TW201226354A - Precursor glass for anode material of lithium ionic secondary cell and crystalline glass for anode material of lithium ionic secondary cell - Google Patents

Abstract

A precursor glass for an anode material of a lithium ionic secondary cell is characterized in containing 20 mole% to 50 mole% of Li2O, 20 mole% to 40 mole% of P2O5, 0 mole% to 40 mole% of Fe2O3, 0 mole% to 60 mole% of MnO2, and 0.1 mole% to 2.4 mole% of Nb2O5, and (Fe2O3+MnO2/2) /P2O5 ≥ 0.85 based on mole ratio.

Description

201226354 VI. [Technical Field] The present invention relates to a precursor glass for a positive electrode material for a clock ion secondary battery used in a portable electronic device or an electric automobile, and a positive electrode for a plasma ion secondary battery. The material is made of crystallized glass. [Prior Art] A lithium ion secondary battery has established a position as a high-capacity, lightweight power source that is indispensable for portable electronic terminals or electric vehicles. Among the positive electrode materials for lithium ion secondary batteries, inorganic metal oxides such as lithium cobaltate (Lic® 2) or lithium manganate (LiMn〇 2) have heretofore been used. However, with the increase in power consumption caused by the high performance of electronic equipment in recent years, it is required to increase the capacity of the secondary battery of the step-by-step. Furthermore, from the viewpoint of environmental protection issues or energy issues, it is required to convert materials with a large environmental burden such as 〇4 Mn into more environmentally compatible materials. In addition, in recent years, the resource has been paid attention to, and from this point of view, it is also expected to be converted into an inexpensive cathode material that replaces lithium cobaltate or lithium manganate. In recent years, transcripts and resources are considered to be good, 21 Ϊ m spar crystal, occupation (10) ^ ϋ and demolition stone crystal (LiF called) by Guan Zhuang' and have made various research and development (Kaiping) Bulletin 9-m725).苴中, _ 1彳如—Japanese Patent Wenlu Stability S 撖 石 型 型 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 结晶 钴 钴 钴 钴 钴 钴 钴 钴 钴 钴 钴 钴 钴 钴 钴 钴And Wei Wei (four) New Zealand caused by Wei Wei

4 201226354 Λ. In addition, the iron sites in the crystals of the known manganese-based spinel type, NASICON type, and olivine type can be replaced by various transition metal ions. For example, Li3Mn2(p〇4)3, LiMnP〇4, Livp〇4, which completely replaces iron with manganese or vanadium, partially replaces iron with bell or hunger Li3 (MnxFeyVl(x+y))2 (P 〇4)3, LiMnxFe(1.x)P04 (0<X<1, 〇<y<i, 〇<x+y<1) and the like also have a function as a positive electrode material. Among them, it is known that when a conductive active material such as carbon powder is mixed in a positive electrode material, electron conductivity is improved. 35. If the conductive active material is mixed in the acid-electrode positive electrode material, the conductive active material may not be efficiently activated on the surface of the lithium iron phosphate particle due to the influence of the gas generated from the iron-iron clock. , the problem of reduced electronic conductivity. Therefore, as a positive electrode material having a small amount of gas generated during firing, a lithium iron phosphate material containing crystallized glass has been proposed (for example, refer to Japanese Patent Laid-Open Publication No. 2009-87933). The precursor glass is substantially free of gas when it is mixed with the carbon powder _ substance to be calcined. Therefore, the conductive active material can be efficiently activated on the surface of the positive electrode material particles, and excellent electron conductivity can be easily achieved. Moreover, by calcining the precursor glass, it is possible to produce a crystallized powder having a homogeneous composition and having a small crystal grain size of iron phosphate clock crystal or iron phosphate-solution crystal, which can be: Conductive Excellent miscellaneous secondary battery cathode material. As described above, the iron phosphate "described in the Japanese Patent No. 8-933 (Japanese Patent Publication No. 8933) has become a positive electrode material which is excellent in both of the materials and the f-conducting. The positive electrode material described in Japanese Patent Publication No. 2-87933 is composed of 201226354 and has a large change in battery capacity at the time of charge and discharge. However, in the publication of Japanese Patent Laid-Open Publication No. Hei. No. 20,879,937, the research on the most preferable composition of the battery capacity is sufficient, and the current situation is that the positive electrode material having a high battery capacity is still available. SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and an object of the present invention is to provide a battery for a battery having a high battery capacity, a positive electrode material for a secondary battery, a precursor glass, and a crystal for a positive electrode material for a lithium ion secondary battery. Glass. Ben, Ming is about the _ sub-secondary battery positive electrode material for the precursor glass Ί 在于 在于 · · 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 朗 百分比 百分比 百分比 百分比 百分比 百分比 百分比 百分比 含 百分比 含 含 含 含~ gene, μ 〇%~60%, Nb2〇5 〇·1%~2 4%, and 莫02η02/2) /Ρ2〇52〇.85.丨, 2u3 + If the precursor glass having the above composition is used, a positive electrode material for a rotor secondary battery having a battery capacity can be produced. "二=璃" means crystallization by heat treatment, and precipitation is second. Preferably, the clock of the present invention is separated from the precursor glass rail by t% and contains 24% = 24% == V2 〇 5l TM?^2+Al2〇3+Ga^ °2 The composition of the above-mentioned knives to improve the glass forming ability. Ϊ́ΐΐ1 change: It is easy to obtain stable vitrification and is difficult to precipitate; it is preferable to use a positive electrode material of the clock ion secondary battery of the present invention 201226354

Li2〇/ ( P2〇5 + Fe2〇3 + in the body glass, in molar ratio

Mn02/2) 20.5. According to the configuration of (4), it is easy to obtain a rotor secondary battery positive electrode material having stable surface formation, difficult to be treated, and high battery capacity. Fourth, it is preferable to use the lithium ion dual-purpose precursor glass of the present invention. Material series, Ll2〇/P2〇5_5 正料

Li20/ (Fe203 + Mn02/2) g〇.85. With or with this configuration, it is easy to obtain vitrification stability: desired heterogeneous crystal, high battery capacity, and secondary battery positive electrode material. The other aspect of the present invention relates to a precursor for a clock ion positive electrode material. The body glass is characterized in that, as a lang composition, the percentage of the moles is 対Li2Q 〜5〇%, ρ2()5 2〇%~4〇%,

Fe203 〇%~40%, Μη02 〇%~60%, Nb2〇5 〇%~2 4%, and Li20/P2〇5g 1.01 in terms of molar ratio. Sixth, the present invention relates to a crystallized glass for a positive electrode material for a lithium ion secondary battery, which is characterized in that, as a glass composition, Li20 is contained in a percentage of 20% to 50%, P2〇5 20% to 40%, Fe203 〇%~ 40%, Mn020%~60%, Nb205 〇.l%~2.4%, a(Fe203 +

Mn02/2) /P2〇5^0.85 〇7, preferably, the crystallized glass for the positive electrode material of the lithium ion secondary battery of the present invention further contains 〇% to 2.4% of Si〇2 + V205 in terms of mole percentage + B2〇3 + Ge02 + Al2〇3 + Ga2〇3 + Sb2〇3 + Bi203. 201226354 Eighth, it is preferred that the clock ion secondary battery of the present invention is using crystallized glass, in molar ratio, Li2Q/(j

Mn02/2) 20.5. 3 ninth' is preferably a crystallized glass towel for a positive electrode of a clock ion secondary battery of the present invention, in terms of a molar ratio, Li2〇/P2Q5^85, and 1 u20/(Fe2〇3 + Mn02/2 ^0.85 ° " Tenth, another aspect of the present invention relates to a crystallized glass for a clock ion two positive electrode material, the ship of which is: as a glass composition, containing Li2〇2G%~5G% in percentage of moles! >2()5 ·~4〇%, Fe2〇3 〇%~40%, Μη02 〇%~6〇%, Nb2〇5 〇%~2 4%,〇

Li2〇/P2〇5gl.〇l. 〇' and the tenth-'preferably, the crystallized glass for the positive electrode material of the clock ion secondary battery of the present invention contains LiMnxFeyl^PO4 crystals (〇$xgl, 〇$% οοο lt; x + y9, Μ is selected from Nb, Ti, V, Cr, ^:,

