is measured by the AC impedance method using a Solartron Analytical SI-1260 impedance / gain phase analyzer. The glass according to this embodiment is cut into an appropriate shape (for example, a size of 6 mm or larger in diameter) in a dry air atmosphere with a dew point of -50 to -70°C, and gold electrodes with a diameter of 4 mm are formed on both sides by vapor deposition in a dry air atmosphere with a dew point of -30 to -50°C to obtain a sample for measurement. Using the obtained sample for measurement, the measurement is performed in an environment with a temperature of 25°C and a dew point of -30°C or lower, with a measurement applied voltage of 10 mV and a frequency of 1 to 10 ７ Measurements are performed in the Hz range. Ionic conductivity is calculated from the electrical resistance obtained from the Nyquist plot, the electrode area, and the plate thickness of the sample excluding the gold electrode.

[0051] The vitrification rate of the glass according to this embodiment is preferably 30% or more, more preferably 60% or more, even more preferably 70% or more, and particularly preferably 80% or more. The vitrification rate may also be 100%. The vitrification rate can be defined as the ratio of the number of flakes in which no crystalline material is observed and which are determined to be amorphous by X-ray diffraction, obtained by observing any 10 or more of the obtained glass flakes with an optical microscope. That is, the ratio of the number of flakes determined to be amorphous by X-ray diffraction to the number of flakes observed with the optical microscope can be defined as the vitrification rate (unit: %).

[0052] In the glass according to this embodiment, the glass transition temperature (Tg) is often 800°C or lower, preferably 600°C or lower, more preferably 500°C or lower, and even more preferably 450°C or lower. Tg is often 100°C or higher, may be 200°C or higher, and preferably 300°C or higher. When Tg is within the above range, it is easy to densify and sinter at low temperatures.

[0053] In the glass according to this embodiment, the first crystallization onset temperature (Tc-on) is preferably 300°C or higher, and more preferably 350°C or higher. Tc-on is often 1000°C or lower, may be 800°C or lower, and is preferably 500°C or lower. When Tc-on is within the above range, a stable glassy state is easily maintained.

[0054] The value of ((Tc-on)-Tg) is often 20°C or higher, preferably 40°C or higher, and more preferably 50°C or higher. Also, ((Tc-on)-Tg) is often 300°C or lower, more preferably 200°C or lower, even more preferably 150°C or lower, and particularly preferably 100°C or lower. Setting ((Tc-on)-Tg) to 20°C or higher makes it easier to obtain dense and stable glass during sintering by heat treatment. Setting ((Tc-on)-Tg) to 300°C or lower is preferable from the viewpoint of suppressing crystallization during glass melting and molding.

[0055] In one embodiment of the glass according to this embodiment, when alkali metal cations are included, the ratio of the alkali metal cation content to the cation content of the first element is preferably 0.1 or higher, more preferably 1 or higher, even more preferably 2 or higher, and particularly preferably 3 or higher, in terms of improving ionic conductivity. Furthermore, from the viewpoint of glass stability, the cation ratio is preferably 7 or lower, more preferably 6 or lower, even more preferably 5 or lower, and particularly preferably 4 or lower.

[0056] In one embodiment of the glass according to this embodiment, Li is used as an alkali metal cation. ＋ If it contains, Li relative to the content of the first element's cation ＋The ratio of the content of is preferably 0.1 or higher, more preferably 1 or higher, even more preferably 2 or higher, and particularly preferably 3 or higher, in terms of improving ionic conductivity. Furthermore, from the viewpoint of glass stability, the cation ratio is preferably 7 or lower, more preferably 6 or lower, even more preferably 5 or lower, and particularly preferably 4 or lower.

[0057] (Form of the glass) The form of the glass according to this embodiment is not particularly limited and may be in the form of a block, a plate, cullet, flake (thin plate), pellet, glass frit, or powder. In order to sinter and densify the glass, it is preferable to use glass frit.

[0058] (Method for manufacturing glass) The method for manufacturing glass according to this embodiment is not particularly limited, but it can be manufactured by the following method, for example.