At least one of Ni is used as a main crystal. The eleventh preferred embodiment of the ion secondary battery positive electrode material of the present invention has a crystal content of LiMnxFeyMWx+y)P〇4 in the crystallized glass of 5 〇% or more. According to a thirteenth aspect, the present invention relates to a method for producing a positive electrode material for a lithium ion secondary battery, which is characterized in that the step of adjusting the raw material powder by the glass composition is as follows: 'Li2〇20 is included as a percentage of moles %~50%, P205 20%~40%, Fe203 〇%~40%, Μη02 〇〇/0~ 60%, Nb205 〇. 1%~2.4%, and in terms of molar ratio, (Fe2〇3 + Mn 〇2/2 ) /P2〇5^〇.85; a step of melting the raw material powder to obtain molten glass;

S 8 201226354 and a step of quenching the molten glass to obtain a precursor glass break. According to a fourteenth aspect, preferably, the method for producing a positive electrode material for a secondary battery of the present invention further comprises the step of heat-treating a glass such as a drive glass to obtain a crystallized glass. [Embodiment] The precursor glass for a positive electrode material for a lithium ion secondary battery of the present invention is characterized in that, as a glass composition, Li2〇20% to 50%, P2〇5 20% to 40%, in terms of a percentage of moles, Fe203 〇%~4〇%, Μη02 0%~60%, Nb205 0.1%~2.4% ' and in terms of molar ratio, (Fe2〇3 + ]v[n〇2/2) /P205 2 〇· 8 5 . The reason why the glass composition is limited to the above is explained below.

The main component of Li2〇疋LiMnxFeyMi_(x+y)P〇4 crystal. Preferably, the content of Li20 is 20% to 50%, 25% to 45%, 30% to 40%, 33% to 37%, particularly 33.5% to 37%. When the content of Li20 is too small, the amount of precipitation of LiMi^FeyMi-^+^PC^ crystals becomes small when the precursor glass is crystallized, and it is difficult to obtain a high battery capacity. On the other hand, when the content of Li20 is too large, it is easy to precipitate undesired heterogeneous crystals (Li3P04, ["(ΜηΜ-χΜΡΟΛ, etc.). As a result, the precipitation amount of LiMnxFeyMHx+y)P〇4 crystals is small, and it is difficult. A high battery capacity is obtained. P2〇5 is also a main component of LiMnxFeyMHx+y)P〇4 crystal. It is preferred that the content of P205 is 20% to 40%, 5% to 35%, and 28% to 35°/. 29% to 33%, particularly preferably 29.5% to 32.5%. When the content of P2〇5 is outside the range, undesired heterogeneous crystals are easily precipitated when the precursor glass is crystallized. The amount of precipitation of LiMi^FeyM^x+joPO4 crystals is small, and it is difficult to obtain a high battery capacity.

Fe203 is a constituent of LiMnxFeyMux+y/C^ crystal. Preferably, the content of Fe203 is 0% to 40%, 10% to 40%, 20% to 35%, particularly 30% to 35%. When the content of Fe2〇3 is too large, it becomes easy to precipitate undesired heterogeneous crystals when the precursor glass is crystallized. As a result, the amount of precipitation of LiMnxFeyMwx+yPO4 crystals is small, and it is difficult to obtain a high battery capacity. Further, FeO or Fe3〇4 may be used as a raw material, and in this case, the amount converted to Fe2〇3 may satisfy the above range.

Similarly to Fe2〇3, Mn〇2 is a constituent of the crystal of LiMnxFeyMi-HPCU. Preferably, the content of Μη02 is 〇%~6〇%, 20%~55〇/〇, 30%~55%, 40%~553⁄4, especially 45%~5〇%. If the content of Mn〇2 is too large, it becomes easy to crystallize the precursor glass.

The scope is sufficient.

3 + Μη〇2/2)/Ρ2〇5 is 〇.85 匕. (Fe203 + Mn02/2) is preferably a molar ratio (Fe2〇3 + or more, 〇·9 or more, especially 〇·95 or more. 201226354 is more likely to precipitate the precursor glass when it is crystallized. It is desirable to obtain a high battery capacity. In addition, it is not preferable that the upper limit is 2 ί; a sufficient amount of LiMnxFeyMl-(X+y)P〇4 crystal is formed, and 1 is preferably 疋2 or less, particularly 1.5 or less. In addition to the composition of the six glass forming ability, except Nb2〇5 SiO, Υ〇*, ten is 〇%~2·4%, especially 〇.1%~2 3%= some, one-time precipitation Unexpectedly, it is easy to make the precursor crystal crystallization of the precursor crystal, and it is difficult to obtain high battery capacity. The precursor of the positive electrode material for lithium ion secondary battery in the body glass is T〇fl , Γ ^ } ^ (P^ + ^〇3 + Mn〇2/2) Γ〇/2ΐ: In particular: ·52 or more, as expected, 1 material is easy (4) Lai's crystallization does not lead to high battery capacity. For the upper limit ^:i^i^iLlMn^W04#, the weight of 疋1 is below, especially below 0.8. Zhao Chuanzi. The positive electrode material of t❶ battery uses more than 1 precursor, especially for the former IS body. When the glass crystallizes, it may not be two or five; a:: In addition, there is no special upper limit: two = 3 xxFeyMl_(x+y)P〇4 crystals, preferably 2 or less, especially 1.5 or less. It is preferable that in the precursor glass of the secondary battery positive electrode material of the present invention, 201226354, in the molar ratio, the secret / (five) is only /2 or more, especially 疋 0.9 or more. If the secret / ... + (10) is too small, the change is easy to precipitate an undesired heterogeneous knot when the precursor glass crystallizes, and it is difficult to obtain a high battery capacity. Further, the shame is not limited, and in order to precipitate a sufficient amount of LiMnxFeyMi, the ρ〇4 crystal is, in particular, 1.5 or less. The other form of the precursor glass for the positive electrode material of the H ion secondary battery of the invention is: as a glass mash, containing in percentage of mole

Ll2〇20%~5G%, P2〇5 2G%~4G%, Fe2〇3 〇%~4G%, Μη02 〇%~6〇%, Nb2〇5 〇%~24%, and in terms of molar ratio, Ll2〇/P2Ogl. (H. In this form, the preferred range of the content of each component and the reason for limitation can be applied. The rotor secondary battery of the present invention can be used as a crystallized glass. In the second embodiment, the negative electrode material is prepared by calcining the precursor with a precursor. The characteristics of the crystallized glass for the positive electrode material of the clock ion secondary battery of the present invention are as follows: It contains Li2020〇/.~50/〇P2〇5 20%~4〇〇/0, Fe2〇3 〇〇/〇~4〇%, Mn〇2 〇%~6〇%,

Nb205 〇.1/0~2.4〇/〇, and (Fe2〇3 + Mn〇2/2) /p2〇5^〇 85. It is also preferred that the crystallized glass for the positive electrode material of the lithium ion secondary battery of the present invention contains SiO 2 + V 2 〇 5 + secret + Ge 〇 2 + in a molar percentage.

Al2〇3 + Ga2〇3 + Sb2〇3 + Bi2〇3 0%~2.4%.车乂佳 is in the crystallized glass for the positive electrode material of the lithium ion secondary battery of the present invention in the 'mole ratio' [sand (P2〇5 + Fe2G3 + Mn02/2) S, 12 201226354 is 0.5 m or more . In the crystallized glass for a positive electrode material for a lithium ion secondary battery of the present invention, Ll2〇/P2〇5 is 0.85 or more. In the crystal material of the positive electrode material for lithium ion secondary battery of the present invention, Lr2〇/(Fe2〇3 + Mn〇2/2) is 0.85 =, the clock ion of the invention The range of the crystallized glass crucible for the secondary battery positive electrode material and the reason for the limitation thereof can be suitably applied to the above-mentioned lithium ion-exclusive precursor glass (10), which is the crystallized glass for the positive electrode material for the ion secondary battery. r 2:r5〇%' ^^ Fe2〇f〇n; 0: zt =〇%'Nb2〇5〇%~2.4%, and Li2〇/P2〇5Sioi. In the $I', the content of each component, I, 3, ^, etc., can be applied to the above. MW® and the reason for limitation are heterozygous "secondary battery positive electrode material (4) crystallized glass containing ν < Γ = Hx + y) P 〇 4 crystal (〇 1, 〇 ¥ 1, 0 < X + as the main crystal. At least the type of milk is more than UMnxFeyMl. The content of P〇4 crystal is 5〇, and it is more than 2 F λΓ%, especially 9〇_. If the content of the crystal is too small, the ionic conductivity becomes too small. It is difficult to obtain a high battery capacity. In addition, the upper limit is not particularly limited to 201226354, and is actually 99.9 wt% or less, particularly 99 wt% or less.

The smaller the crystal grain size of the LiMnxFeyMi-a+ePO4 crystal, the smaller the particle size when the crystallized glass is powdered, and the conductivity can be improved, and the surface is LiMnxFeyMi_(^ The crystal grain size of the p〇4 crystal is 1 〇〇 nm or less, particularly 8 Å or less. The lower limit is not particularly limited, and is actually 1 nm or more, particularly j U) two or more. Further, the crystal size of the LlMnxFeyMi (x+y)p〇4 crystal can be determined according to the Scherrer's formula based on the analysis result of the powdered ray diffraction of the crystallized glass powder. σ is a powdered glass of a positive electrode secondary battery. On the other hand, the surface area as a whole of the positive electrode material becomes large, and exchange of ions or electrons is facilitated. It is preferable that the flattened diameter of the crystallized glass powder for the positive electrode material of the clock ion secondary battery is 5 or less, which is 20 μm or less. Regarding the lower limit, the inconsistency is 0.05 μm or more. Brother = /, there are known SI phase reaction methods or hydrothermal synthesis methods. In these methods, neutrons have the following problems: it is easy to mix magnetic particles such as metal iron to form a dendritic crystal by charging and discharging, which is a cause of short circuit. . In addition, by the glass melting method, the positive electrode = rMX + y) PQ4 street which can be melted and melted by metal smelting, 嶋嶋 homogeneous and dense body glass: = 2 _ _ _ sub-secondary battery positive electrode material precursor The glass 1 is produced by a manufacturing method including the following steps: a step of adjusting the raw material powder by the method of breaking the glass group 201226354, and containing U2 〇 20% 〜 50%, P2 〇 5 20% by the percentage of the mole % 40%, Fe2〇3 〇〇/. ~ 40%, Μιι02 〇%~60%, Nb2〇5 0.1%^~2.4% ' and Mohr ratio & ten' (Fe2〇3 + Mn〇2/2) /Ρ2〇5 2〇·85; a step of melting the raw material powder to obtain molten glass; and a step of quenching the molten glass. Further, the precursor glass for a positive electrode material for a lithium ion secondary battery can be further subjected to heat treatment to be crystallized, whereby a crystallized glass for a positive electrode material for a lithium ion secondary battery can be obtained. In addition, the valence of Fe and Μη in the crystal of LiMr^FeyM^^PO4 is +2, so if it is melted for a long time in the open atmosphere, then the relationship between the self-oxidation-reduction equilibrium is easily oxidized to Η price and +4 price. Therefore, in order to control the valence state, it is preferred to add a reagent of +2 valence such as iron oxalate to the raw material when the precursor glass is used, or to add a reducing agent containing carbon such as glucose to the melting of the precursor glass; Further, a method of melting a reaction vessel which is excellent in airtightness of a reducing gas is also preferable. The crystallized glass can be made from the precursor glass by means of an electric furnace capable of controlling temperature and environment. Since the heat treatment temperature differs depending on the precursor glass = the target or the target grain size, it is not particularly flawed, and preferably = at least the glass transition temperature or higher, particularly the crystallization temperature. In the form of a film, it is preferred that the heat treatment temperature is 5 〇〇t or more. If the heat treatment temperature is too low, there is a enthalpy

The tendency of Si to be poor in electrical conductivity. On the other hand, the upper limit is not particularly limited, and if the right heat treatment temperature is too high, there is a crystallization of 结晶, so it is 15 201226354 1000 〇 C or less, particularly 950. 〇The following. Move, - near the production: two and other burns, that is, the precursor glass is transferred, the heat treatment is carried out for a certain period of time near the dish, and the second-stage calcination is carried out by heat treatment, thereby changing (2) uniform crystal grain Crystallized glass. It is paid to have a suitable heat treatment time to make the precursor glass of the precursor glass fully charged. Specifically, the heat treatment time is preferably 'σΒΘ, particularly 20 minutes to 40 minutes. Preferably, the environment is from 10 minutes to 60 minutes, and the heat treatment environment is preferably hydrogen, ammonia, and a river, thereby making it easy to obtain the olivine-type LiMnxF 1 and ^ ° x yM "(x + y) P 〇 4 crystal. ▲ When the organic binder is added to the heat treatment of the enamel glass, the valence of the molten iron is changed to +2 before the crystallization before the crystallization of the far-organic binder, so LiMnxFeyMi- can be obtained at a high content rate. (x+y) P〇4 crystals. Further, in order to improve conductivity, it is preferable to mix electrons with high conductivity and stable electrical conductivity with respect to the crystallized glass (IV). The conductive active material may, for example, be graphite or acetylene black. A carbon-based conductive active material such as amorphous carbon or a metal-based conductive active material such as metal powder. The amorphous carbon is preferably not detected in the FTIR analysis as a CO bond which causes a decrease in conductivity of the positive electrode material. Amorphous carbon having a peak or a peak of a CH bond. For example, it is preferred to carry out sintering in a state in which an interface of a crystallized glass powder is carried with a conductive active material. As a method of carrying a conductive active material at an interface of the crystallized glass powder, Column Conductive 201226354 ring precursor powder, such as glucose, carboxylic acid such as aliphatic carboxylic acid or aromatic carboxylic acid, or organic compound such as organic binder, is mixed and mixed, and is heat-treated in an inert precursor such as nitrogen. Residual conduction; the amorphous form of the active substance is 'an aliphatic tetamine can be listed with ethyl resin, polyethylene glycol, polycarbonate extension 2 base C-butyl §|, polymethacrylic acid B6, polymethyl propyl The dilute acid-guided thunder method can uniformly carry 'Bei' at the interface of the crystallized vitreous end. Moreover, the organic binder contributes to the two characteristics of the formation of the positive electrode material and the conductivity. That is, it becomes acceptable (4) It is formed into a sheet shape, and the crucible can be used as a positive electrode material for a battery without being pulverized again after calcination. It is preferable that the positive electrode material for a clock ion secondary battery of the present invention has a conductivity of 1.0 Χ 10·8 S · cm or more. i, 〇1〇·6 s · coffee] or more, particularly l, 〇xl 〇 -4 S · cm·1 or more. [Examples] Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto. These examples. Table 1 to Table 3 show examples of the present invention (sample N〇1~ Sample No. 19) and Comparative Example (sample n〇2〇 to sample n〇22) 17 201226354 [Table i] 1 2 3 4 5 6 7 8 9 10 Li2〇33.2 34.2 35.2 36.2 37.2 38.2 32.2 34.8 34.4 30.4 P2〇5 33.2 32.7 32.2 31.7 31.2 30.7 33.7 34.8 34.4 30.4 Fe2〇3 Mn〇2 33.2 32.7 32.2 31.7 31.2 30.7 33.7 29.9 30.7 38.7 Nb203 Si02 Al2〇3 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (Fe+Mn /2) /P 1.00 1.00 1.00 1.00 1.00 1.00 1.00 0.86 0.89 1.27 Li/ ( P+Fe+Mn/2 ) 0.50 0.52 0.55 0.57 0.60 0.62 0.48 0.54 0.53 0.44 Li/P 1.00 1.05 1.09 1.14 1.19 1.24 0.96 1.00 1.00 1.00 Li / (Fe+Mn/2) 1.00 1.05 1.09 1.14 1.19 1.24 0.96 1.17 1.12 0.79 Vitrification ο ο ο ο ο ο ο ο ο ο crystallization amount (%) 94.0 96.3 96.9 94.7 94.0 91.6 88.0 96.0 93.0 86.0 Discharge capacity (mwh/ g) 130 137 141 138 135 130 120 137 128 100 18 s 201226351 [Table 2] 11 12 13 14 15 16 17 18 19 Li20 34.5 34.5 34.5 24.8 26.8 32.4 30.4 29.1 28.8 P2〇5 31.6 31.6 31.6 24.8 23.8 30.9 28.9 28.1 27.3 Fe203 31.6 31.6 31.6 24.7 17.1 13,7 10.6 Mn02 49.8 48.8 11.7 23. 6 28.6 33.3 Nb2〇3 2.4 0.9 0.9 0.5 0.5 0.5 0.5 0.5 0.5 Si02 1.5 Al2〇3 1.5 (Fe+Mn/2) /P 1.00 1.00 1.00 1.00 1.03 0.99 1.00 1.00 1.00 Li/ ( P+Fe+Mn/2 ) 0.55 0.55 0.55 0.50 0.56 0.53 0.53 0.52 0.53 Li/P 1.09 1.09 1.09 1.00 1.13 1.05 1.05 1.04 1.05 Li/ ( Fe+Mn/2 ) 1.09 1.09 1.09 1.00 1.10 1.06 1.05 1.04 1.06 Vitrification 0 0 0 0 0 0 0 0 0 Crystallization amount (%) 93.0 93.5 92.8 92.0 96.0 92.0 91.0 90.0 88.0 Discharge capacity (mwh/g) 128 131 126 120 135 125 119 115 110 19 201226354 [Table 3] 20 21 22 Li20 30.3 26.9 29.0 p2〇5 38.3 38.6 29.0 Fe203 30.8 31.9 37.0 Μη02 Nb203 0.5 2.6 5.0 Si02 ai2〇3 (Fe+Mn/2) /P 0.80 0.83 1.28 Li/ ( P+Fe+Mn/2 ) 0.44 0.38 0.44 Li/P 0.79 0.70 1.00 Li/ ( Fe+Mn /2 ) 0.98 0.84 0.78 Vitrification 0 X 0 Crystallization amount (%) 70.0 80.0 Discharge capacity (mwh/g) 40 - 88 First, the glass raw materials are blended so as to have the respective compositions shown in Tables 1 to 3. Platinum is carried out for 1 hour at ll 〇〇 ° C to 1400 ° C. The molten glass is poured into a pair of forming members, and is formed into a film shape by quenching, whereby a precursor glass is produced. Thereafter, the precursor glass was pulverized in a ball mill to obtain a precursor glass powder having an average particle diameter of 2 μm. With respect to the precursor glass powder 100 201226354. 5 parts by weight of the mixed phenol resin (an equivalent amount in terms of graphite) and 15 parts by weight of ethanol as a solvent After forming into a sheet having a thickness of 5 Å by a doctor blade forming method, it was 80. (The following drying was carried out for about several hours. Next, the obtained sheet-like formed body was cut into a predetermined size, and subjected to heat treatment for 30 minutes in a nitrogen atmosphere to be crystallized. Thereby, a positive electrode material (sintered body of crystallized glass powder) was obtained. The content of LiMnxFeyM1 such as y)P〇4 crystal in the positive electrode material was measured by powder ray diffraction. Next, with respect to the obtained positive electrode material, the discharge capacity at a 0.1 C rate was evaluated by the following manner. The positive electrode material: the binder: the conductive material ^ is used to weigh the positive electrode material, the handle mixture is 7, the y chemical solution 2 2 >, as the conductive substance of the Ketjen black, the materials are dispersed in N_ ii = After r (NMP), the mixture was slurried by auto-rotation and revolutionary mixer charging. Secondly, the closing gap is 15G _. The material = the thickness of the positive body 1 body 2 () μιη purely coated by the coating of the middle, 28 (dry under rc, through a pair of spin The press machine ^u lt/em is pressed (9) to obtain the electrode sheet. By electrode = machine 3 sheet punching (four) straight through llmm, at 14. 〇 under the drying 6 J 呀 'get a round working electrode. The 18th surface of the differential electrode is placed on the button-type battery and placed under the machine for 8 hours under reduced pressure drying. The company ΪΓ6 _ contains polypropylene to the porous membrane (H-celanese ^Celgard) #2400) The separator, and as the opposite electrode 21 201226354