[0059] First, the raw materials are mixed to prepare the raw material mixture. The raw materials are not particularly limited as long as they are the raw materials used in the manufacture of ordinary oxide-based glass, and oxides and carbonates can be used. For example, Li can be used as an oxide raw material. ２ CO ３ Li ２ O, LiOH, etc. can be used as raw materials. ４ ２－ It may include the source. SO ４ ２－ As a source, for example, sulfates of elements contained in the above-mentioned cation components can be cited, for example, Li ２ SO ４ , Y ２ (SO ４ ) ３ , Zr(SO ４ ) ２ , or La ２ (SO ４ ) ３This may also be the case. Furthermore, if the resulting glass contains halogen ions as an anionic component, the raw materials include one or more halogen ion sources. Examples of halogen ion sources include halides of the elements contained in the above-mentioned cationic components, such as lithium halide, yttrium halide, zirconium halide, lanthanum halide, or germanium halide. Cl － As a source, for example, LiCl is preferred, and YCl ３ , ZrCl ４ LaCl ３ , PCL ５ Alternatively, GeCl ４ That's fine.

[0060] Next, the raw material mixture is heated by a known method to obtain a molten product. The heating temperature (melting temperature) can be set as appropriate, but 800°C or higher is preferred, and 900°C or higher is more preferred. The above melting temperature is often 1600°C or lower. The heating time (melting time) during melting is not particularly limited, but shortening the melting time will reduce the CO content in the glass. ２ By increasing the CO content and lengthening the melting time, the CO content in the glass increases. ２ The content can be reduced. Specifically, the CO content in glass ２ In terms of reducing the content, heating time is often 5 minutes or more, preferably 10 minutes or more, and more preferably 30 minutes or more. Although adjustments are necessary as appropriate depending on the amount prepared, by setting the melting temperature to 850°C or higher and the heating time to 30 minutes or more, the CO content in terms of oxides in the glass can be reduced. ２ The content can be reduced to less than 10% by weight.

[0061] Also, CO2 in terms of oxides in glass ２ There are no particular limitations on how to increase the CO content to, for example, 0.4% by weight or more, but by covering the glass with a refractory lid during melting, melting the raw materials in an atmosphere containing carbon dioxide, or bubbling carbon dioxide during the melting of the raw materials, CO can be incorporated into the glass. ２ CO2 can be retained in terms of oxides in glass. ２There are no particular limitations on how to reduce the CO content to less than 10% by weight, but by reducing the amount of carbonate raw material used, using halogens in the raw material, etc., the CO content in the glass can be reduced. ２ The content can be reduced.

[0062] Next, the obtained molten material is cooled and solidified to obtain the glass according to this embodiment. The cooling method is not particularly limited, and known cooling methods can be applied. Examples of cooling methods include using a roll-out machine or a press machine. Alternatively, it may be atomized or rapidly cooled by dropping it into a cooling liquid.

[0063] The resulting glass is preferably amorphous.

[0064] Furthermore, the obtained glass may be processed to achieve a desired shape. For example, to obtain glass frit, the obtained glass can be crushed. The crushing method is not particularly limited, and known methods can be applied.

[0065] <Solid Electrolyte> The solid electrolyte according to this embodiment is made using the glass according to this embodiment described above. For example, it can be obtained by sintering glass frit, which is the glass according to this embodiment. Alternatively, a plate-shaped glass according to this embodiment may be used as is as the solid electrolyte. The solid electrolyte according to this embodiment densifies at low temperatures and exhibits high ionic conductivity, so it can be applied to various applications. For example, all-solid-state lithium-ion secondary batteries, solid oxide fuel cells, oxygen sensors, CO2 ２It can be used in sensors, gas sensors such as ammonia and nitric oxide, metal-air batteries, etc. The solid electrolyte according to this embodiment is characterized by having a low proportion of crystalline components and being dense, but it may contain crystalline components. The crystalline components may be crystalline components added to the glass according to this embodiment when obtaining the solid electrolyte, or crystalline components precipitated by heat treatment of the glass according to this embodiment. Examples of crystalline components other than the glass according to this embodiment include ion-conducting crystals. The solid electrolyte according to this embodiment preferably contains 40% by volume or more of components derived from the glass according to this embodiment, preferably 70% by volume or more, and preferably 80% by volume or more. Furthermore, the solid electrolyte according to this embodiment may contain 100% by volume of components derived from the glass according to this embodiment, that is, it may consist of the glass according to this embodiment. The components derived from the glass according to this embodiment include the glass according to this embodiment, a sintered body obtained by sintering the glass, or mixtures thereof.

[0066] <Oxide Crystallized Glass> The oxide crystallized glass according to this embodiment is a crystallized glass obtained using the glass according to this embodiment described above as the base glass (obtained as the base glass). For example, it can be obtained by cooling and solidifying the glass according to this embodiment using the method described above, then reheating it to near the first crystallization temperature and holding it in that state for a certain period of time to induce crystallization. By gently cooling it after the completion of crystallization, a highly uniform oxide crystallized glass can be obtained. Furthermore, the oxide crystallized glass according to this embodiment may be processed to form a desired shape.

[0067] <Applications> The glass according to this embodiment, and the solid electrolyte containing components derived from the glass according to this embodiment, can be applied to a variety of uses. For example, the solid electrolyte containing components derived from the glass according to this embodiment exhibits high ionic conductivity and is therefore suitably used in the solid electrolyte layer of all-solid-state lithium-ion secondary batteries. Furthermore, the glass according to this embodiment has the characteristic of being easily sintered at low temperatures, which prevents oxidation of electrodes at high temperatures and makes it suitable for use as an electronic component. For example, the glass according to this embodiment is useful as a binding binder when manufacturing multilayer ceramic capacitors, and as a sintering binder when manufacturing low-temperature co-fired ceramic multilayer substrates.

[0068] (All-Solid-State Lithium-Ion Secondary Battery) Figure 2 shows a schematic cross-sectional view of an all-solid-state lithium-ion secondary battery having a solid electrolyte according to this embodiment. In the all-solid-state lithium-ion secondary battery 10 shown in Figure 2, three stacked units 20 are arranged between a positive electrode current collector 24 and a negative electrode current collector 26, and an electron conductor layer 22 is arranged between the stacked units 20. Each stacked unit 20 has a positive electrode layer 12, a solid electrolyte layer 16, and a negative electrode layer 14 in this order. In each stacked unit 20, the positive electrode layer 12 is arranged on the upper side of the paper. The positive electrode current collector 24 is electrically connected to the adjacent positive electrode layer 12, and the negative electrode current collector 26 is electrically connected to the adjacent negative electrode layer 14. Furthermore, the electron conductor layer 22 provides an electrical connection between the positive electrode layer 12 and the negative electrode layer 14, enabling the transfer of electrons between the stacked units 20. The positive electrode layer 12 is Li ＋ The positive electrode active material includes a material that releases and absorbs Li, and the negative electrode layer 14 contains Li ＋ It contains a negative electrode active material that releases and absorbs current. In the all-solid-state lithium-ion secondary battery 10 shown in Figure 2, charging or discharging occurs when electrodes are connected to the positive electrode current collector 24 and the negative electrode current collector 26.

[0069] In the laminated unit 20, Li in the positive electrode active material contained in the positive electrode layer 12 ＋ The standard electrode potentials of the release and storage reactions, and the Li in the negative electrode active material contained in the negative electrode layer 14. ＋A voltage is generated corresponding to the difference between the standard electrode potential and the release and storage reactions of Li. Here, the solid electrolyte layer 16, which is placed between the positive electrode layer 12 and the negative electrode layer 14, is Li ＋ By conducting electrons and blocking them, the stacked unit 20 can be charged and discharged. Furthermore, by stacking multiple stacked units 20 via an electron conductor layer 22 as needed, the voltage that can be extracted can be increased.

[0070] The positive electrode active material contained in the positive electrode layer 12 is not particularly limited, and known positive electrode active materials can be used. For example, LiCoO ２ LiNiO ２ LiMn ２ O ４ , and LiFePO ４ These are some examples. In addition, active materials in which some of the elements of the above-mentioned active material are replaced with other elements can also be applied.