The metal clock is used to make a §-type battery. You Tian ^ μ T 伸乙# DEC (Ethylene carbonate 2 6 solution / EC (carbonation is carried out in the environment where the junction temperature is below 1C. The test battery is used, and the battery is charged by 2VM2VUC (value constant current). Charging (reducing ions from the positive electrode material), discharging it from 4.2 V to 2 V and discharging (dissolving ions in the positive electrode material), and measuring the discharge valley. The results are shown in Table 1 to Table 3. It can be seen from Table 1 to Table 3. The positive electrode material of the sample N〇1 to sample n〇19 as an example shows a good discharge capacity of 1 〇〇 mwh/g or more. The glass for the positive electrode material of the sample No. 20 and the sample No. 22 of the comparative example did not satisfy the predetermined glass composition, and the discharge capacity was as low as 88 mwh/g or less. Further, the sample No. 21 was not vitrified, so The discharge capacity is not measured. [Simple description of the diagram] Yiyi [main component symbol description]

S 22

Claims (1)

20122635^ VII. Scope of application for patents: 1. Precursor glass for the anode material of the ion-sub-battery, which is characterized by: as a glass contact, it contains a piece of material ~ 50/〇, P205 20/〇 ~40%, Fe2〇3 〇%~4〇%, Mn〇2 〇%~6〇0/〇, Nb205 0.1%~2.4% ' and in terms of molar ratio, (Fe2〇3 + Mn〇2/2 ) /Ρ2〇5$〇·85. 2. The precursor glass for a positive electrode material for a petal secondary battery according to claim 1, wherein the SiO2 + V205 + b2〇3 + Ge〇 is further contained in a percentage of moles. 2 + Al2〇3 + Ga2〇3 + %2〇3 + ΒΪ2〇3 0 3. For the positive electrode precursor glass of the chain ion secondary battery as described in claim 1 or 2, wherein Ear ratio meter, Li2〇/(P2〇5 + Fe203 + Mn02/2 ) $ 〇5. 4. The precursor glass for a positive electrode material for a clock ion secondary battery according to any one of the first to third aspects of the invention, wherein the molar ratio is Li2O/P2〇5^0.85 ' Li2 〇 / (Fe203 + Mn02/2 ) ^0.85 55. A precursor glass for a lithium ion secondary battery positive electrode material, characterized in that the glass composition 'containing Li2〇2〇% to 50/% by mole percentage 〇, P2〇5 20%~40%, Fe2〇3 〇%~4〇%, Mn〇2 〇%~6〇%, Nb2O50%~2.4%, and 莫1 in terms of molar ratio. 6. A crystallized glass for a positive electrode material for a lithium ion secondary battery, characterized in that it comprises, as a glass composition, Li2〇2〇%~50%, P2〇5 20%~40%, Fe2〇 as a percentage of moles. 3 〇%~4〇%, Mn〇2 〇%~6〇%, Nb2O50.1%~2.4%, and (Fe2〇3 + Mn〇2/2) /ρ2〇5^〇85. The crystallized glass for a positive electrode material for a lithium ion secondary battery according to claim 6, wherein the SiO 2 + V2 〇 5 + b203 + Ge02 further contains 〇% to 2.4% in terms of mole percentage. Α12〇3 + Ga203 + Sb203 + Bi2〇3 o 8. The crystallized glass for a positive electrode material for a chain ion secondary battery according to claim 6 or 7, wherein the molar ratio is Li20 / (P205 + Fe203 + Mn02/2) g〇.5. 9. The crystallized glass for a positive electrode material for a lithium ion secondary battery according to any one of claims 5 to 8, wherein the molar ratio is Li20/P2〇5g〇85, and/or Or Li2〇/(Fe2〇3 + Mn〇2/2) 85. - Crystallized glass for a positive electrode material for a clock ion secondary battery, characterized in that, as a glass composition, Li20 is contained in a percentage by mole of 20% to 5 〇 ° / 〇, P 2 〇 5 20% to 40%, and Fe 203 % ~40%, Μη02 0%~60%, Nb2〇5 〇%~2.4%, and Li20/P2〇5^l.〇l. 11. The crystallized glass for a positive electrode material for a clock ion secondary battery according to any one of claims 6 to 10, which contains 113^^]\41.(};+#〇4 Crystallization (〇$5^1, 〇^丫$1, 〇<又+ 丫^1, Μ疋 is selected from at least one of Nb, Ti, V, Cr, Co, and Ni) as the main crystal. The crystallized glass for a lithium ion secondary battery of the above-mentioned item, wherein the content of the LiMnxFeyMWx+y&gt;P04 crystal is 50 wt% or more. 13. A method for producing a lithium ion secondary battery positive electrode material , which is characterized by: 24 201226354^ The composition of glass is such that Li20 contains 20% to 50%, P205 20% to 40%, Fe203 0% to 40%, Μη02 0% to 60%, Nb2O50.1% to 2.4%, and a step of adjusting a raw material powder by a molar ratio (Fe2O3 + MnO2/2) / P2 〇 5 ^ 0.85; a step of melting the raw material powder to obtain molten glass; and quenching the molten glass to obtain The step of the precursor glass. 14. The method of producing a lithium ion secondary battery positive electrode material according to claim 13, further comprising the step of thermally treating the precursor glass to obtain crystallized glass. 25 201226354 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None 0 201226354 4uyyzpiii __ is the Chinese manual of No. 100146243 without a slash correction. Date: 1 February 2 23 | Invention patent specification - ( Please do not change the format and order of this manual. Please do not fill in the ※ part. ※Application number: ※Application date·Classification: 1. Name of the invention: (Chinese/English) Precursor for positive electrode material for lithium ion secondary battery Glass and Lithium Ion Secondary Battery Cathode Glass PRECURSOR GLASS FOR ANODE MATERIAL OF 〇^ LITHIUM IONIC SECONDARY CELL AND CRYSTALLINE GLASS FOR ANODE MATERIAL OF LITHIUM IONIC SECONDARY CELL II. Abstract: A lithium ion secondary battery cathode material The precursor glass is characterized in that, as a glass composition, Li20 is contained in a percentage by mole of 20% to 50%, P2〇5 is 20% to 40%, Fe203 is 0% to 40%, and Μη02 is 0% to 60%. The order is 2〇50.1%~2.40/0, and in terms of the molar ratio, he 〇3 + ]^11〇2/2) /P2〇5^〇.85 ° A precursor glass for an anode material of a lithium ionic secondary cell is characterized in containing 20 mole% to 50 mole% of Li20, 20 mole% to 40 mole% of P2O5, 〇mole% to 40 mole% of Fe203, 0 Mole% to 60 mole% of 201226354 4〇992pifl Revision date: February 23, 2003 Stomach and stomach 100146243 Chinese manual without sizing corrections 6. Description of the invention: [Technical field of invention] The present invention relates to a portable The front can glass for a positive electrode material for a rotor secondary battery used in an electronic device or an electric vehicle, and the crystallized glass for a positive electrode material of a clock ion secondary battery. [Prior Art] The petal secondary battery has established a position as a high-capacity, lightweight power source which is indispensable for a portable electronic terminal or an electric vehicle. Among the positive electrode materials for the secondary battery of the valve, an inorganic metal oxide such as a building (Lic〇〇2) or a eucalyptus clock (LiMn〇2) has hitherto been used. However, with the increase in power consumption caused by the high performance of electronic devices in recent years, it is required to increase the capacity of the ion secondary battery. Moreover, from the perspective of environmental preservation or this source issue, it is required to be from C. Materials that are environmentally burdened, such as Μη, are converted into more environmentally compatible materials. In addition, in recent years: Drilling resources __ correction, from this axis considerations, Qianwang converted to cheap cathode material instead of lithium cobalt oxide or lithium manganate. In the right years, it is beneficial to consider the cost and resources. In the compound of the 3rd bell, the spinel crystal, the NASICON type, and the -.曰曰 (Ll3Fe2(P〇4)3) and olivine-type sputum (uFep〇4) have been paid attention to, and various studies and developments have been made (for example, refer to Japanese Patent Laid-Open No. II34725). The towel's stalk stone type crystal is more excellent in the degree of service than the bell, and can be expected to operate safely at high temperatures. Further, since Wei is a structure of the skeleton, the charge and discharge reaction is recorded, so that the structural deterioration is excellent. 201226354 4U992pitl Revision date··February 23, 2011 is No. 100146243 Chinese manual No picture [J line correction this other 'known manganese manganese spinel type, NASICON type and sapphire type crystal The site can be replaced by various transition metal ions. For example, Li3, which is completely replaced by manganese or vanadium, is replaced by Li3Mn2 (;P04)3, LiMnI&gt;C)4, LiVP〇4, etc., which is partially replaced by manganese or vanadium Li3 (MnxFeyV1.(x+y)) 2(P〇4)3 &gt; LiMnxFe(ix)P04 ( 0 &lt; χ &lt; 1 λ 〇 &lt; y &lt; l, 0 &lt; x + y &lt; l) and the like also have a function as a positive electrode material. In the above, it is known that when a conductive active material such as carbon powder is mixed in the positive electrode material, the electron conductivity is improved. However, when the lithium iron phosphate cathode material is mixed and the conductive active material is mixed and calcined, the conductive active material cannot be efficiently activated on the surface of the iron phosphate clock particles due to the influence of the gas generated from the lithium iron phosphate cathode, and the electron conductive material is electrically conductive. The problem of reduced degrees. Therefore, a lithium iron phosphate material containing crystallized glass has been proposed as a positive electrode material in which a small amount of gas is generated during calcination (see, for example, Japanese Patent No. 2-9-93733). The precursor (4) is substantially free of gas when it is mixed with the carbon powder conductive active material to be calcined. Therefore, the conductive active material can be efficiently activated on the surface of the positive electrode material particles, and excellent electron conductivity can be easily achieved. Further, by calcining the precursor _, a crystallized glass powder having a uniform crystal grain size and having a small crystal grain size, or a crystallized glass powder filled with a solid solution crystal, can be obtained. Sub-secondary battery cathode material. As described above, the positive electrode material which is excellent in __ as described in JP-A-2009-87933 is used. ^ The positive electrode material described in Japanese Patent No. 2_87933 is issued by the Japanese Patent No. 2_-87933. The date of revision is: 201212354 40992pifl Revision Date: February 23, 2011 No. 100146243 Chinese Manual No line correction The battery capacity of the new battery is big change. The current state of 'the most adequate battery capacity' in the publication of the Japanese Patent Publication No. 2(8793) is not yet proposed as a positive electrode material having a high battery capacity. SUMMARY OF THE INVENTION The present invention is based on the fact that the battery ion of the battery capacity is high in view of such a situation, and the purpose is to obtain a crystal for the positive electrode material of the sub-battery: the _ body glass glass is used. The material used for precursor curry ~5〇%, ρ2〇5 2 g to f percentage includes 〇%-60〇/〇. Nb2〇5 〇.1〇/_2 4〇^〇/〇' Fe^ 〇%^ 40〇/〇. Mn〇2 Μη02/2) /Ρ2〇5^〇·85. ° In terms of the molar ratio, (Fe203 + has the above-mentioned composition of the front surface, it can be made into an ancient drive glass) means: by ^; pole material. In addition, the glass of the Qi. The precipitation of the target crystal precursor glass is the lithium ion secondary battery positive electrode material. The above components are used to break the _ heart 2 ^ Sb2 〇 3 + Bl2 〇 3. Some components are easily obtained by breaking the b component. Adding the heterogeneous crystal, the battery capacity Gub # b stable, difficult to precipitate the undesired: r, θ W lithium ion secondary battery cathode material. The lithium ion secondary battery cathode material 201226354 40992pifl No. 100146243 Chinese manual without slash correction This revision period: January 20, 2011 Li20/ (P2〇s + Fe2〇3 + in precursor glass, in molar ratio, Mn02/2) -0.5 With this configuration, undesired heterogeneous crystals and materials are obtained. The battery capacity is high. Fourth, it is preferable that in the precursor glass for a positive electrode material for an ion secondary battery of the present invention, in terms of a molar ratio, Li2〇 /P2〇5^85, and/or Li20/ (Fe2〇3 + Mn02/2) ^0.85 ° With this configuration, it is easy to obtain a lithium ion secondary battery positive electrode material which is stable in vitrification, is difficult to precipitate, and has a high battery capacity. The fifth aspect of the present invention relates to a silver ion. A precursor glass for a secondary battery positive electrode material, characterized in that, as a glass composition, Li20 20% to 50%, P2O5 20% to 40%, Fe203 0% to 40%, Μη02 〇% to 60% by mole percentage %, Nb205 0%~2.4%, and in terms of molar ratio, Li20/P2〇5^l.〇i. The sixth invention relates to a crystallized glass for a positive electrode material for a ionic secondary battery, characterized in that : as a glass composition, containing Li20 20%~50%, P2〇5 20%~40%, Fe203 〇〇/〇~40%, Μη02 0%~60%, Nb205 0.1%~2.4%, based on the percentage of moles. And (Fe203 + Μη02/2) /Ρ2Ο5^0·85. Seventh, it is preferable that the crystallized glass for the positive electrode material of the ion secondary battery of the present invention contains 0% to 2.4% of SiO 2 in terms of the percentage of moles. + V2O5 + B2O3 + Ge〇2 + Al2〇3 + Ga2〇3 + Sb2〇3 + Bi2〇3. 7 201226354 40992pifl Date: February 23, 101 is the Chinese manual of No. 100146243. The eighth paragraph is not modified. The preferred embodiment is the lithium ion secondary crystallization glass of the present invention, in terms of molar ratio, 4 ^ ^ Mn02/2) ^0.5. 5 2U3 + ninth' is preferably a crystallized glass for the positive electrode of the ion secondary battery of the present invention, in terms of molar ratio, Ll2〇/P2 (^a85, and Li2〇/(Fe2〇3 + Mn02) /2) ^0.85° Tenth, another aspect of the present invention relates to a crystallized glass for a secondary positive electrode material, characterized in that, as a glass composition, Li2〇20%~5 is contained in a percentage of moles. 