[0071] The negative electrode active material contained in the negative electrode layer 14 is not particularly limited, and known negative electrode active materials can be used. Examples of negative electrode active materials include metallic Li, Li alloys, graphite, metallic Si, and lithium titanate. Other materials not exemplified above for the positive electrode active material and negative electrode active material can also be used as appropriate.

[0072] The stacked unit 20 of the all-solid-state lithium-ion secondary battery 10 shown in Figure 2 may have layers other than the positive electrode layer 12, the negative electrode layer 14, and the solid electrolyte layer 16. Furthermore, the all-solid-state lithium-ion secondary battery 10 shown in Figure 2 may have layers other than the stacked unit 20 and the electron conductor layer 22. Also, the number of stacked units 20 in the all-solid-state lithium-ion secondary battery 10 may be one, two, three, or four or more. While the all-solid-state lithium-ion secondary battery 10 is a series type with multiple stacked units 20 stacked via an electron conductor layer 22, it may also be a parallel type. To create a parallel type, the positive electrode layers 12 and negative electrode layers 14 in the stacked units 20 can be connected via wiring.

[0073] The manufacturing method for an all-solid-state lithium-ion secondary battery, as shown in Figure 2, is not particularly limited, but it can be manufactured by, for example, the following method.

[0074] First, a positive electrode green sheet containing a positive electrode active material and the glass according to this embodiment, a solid electrolyte green sheet containing the glass according to this embodiment, and a negative electrode green sheet containing a negative electrode active material and the glass according to this embodiment are prepared. A method for manufacturing each green sheet includes, for example, preparing a paste or slurry containing each material, coating it onto a substrate, and drying it. The paste or slurry can be prepared by known methods, such as mixing each material with a solvent. Furthermore, the coating method for the paste or slurry is not particularly limited, and known methods such as die coating, screen printing, blade coating, slit coating, and roll coating can be applied. Alternatively, the paste or slurry may be coated in a pattern.

[0075] A resin substrate is preferred as the base material used in the manufacture of the above-mentioned green sheet, and for example, a polyethylene terephthalate resin substrate is preferred. Furthermore, the paste or slurry may also contain a binder resin as described later.

[0076] Next, the obtained green sheets are stacked in order, and alignment and cutting are performed as necessary to create a laminate. If necessary, the stacking may be performed so that the end faces of the positive electrode green sheet and the negative electrode green sheet do not coincide.

[0077] Next, a solid-state lithium-ion secondary battery is obtained by pressing and firing the resulting laminates. When pressing the laminates, heating may be performed, and the heating temperature is preferably 40 to 80°C. Furthermore, the firing is preferably carried out in an air atmosphere, and the firing temperature is preferably 20°C or more higher than the Tg of the glass according to this embodiment and less than the Tc-on of the glass according to this embodiment. Specifically, the firing temperature is preferably 280 to 1000°C, more preferably 280 to 800°C, even more preferably 280 to 700°C, particularly preferably 280 to 600°C, and most preferably 280 to 500°C. The firing time is, for example, 10 minutes to 3 hours.

[0078] A solid-state lithium-ion secondary battery can be obtained by following the above procedure. The above procedure may include steps for providing the configurations that the aforementioned solid-state lithium-ion secondary battery may have.

[0079] The above procedure describes a method for heating the laminate, but other methods may also be used. For example, the laminates may be heated individually before being stacked to obtain an all-solid-state lithium-ion secondary battery. Alternatively, for example, the positive electrode green sheet, the solid electrolyte green sheet, and the negative electrode green sheet may be heated individually before being stacked to obtain an all-solid-state lithium-ion secondary battery.

[0080] (Multilayer ceramic capacitor) The following describes a multilayer ceramic capacitor manufactured using the glass according to this embodiment.

[0081] Figure 3 is a schematic cross-sectional view showing an example of the configuration of a multilayer ceramic capacitor. The multilayer ceramic capacitor 30 shown in Figure 3 comprises a dielectric layer 32, an internal electrode layer 34, and an external electrode 36. Dielectric layers 32 are arranged between each internal electrode layer 34, and the internal electrode layers 34 are alternately connected to the external electrode 36. In the above multilayer ceramic capacitor 30, the glass according to this embodiment is included in the dielectric layer 32. The manufacturing method of the multilayer ceramic capacitor 30 will be described below as the green sheet method. Note that the manufacturing method of the multilayer ceramic capacitor 30 is not limited to the green sheet method, and may also be by printing or other methods.

[0082] First, a mixed powder is obtained by mixing the powder of a functional ceramic constituting the dielectric layer with the glass (glass frit) according to this embodiment. The functional ceramic is selected as appropriate, but for example, barium titanate (BaTiO) ３ Examples include the following. The glass content according to this embodiment relative to the total volume of the mixed powder is preferably, for example, 1 to 10% by volume.

[0083] Next, a dielectric paste or dielectric slurry is prepared containing the mixed powder, a solvent, and the binder resin described below. The dielectric paste or dielectric slurry may contain at least one of a plasticizer and a dispersant. The prepared dielectric paste or dielectric slurry is coated onto a substrate and dried to form a green sheet. The substrate and coating method are the same as those for the all-solid-state lithium-ion secondary battery described above, so a description is omitted.

[0084] Examples of the binder resins mentioned above include polyvinyl butyral, acrylic resins, polyvinyl alcohol, ethylcellulose, methylcellulose, nitrocellulose, butyl cellulose acetate, propyl cellulose acetate, poly-α-methylstyrene, polypropylene carbonate, and polyethylene carbonate. The binder resin can be appropriately selected depending on the firing temperature and other factors described later.

[0085] Next, a conductive paste containing one or more metal particles selected from the group consisting of copper, silver, and nickel is applied to the required portion of the green sheet to form an internal electrode layer. The glass (glass frit) according to this embodiment may also be added to the conductive paste. Adding the glass according to this embodiment to the conductive paste makes it easier to obtain a multilayer ceramic capacitor with excellent adhesion between layers, dielectric properties, and stability over time. Subsequently, multiple green sheets coated with the conductive paste are stacked and bonded together by applying heat and pressure to obtain a laminated sheet. The method of applying the conductive paste is not particularly limited and examples include screen printing and gravure printing. The heating temperature during the bonding process can be, for example, 40 to 80°C.

[0086] Next, the obtained laminated sheet is cut into individual pieces (chips), heated to remove the binder resin component, and the dielectric layer and conductive paste are sintered to obtain a fired laminate. By forming a multilayer ceramic capacitor by firing the laminated sheet in this manner, a multilayer ceramic capacitor can be obtained that has excellent adhesion between each layer, as well as excellent dielectric performance and stability over time.

[0087] Heating and sintering are carried out using a firing furnace in a predetermined atmosphere, such as air, an inert gas, or under reduced pressure. The heating temperature is preferably 20°C or more higher than the Tg of the glass according to this embodiment, and less than the Tc-on of the glass according to this embodiment. Specific temperatures are preferably 280 to 1000°C, more preferably 280 to 800°C, even more preferably 280 to 700°C, particularly preferably 280 to 600°C, and most preferably 280 to 500°C. The firing time is, for example, 10 minutes to 3 hours.

[0088] Subsequently, a conductive paste that will serve as an external electrode is applied to the fired laminate, dried, and fired, and a plating layer of Ni and Sn, etc., is formed as needed. By following the above procedure, a multilayer ceramic capacitor having a dielectric layer containing glass-derived components according to this embodiment is obtained.

[0089] (Low-temperature co-firing ceramic multilayer substrate) The following describes a low-temperature co-firing ceramic multilayer substrate (hereinafter also simply referred to as "ceramic multilayer substrate") manufactured using the glass according to this embodiment.

[0090] A ceramic multilayer substrate is composed of a laminate (hereinafter also referred to as a "laminated unit") that forms three-dimensional wiring in which electrode wiring layers are separated and arranged by insulating layers. The ceramic multilayer substrate may have one laminated unit, or it may have two or more laminated units.