〇%, p2〇5 2〇%~4〇%, Fe2〇3 〇%~40%, Μη02 〇%~6〇%, Nb2〇5 〇%~2 4%, 〇Li20/P2〇5gl_〇l '〇' and tenth-, preferably, the crystallized glass for the positive electrode of the clock ion secondary battery of the present invention contains LiMr^FeyMi-^PO4 crystal 〇 each ySl, 0 &lt; x + y^l, Μ is selected from At least one of Nb, Ti, v, Cr, 〇, and Ni is used as a main crystal. Further, the twelfth, preferably, the positive electrode material of the ion secondary battery of the present invention has a crystal content of LiMnxFeylV^x+ePO4 in the crystallized glass of 5 〇% or more. Thirteenth, the present invention relates to a method for producing a positive electrode for a plasma ion secondary battery, comprising the steps of: adjusting a raw material powder by a glass composition in such a manner as to contain Li2〇2〇〇 in terms of a percentage of moles / 〜50%, P2〇5 20%~40%, Fe203 〇〇/〇~40%, Mn〇2 〇%~0 60%, Nb205 0·1%~2.4% ' and in terms of molar ratio, ( Fe2〇3 + M2n〇: /Ρ2〇520·85 ; The step of melting the raw material powder to obtain the molten glass $$201226354 4uyy2piti mm 100146243 Revision date: February 23, 101 and the melting _ quenching Step of the glass. The steps of the process are the preparation of the positive electrode material of the secondary battery of the modified secondary battery. The heat treatment is performed on the precursor surface to obtain the crystallized glass. [Preparation] The precursor glass for the positive electrode material of the lithium ion secondary battery is used. As a glass composition, it contains Li2〇20%~5〇%, P2〇5 20%~40%, Fe2〇3 〇%~4〇%, Mn〇2 〇%~6 in terms of the percentage of moles. 〇%, N 2〇5&gt;0.1/〇~2.4%, and in terms of molar ratio, (r at + Mn〇2/2) /Ρ2〇5 $ 〇·85. The reason why the composition is limited to the above is explained as follows. The main component of the crystal of Ll2〇疋LiMnxFeyMHx+y/O4 is preferably 20%~50%, 25%~45%, 30%~ 40%, 33%: 37%, especially 33.5%~37%. If the content of Li20 is too small, the precipitation of LiMnxFeyMi-^+^PC^ crystals becomes difficult to obtain a high battery when crystallizing the moon/body glass. On the other hand, if the content of Li20 is too large, it is easy to precipitate undesired heterogeneous crystals (Li3p〇4, 〇Lsl3(MnxFei-x)2(P〇4)3, etc.), and as a result, LiMnxFeyMHxiPC^ The precipitation amount of the crucible is small, and it is difficult to obtain a high battery capacity. Ρζ〇5 is also a main component of LiMnxFeyMHX+y)P〇4 crystal. Preferably, the content of P2〇5 is from 2% to 40%, from 5% to 35%, from 28% to 35%, from 29% to 33%, and particularly preferably from 29.5% to 32.5%. When the content of P2〇5 is outside this range, it is easy to precipitate undesired crystals when the precursor glass is crystallized. As a result, the amount of precipitation of crystals is small, and it is difficult to obtain a high battery capacity. 9 201226354 40992pifl is the Chinese version of the 100146243 without a slash correction. Revision date: February 23, 2011. Fe2〇3疋LiMnxFeyMi_(x+y)P〇4 crystal constituents. Preferably, the content of Fe2〇3 is 〇% to 40%, 10% to 4%, 20% to 35%, particularly 30% to 35%. When the content of Fe2〇3 is too large, it becomes easy to precipitate undesired heterogeneous crystals when the precursor glass is crystallized. As a result, the amount of precipitation of LiMnxFeyMi^x+yfO4 crystals is small, and it is difficult to obtain a high battery capacity. Further, FeO or pe3〇4 may be used as a raw material, and in this case, the amount converted to Fe2〇3 may satisfy the above range. Similarly to Fe2〇3, Mn〇2 is a constituent of LiMnxFeyMHx+y)P04 crystal. Preferably, the content of Νίη〇2 is 〇%~6〇%, 20%~55%, 30%~55%, 40%~55%, especially 45%~50%. If the content of Μη〇2 is too large, it becomes easy to precipitate undesired heterogeneous crystals when the precursor glass is crystallized. As a result, the amount of precipitation of LiMnxFeyMHx+y)P〇4 crystals is small, and it is difficult to obtain a high battery capacity. Further, Mn 〇 or the like may be used as a raw material, and in this case, the amount converted to Mn 〇 2 may satisfy the range. Potassium) 5 is a component which improves the glass forming ability of the precursor glass. By actively adding Nb2Q5, it is easy to obtain a positive electrode with high battery capacity. Nb2〇5^^*4 〇, 〇/〇.2&gt;4% ^ 〇25〇/_2 3% ^ /〇~2%. However, if the content of Nb2〇5 is too much, it will be difficult to lick the same battery capacity.乂熳 较 = = = 莫 计 = = = ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The specification has no underline repair date: February 23, 2011 / P2〇5 is too small, it becomes easy to precipitate undesired heterogeneous crystals in the crystal of the precursor glass. It is difficult to obtain high electric ground capacity. The upper limit is not particularly limited, and in order to precipitate a sufficient amount of LiMnxFeyMl-(x+y)p〇4 crystal, it is preferably 2 or less, particularly preferably 1.5 or less. Further, as a component for improving glass forming ability, in addition to Nb205 In addition, SiO2, v2〇5, b203, Ge02, Al2〇3, Ga203, Sb203, Bi2〇3 〇 may be added in a total amount of 〇% to 2.4%, particularly 0.1% to 2.3%. When the content of these components is too large, it becomes easy to precipitate undesired heterogeneous crystals when the precursor glass is crystallized, and it is difficult to obtain a high battery capacity. It is preferable that the precursor glass for a positive electrode material for a lithium ion secondary battery of the present invention has a molar ratio of 'Li20/(P2〇5 + Fe2〇3 + Mn〇2/2) of 0.5 or more, particularly 0.52 or more. When Li2〇/(P2〇5 + Fe2〇3 + Mn〇2/2) is too small, it becomes easy to precipitate undesired heterogeneous crystals when the precursor glass is crystallized, and it is difficult to obtain a high battery capacity. Further, the upper limit is not particularly limited, and it is preferably 1 or less, particularly 0.8 or less, in order to precipitate a sufficient amount of LiMnxFeyMi p@4 crystal. Preferably, in the precursor glass for a positive electrode material for a clock ion secondary battery of the present invention, in terms of a molar ratio, the secret/execution is G or more, Q 9 or more, 1 22, and particularly 1 G1 or more. If Li2〇/P2〇5 is too small, it will become the second. = Undesirable heterogeneous knots will be formed when the body glass crystallizes. In addition, it is fixed for the purpose of the scale, in order to precipitate the other than 1.5. Preferably, it is used in the precursor of the positive electrode material for the secondary battery of the present invention. 11 201226354 40992pifl Correction period: January 1, 23, 2011, No. 100146243 Chinese manual without scribe line correction in the body glass The LhO/(Fe2〇3 + Mn02/2) is 0.85 or more, particularly 0.9 or more. When Li20/(Fe2〇3 + Mn〇2/2) is too small, it becomes easy to precipitate undesired heterogeneous crystals when the precursor glass is crystallized, and it is difficult to obtain a high battery capacity. Further, the upper limit is not particularly limited, and in order to precipitate a sufficient amount of LiMiixFeyMHxiPO4 crystal, it is preferably 2 or less, particularly 1.5 or less. The other aspect of the precursor glass for a positive electrode material for a lithium ion secondary battery of the present invention is characterized in that, as a glass composition, Li 2 〜 20% to 50%, P 2 〇 5 2 G % Å, 〇 % 〜 % by mole percentage 60%, Nb2〇5 〇%~24%, and Ll2(10)2〇5m in the range of the molar ratio, the preferred range of the content of each component, the reason for limitation, and the like can be applied. The hybrid secondary battery of the present invention is exemplified by the use of precursor glass for the secondary battery positive electrode material to be calcined by the precursor glass. In the case of % of moles, it contains ~ -2 〇 5 〇〇 / ^ 60% '. Preferably, the glass of the present invention is ridiculous: crystallization of human battery cathode material Al2 〇 3 + Ga 〇: it £^# Sl〇^V205 + B2〇3 + Ge〇2 + ^ 2 3 + Sb2〇3 + Bi2〇3 〇〇/0~2.4〇/〇.破 =1 ================================================================================================================== The date of the 100,146,243 medium-sized book without a slash correction is 0.5 or more. In the crystallized glass for a positive electrode material for a secondary battery of the present invention, Li2〇/P2〇5 is 〇85 or more. In the crystallized glass for a positive electrode material for a secondary battery of the present invention, Li2Q/(Fe2C^M (4) or more in terms of a molar ratio. About the crystallized glass for a positive electrode material for a rotor secondary battery of the present invention The composition range of the bismuth and the reason for the limitation can be applied to the preferred composition range of the precursor glass for the secondary battery positive electrode material and the reason for the limitation. The lithium ion secondary battery positive electrode of the invention. The other sorrow of the crystallized glass for materials is characterized by: as a glass composition, L〇i2〇20/.~50%, p2〇5 20%~40%, Fe2〇3 〇%~ as a percentage of moles. 40%, Μη02 ～60%, Nb2 〇5 〇%~2 4%, and (10)/(9) 〇 In this form, the above-described range of the preferred range of the content of each component, the reason for limitation, and the like can be applied. Preferably, the crystallized glass for the positive electrode material of the lithium ion secondary battery contains iMnxFeyMi-(x+y)P〇4 crystals (〇Sx$l, OSygi, 〇&lt;χ + d, Μ is selected from Nb, Ti , at least one of V, Cr, Co, and Ni) is the main crystal. It is more than 疋LiMiixFeyMijx+e The content of the PO4 crystal is 5 〇 wt% or more, 7 〇 wt% or more, and particularly 90 wt 〇 / 〇. If the content of the LiMnxFeyMiA + eO4 crystal is too small, the ionic conductivity becomes insufficient, and it is difficult to obtain a high battery capacity. In addition, there is no special limit for the upper limit. 201226354 40992pifl is the Chinese version of the No. 46243, which has no underline correction. The date of this revision is February 23, which is actually 99.9% wt% or less, especially 99 wt°/ The smaller the crystal grain size of the LiMi^FeyM^+wPO4 crystal, the smaller the particle size when the crystallized glass is made into a powder, and the conductivity can be improved. The crystallite size of the LiMnxFeyMi_p〇4 crystal is preferably 100 nm or less, particularly 8 Å or less. The lower limit is not particularly limited, and is actually 1 nm or more, particularly 10 run or more. In addition, UMn^ The grain size of the ^Mw+^O4 crystal can be determined according to the Scherrer formula of the powdered ray diffraction of the crystallized glass powder. It is difficult to use the crystallized glass for the positive electrode material of the rotor secondary battery as a powder. This makes it The surface area of the positive electrode material becomes larger, and it becomes easier to exchange ions or electrons. (4) The average particle diameter of the crystallized glass powder for the positive electrode material of the hybrid secondary battery is 5 〇 or less, and % _ := is 2 〇ΡThe following. The lower limit 'is not particularly limited, and the current 疋0.05 μηι or more. ^ LiMnxFeyM, (x+y)P〇4Maa^s Known solid phase reaction method or hydrothermal synthesis method, Medium: anti-C: It is easy to mix magnetic particles such as metal iron as impurities, and it is difficult to form a hard crystal by the electric charge of j, and the reason for the light road is to make the metal iron concrete by the glass melting method. In other words, the lithium ion secondary power of the present invention can be manufactured by the method including the following steps: two materials = 14 201226354 4uyy2piti is the Chinese manual of the number 100146243 without a slash correction. The revision date is: February 23, 2011. The step of adjusting the raw material powder in the following manner includes Li2〇2〇〇/0~50%, p2〇5 20%~40%, Fe2〇3 0%~4〇%, Mn〇2 as a percentage of moles. 〇%~60%, Nb2〇5 0.1%~2.4%, and with molar ratio (1 (_Fe2〇3 + Mn〇2/2) /P2〇52〇·85; a step of melting the raw material powder to obtain a molten glass; and a step of quenching the molten glass. Further, the precursor glass for a lithium ion secondary battery positive electrode material may be further subjected to heat treatment to be crystallized, whereby a crystallized glass for a positive electrode material for a lithium ion secondary battery can be obtained. In addition, the original J price of Fe and the crystallization of LiMnxFeyMHx+yfC^ crystals is +2, so if it is in the open atmosphere for a long time: ^, considering the meaning of the redox balance, the pure oxidation is 仏= and +4 price. Therefore, in order to control the valence state of the valence, it is preferred to add a reagent of +2 valence such as iron oxalate to the raw material of the glass, or to add a reducing agent containing carbon such as glucose to the precursor of the fused silica: A method of reacting with a gas-filling property which is excellent in airtightness of a reducing gas is also preferable. The crystallized glass is produced by the electric radiation of the temperature and the environment. The heat treatment temperature 』 = or the target crystal grain size varies, so there is no particular limitation = ^ 疋 ί less than the glass transition temperature, especially the crystallization temperature or higher. And 5, it is preferred that the heat treatment temperature is 5 Torr. 〇 Above, especially % If the heat treatment temperature is too high, in the case of crystallization == is 15 201226354 40992pifl Revision date: 1 2 1 February 23 No. 46243 Chinese manual No face correction This 1000 ° C or less, especially 95 (rc or less. In addition, by performing two-stage calcination, that is, the precursor glass is subjected to reduction in the vicinity of the glass transition temperature for a certain period of time, the second-stage calcination of the heat treatment is progressed near the crystallization temperature, thereby changing It is easy to obtain a crystallized glass having a uniform crystal grain size. The heat treatment time can be appropriately adjusted to sufficiently carry out crystallization of the precursor glass. Specifically, the heat treatment time is preferably from 10 minutes to 60 minutes, particularly 20 minutes. ~4〇 minutes. “The environment for heat treatment is preferably a reducing environment such as hydrogen, ammonia, carbon monoxide, etc. By this, a crystal of LiMnxFeyMl.(x+y)P〇4 is obtained. ▲If heat treatment is applied to the precursor glass When an organic binder is added, the amount of iron in the glass is diamonded to +2 ' before crystallization, so that LlMnXFeyMHX+y can be obtained at a high content rate. P〇4 crystallization. In order to improve the conductivity, it is preferable to mix the electron-conducting ancient gorilla--the middle of the mouth, the mouth and the day, and the m% conductive active material f. The active or metal is a carbon-transferred active material such as acetylene black or amorphous carbon = ΐ"conductive active material f or the like. The amorphous carbon is preferably a knife, and the amorphous carbon which becomes the conductivity of the positive electrode material due to the gold value or the peak value of the ruthenium bond is not detected on the product. The activity is carried out at the interface of the crystallized glass powder. Conductive surface ====.