[0091] Figure 4 shows a schematic cross-sectional view illustrating an example of the configuration of a ceramic multilayer substrate. The ceramic multilayer substrate 40 shown in Figure 4 has a substrate body composed of a dielectric layer 42, and has a plurality of planar electrodes 50 on the inside and outside of the substrate body, each having a main surface parallel to the main surface of the substrate body. Furthermore, it has internal vertical electrodes 52 extending along the thickness direction of the substrate, which are arranged inside the substrate body to electrically connect predetermined planar electrodes 50 to each other. In addition, internal mounting components 46 are arranged inside the substrate body so as to contact the planar electrodes 50 arranged inside the substrate, and surface mounting components 44 are arranged so as to contact the planar electrodes 50 arranged outside the substrate. The surface mounting components 44 have electrodes, and these electrodes and other planar electrodes 50 are electrically connected by conductive wires 56. The ceramic multilayer substrate 40 has heat dissipation vias 54 that penetrate the substrate body, and surface mounting components 44 are mounted directly above them.

[0092] In such a ceramic multilayer substrate 40, the glass according to this embodiment is used, for example, to form a dielectric layer 42. Methods for forming the ceramic multilayer substrate include printing and the green sheet method, but the green sheet method will be described below.

[0093] First, a mixed powder is obtained by mixing the glass (glass frit) according to this embodiment with the powder of a functional ceramic constituting the dielectric layer. The functional ceramic can be appropriately selected, but alumina is an example. The content of the glass according to this embodiment relative to the total volume of the mixed powder is preferably, for example, 40 to 70 volume%.

[0094] Next, a green sheet is obtained in the same manner as the manufacturing method for the multilayer ceramic capacitor described above.

[0095] Next, a conductive paste containing at least one of silver and copper is applied to the required portion of the green sheet to form internal wiring or planar electrodes. The glass according to this embodiment may also be added to the conductive paste. Adding the glass according to this embodiment to the conductive paste makes it easier to obtain a ceramic multilayer substrate with excellent adhesion between layers. When forming a resistor layer, a method using a resistor paste mainly composed of ruthenium oxide can be used. Internal vertical electrodes can be formed by pre-drilling holes in the green sheet and filling those holes with the conductive paste. Heat dissipation vias can be formed similarly by pre-drilling holes in the green sheet and filling those holes with a paste containing a material with high thermal conductivity. Internal mounting components may also be placed as needed. The method of applying the paste is not particularly limited and can be, for example, by screen printing and gravure printing. After that, multiple sheets are stacked and pressed together by applying appropriate heat and pressure to obtain a laminated sheet. The heating temperature during pressing can be, for example, 40 to 80°C.

[0096] Next, the obtained laminated sheet is heated to remove the binder resin, etc., and then the functional ceramic and glass according to this embodiment contained in the green sheet, as well as the conductive paste, etc., are sintered to obtain a fired laminate. In this way, by firing the laminated sheet all at once to manufacture a ceramic multilayer substrate, a ceramic multilayer substrate with excellent adhesion between each layer tube, high reliability, and excellent stability over time can be obtained.

[0097] Heating and sintering are carried out using a firing furnace in a predetermined atmosphere, such as air, an inert gas, or under reduced pressure. The heating temperature is preferably 20°C or more higher than the Tg of the glass according to this embodiment, and less than the Tc-on of the glass according to this embodiment. Specific temperatures are preferably 280 to 1000°C, more preferably 280 to 800°C, even more preferably 280 to 700°C, particularly preferably 280 to 600°C, and most preferably 280 to 500°C. The firing time is, for example, 10 minutes to 3 hours.

[0098] Subsequently, as needed, the portions that will become the external electrodes of the fired laminate are plated with Ni, Au, or the like. Alternatively, if necessary, the laminated sheet can be half-cut before firing and then cut into chips after firing. Alternatively, chipping can be done using a dicing saw. Furthermore, surface mount components and conductive wires connecting the electrodes of the surface mount components to the external electrodes are provided on the external electrodes. Known methods can be applied to the above procedure. By following these steps, a ceramic multilayer substrate is obtained.

[0099] The materials, quantities, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples. Examples 1 to 16 and 21 to 35 described later are examples, and Examples 17 to 20 are comparative examples.

[0100] 1. Manufacturing Method Each raw material was weighed and mixed to prepare the glass. Next, the mixed raw materials were placed in a platinum crucible and melted in an electric furnace at 800 to 1600°C for about 0.5 to 4 hours. The melt was then rapidly cooled using a roll-out machine to produce glass flakes. At this time, the melting temperature and melting time for each example were changed as shown in Table 2 or Table 4 below. The roll was rotated at 10 to 20 rpm, and the flakes after passing through the roll were collected in a dry air flow environment. Various conditions were adjusted so that the cooling rate in each example was a constant value. The glass for each example was obtained using the above procedure.

[0101] 2. Measurement (CO ２Quantity) CO2 in oxide terms, measured by the TG-MS or TG-DTA measurements described above. ２ The quantity was measured. Note that in TG-MS measurement, the sample was heated in a helium atmosphere from 50°C to 600°C for 10°C mins. －１ For the CO2 test, the weight change was measured and the gases generated during heating were analyzed when the sample was heated and held at 600°C for 60 minutes. For the TG-DTA measurement, the weight change was measured and differential heat analysis was performed when the sample was similarly heated and held under a nitrogen atmosphere. ３ ２－ The anion percentage was calculated using the following procedure. First, assuming a sample of 100g as the starting amount, the measured value of SO was obtained using the method described above. ３ (wt%), CO ２ Based on (weight %) and Cl (weight %), the remaining SO ４ ２－ CO ３ ２－ and Cl － The mass and number of moles were determined. Then, the measured SO ３ and CO ２ Based on the composition of the preparation, the SO2 decomposed during the melting process. ４ ２－ and CO ３ ２－ The number of moles of was calculated, and the number of moles of oxygen atoms corresponding to them was determined. Furthermore, the number of moles of oxygen atoms obtained from the oxide composition derived from the initial stage (derived from cations other than Li) and the number of moles of oxygen atoms derived from the above decomposition were added together to calculate the total number of moles of oxygen atoms in the glass. This total number of moles was O ２－ Considering this as the number of moles of Cl, － The number of moles and the remaining SO ４ ２－ CO ３ ２－ The number of moles of SO4 is calculated by combining it with the number of moles of SO4, and the number of moles of SO4 is calculated for the total number of moles of all anion species. ４ ２－ CO ３ ２－ , O ２－ , Cl － By calculating the ratio of the number of moles of each, CO ３ ２－The anion percentage (mol%) of each anionic component, including the anion percentage (mol%) of the given anion, was determined. (Ionic conductivity) The ionic conductivity at 25°C was measured for each example of glass obtained using the method described above. The method for measuring ionic conductivity is as described above. The results are shown in Tables 2 and 4 below. (Tg and Tc-on) Tg and Tc-on were measured for each example of composition using the method described above. The results are shown in Tables 2 and 4 below.

[0102] 3. Results The composition, cation composition, and anion composition of the glass for each example are shown in Tables 1 and 3. In Tables 1 and 3, the cation composition and anion composition are expressed in mole percent. The melting conditions and measurement results for each example are shown in Tables 2 and 4. In Tables 2 and 4, CO ２ CO2 is the oxide equivalent. ２ The values ​​represent the content (by weight %). In the table, a "-" in the "Measurement" column indicates that measurement was not performed.

[0103]

[0104]

[0105]

[0106]

[0107] From the results shown in Table 2, CO2 in terms of oxides ２ In Examples 1-16 and 21-35, where the content was less than 10% by weight, it was confirmed that the ionic conductivity was higher than in Examples 17-20. Furthermore, from a comparison of Examples 1, 2, and 3, it was found that the longer the melting time, the higher the CO2 oxide equivalent. ２ It was confirmed that the content decreased and the conductivity increased. In addition, all examples had low glass transition temperatures (Tg) and were capable of low-temperature sintering.

[0108] Furthermore, CO2 in terms of oxides ２ Example 7, where the content is 0.08% by weight, and CO ２ Compared to Example 6, which has a content of 0.3% by weight, Example 6 had a lower glass transition temperature than Example 7. From this, the CO2 oxide equivalent ２Glass containing 0.3% by weight or more CO ２ It can be seen that it exhibits superior low-temperature sintering performance compared to glass with a content of 0.1% by weight or less.

[0109] Although various embodiments have been described above, it goes without saying that the present invention is not limited to these examples. It is clear to those skilled in the art that various modifications or alterations can be conceived within the scope of the claims, and these will naturally also fall within the technical scope of the present invention. Furthermore, the components in the above embodiments may be combined in any way without departing from the spirit of the invention.

[0110] This application is based on a Japanese patent application (JP 2025-042560) filed on March 17, 2025, the contents of which are incorporated herein by reference.

[0111] 10 All-solid-state lithium-ion secondary battery 12 Positive electrode layer 14 Negative electrode layer 16 Solid electrolyte layer 20 Stacked unit 22 Electronic conductor layer 24 Positive electrode current collector 26 Negative electrode current collector 30 Multilayer ceramic capacitor 32 Dielectric layer 34 Internal electrode layer 36 External electrode 40 Ceramic multilayer substrate 42 Dielectric layer 44 Surface mount component 46 Internal mount component 50 Planar electrode 52 Internal vertical electrode 54 Heat dissipation via 56 Conductive wire

Claims

1. CO2 in terms of oxides ２ Glass having a content of less than 10% by weight, and the total content of cations of one or more first elements selected from the group consisting of Si, B, P, Ge, As, Sb, Bi, Te, and V is 5% or more in terms of cation percentage.

2. The glass according to claim 1, which contains one or more alkali metal cations in an amount greater than 0.0% and less than or equal to 90% in cation percentage.

3. B as the cation of the first element. ３＋ and Si ４＋ It includes, and the alkali metal cation is Li ＋ It contains, and the content of each is expressed in cation percentage, B ３＋ Si ４＋ Li ＋ The percentage is between 50% and 80%, and furthermore, as an anion, O ２－ The glass according to claim 2, including the glass described in claim 2.

4. The said O ２－ and CO ３ ２－ has a total content of 70% or more and 100% or less in terms of anion percentage, according to the glass of claim 3.

5. B as the cation of the first element. ３＋ and Si ４＋ It contains, and the content of each is expressed in cation percentage, B ３＋ If the amount is more than 1.0% and 23% or less, and Si ４＋ The glass according to claim 3, wherein the content is more than 5.0% and 20% or less.

6. Y ３＋ La ３＋ , and Zr ４＋ It further contains one or more cations selected from the group consisting of Y ３＋ La ３＋ , and Zr ４＋ The glass according to any one of claims 1 to 5, wherein the total content is greater than 0% and 10% or less in terms of cation percentage.

7. Furthermore, Cl as an anion － Includes Cl － The glass according to claim 6, wherein the content of is 0.0% or more and 4.0% or less in anion percentage.

8. The ionic conductivity at 25°C is 2.0 × 10⁻⁶. －６ The glass according to claim 7, wherein the density is S / cm or greater.

9. CO2 in terms of oxides ２ The glass according to any one of claims 1 to 5, wherein the content is 0.4% by weight or more and less than 10% by weight.

10. The glass according to claim 9, wherein the glass transition temperature is 800°C or lower.

11. The glass according to claim 9, wherein the first crystallization onset temperature is 300°C or higher.

12. The glass according to claim 9, wherein ((Tc-on)-Tg) is 20°C or more and 150°C or less, when the glass transition temperature is Tg and the first crystallization onset temperature is Tc-on.

13. The glass according to claim 9, wherein the ratio of the alkali metal cation content to the cation content of the first element is 0.1 or more and 7 or less.

14. Li as the alkali metal cation ＋ Including the cation content of the first element, ＋ The glass according to claim 13, wherein the ratio of the content of is 0.1 or more and 7 or less.

15. A solid electrolyte comprising a glass-derived component according to any one of claims 1 to 5.

16. Oxide crystallized glass having the glass described in any one of claims 1 to 5 as the base glass.

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