=The boundary of the crystallized glass powder is scented with sulphuric acid; organic compounds such as organic binders, etc. Conductive 16 201226354 W^Zpitl is the Chinese manual of W0146243 without a slash correction. February 23rd.....卞z&quot;t The active substance is added to the precursor of the broken glass powder human environment or hydrogen, ammonia, carbon monoxide in the helium gas, the precursor powder, the crystallization of the powder, and heat treatment in the crucible Residual = amorphous terminal interfacial adhesive of a conductive active material may be, for example, a resin, an acrylic acid, an organic cellulose, or the like. Examples of the acrylic resin include butyl acrylate, polymethyl methacrylate, and polymethyl propylene. By the method, the acid can uniformly carry the conductive active material f at the crystallization-powder interface. Moreover, the organic binder contributes to the two characteristics of the forming of the positive electrode material, that is, it becomes easy. Formed into pieces It is also possible to use it as a positive electrode material for a battery without re-pulverization after calcination. It is preferable that the positive electrode material for a lithium ion secondary battery of the present invention has a conductivity f of ^10-8 S · cm·1 or more and 1.0 X KT6. s · cnr1 or more, especially ◎ 疋i.oxio-4 s.cm-i or more. [Examples] Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the examples. Table 1 to Table 3 show Examples of the present invention (sample No. i to sample No. 19) and comparative examples (sample Νο·2〇 to sample No. 22) 17 201226354 40992pifl No. 100146243 Chinese manual without sizing correction of this correction Date of the year February 23 [Table 1] 1 2 3 4 5 6 7 8 9 10 Li20 33.2 34.2 35.2 36.2 37.2 38.2 32.2 34.8 34.4 30.4 P2〇5 33.2 32.7 32.2 31.7 31.2 30.7 33.7 34.8 34.4 30.4 Fe203 Mn〇2 33.2 32.7 32.2 31.7 31.2 30.7 33.7 29.9 30.7 38.7 Nb203 Si02 A1203 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (Fe+Mn/2) /P 1.00 1.00 1.00 1.00 1.00 1.00 1.00 0.86 0.89 1.27 Li/ ( P+Fe+Mn/ 2) 0.50 0.52 0.55 0.57 0.60 0.62 0.48 0.54 0.53 0.44 Li/P 1.00 1. 05 1.09 1.14 1.19 1.24 0.96 1.00 1.00 1.00 Li/ (Fe+Mn/2) 1.00 1.05 1.09 1.14 1.19 1.24 0.96 1.17 1.12 0.79 Vitrified 〇ο ο ο ο ο 〇ο ο 〇 Crystallization (%) 94.0 96.3 96.9 94, 7 94.0 91.6 88.0 96.0 93.0 86.0 Discharge capacity (mwh/g) 130 137 141 138 135 130 120 137 128 100 18 201226354 4,2pitl No. 100146243 Chinese manual without slash correction This revision date: 丨〇1年23月23 Day [Table 2] 11 12 13 14 15 16 17 18 19 Li20 34.5 34.5 34.5 24.8 26.8 32.4 30.4 29.1 28.8 p2〇5 31.6 31.6 31.6 24.8 23.8 30.9 28.9 28.1 27.3 Fe203 31.6 31.6 31.6 24.7 17.1 13.7 10.6 Mn02 49.8 48.8 11.7 23.6 28.6 33.3 Nb203 2.4 0.9 0.9 0.5 0.5 0.5 0.5 0.5 0.5 Si02 1.5 Al2〇3 1.5 (Fe+Mn/2) /P 1.00 1.00 1.00 1.00 1.03 0.99 1.00 1.00 1.00 Li/ ( P+Fe+Mn/2 ) 0.55 0.55 0.55 0.50 0.56 0.53 0.53 0.52 0.53 Li/P 1.09 1.09 1.09 1.00 1.13 1.05 1.05 1.04 1.05 Li/ ( Fe+Mn/2 ) 1.09 1.09 1.09 1.00 1.10 1.06 1.05 1.04 1.06 Vitrification 0 〇〇〇〇〇〇〇0 Crystallization (%) 93.0 93.5 92, 8 92.0 96.0 92.0 91.0 90.0 88.0 Discharge capacity (mwh/g) 128 131 126 120 135 125 119 115 110 19 201226354 40992pifl No. 100146243 Chinese manual No picture correction date: February 23, 2003 [Table 3] —-- - ------ Li20 20 j----- 21 ------- 22 30.3 26.9 29.0 p2〇5 38.3 38.6 29.0 Fe203 30.8 31.9 37.0 Μη02 —----- Nb203 0.5 2.6 5.0 Si02 Al2 〇3 ------ (Fe+Mn/2 /P 0.80 0.83 1.28 Li/ (P+Fe+Mn/2) Li/P 0.44 0.38 0,44 Li/ ( Fe+Mn/2 ) 0.79 0.70 1.00 ^----- 0.98 0.84 0.78 Recycling 0 X 〇,·吉晶量(%) 70.0 - 80.0 ^ 1 Capacity 1 xnwh/g ) -------- 40 - 88 *When first, the way to become the components shown in Table 1 to Table 3 Adjust the glass material, use platinum ruthenium and let it shine underneath. The molten glass was poured into a pair of forming bars, and was formed into a film shape by rapid cooling, whereby the precursor was broken. Thereafter, the precursor glass was pulverized by a ball mill to obtain a precursor glass powder having an average diameter of 2 μm. Relative to the precursor glass powder powder 20 201226354 ^uyy/pirl Revision date: February 23, 2011 is the number 100146243 Chinese manual without the underline repair weight, 混合 mixed resin 5 parts by weight (in terms of graphite </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; After about 1 hour, the resulting shape is cut into a shape, and in a pure gas atmosphere, 80 (rcT = 3 〇 minutes 4 m heat _ is crystallized, # obtaining a positive electrode material, crystallization Sintered body of glass powder. The content of LlMnXFeyMl in the ruthenium cathode material is determined by powder χ ray diffraction. . The cathode material of the second is evaluated by the following method: positive electrode material: binder: conductive material = 85 : iq : 5 (weight is a positive electrode material, polyethylene as a binder, a substance of a substance) Qin black, the material is dispersed in the Ν_methyl 岭定^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^行;=== dry-pole sheet punching 2: electric == machine will be electric round working electrode. 々14 (^ under green for 6 hours, get below i'1 吏 working electrode _ face down The laminate containing the button-type battery is dried under reduced pressure at 60 ° C for 8 hours, and the public 包含 ϋ contains the porous film of polypropylene (Cel_#2_ manufactured by Η t t Cela As 201226354 40992pifl Revision date: February 23, 1st, February 1st, No. 100146243 Chinese manual, unlined metal lithium, making test battery. Your field] / electricity also. Use 1 M LiPF6 solution / EC (carbonated ethylene vinegar) ): (diethyl carbonate g: 1 : i as an electrolyte. The environment is tested under the dew point temperature Assembly of the pool. Use the test battery 'charged by 2 CC to 4.2 V CC (quirk current) charging (discharges lithium ions from the positive electrode material), and further discharges it from 4·2 V to 2 V to discharge ( The discharge capacity was measured by absorbing the ion in the positive electrode material. The results are shown in Tables 1 to 3. From Tables 1 to 3, the glass for the positive electrode material of the sample Ncu~sample Ν〇19 as an example is known. A good discharge capacity of 100 mwll/g or more was exhibited. On the other hand, the glass for the positive electrode material of the sample Νο. 20 and the sample No. 22 of the comparative example did not satisfy the predetermined glass composition, and the discharge capacity was as low as 88. Mwh/g or less. Further, since sample No. 21 was not vitrified, the discharge capacity was not measured. [Simplified description of the drawing] Benefits [Explanation of main component symbols] 益〇22 201226354 4uyyzpiii __ No. 100146243 Chinese manual without slash correction Date: 1〇1年23月23 | Invention patent specification - (The format and order of this manual, please do not change any more, please do not fill in the ※ part) ※Application number ※Application date·Classification: I. Name of the invention: (Chinese/English) Precursor glass for lithium ion secondary battery positive electrode material and crystallized glass for lithium ion secondary battery positive electrode material PRECRESOR GLASS FOR ANODE MATERIAL OF 〇^ LITHIUM IONIC SECONDARY CELL AND CRYSTALLINE GLASS FOR ANODE MATERIAL OF LITHIUM IONIC SECONDARY CELL II. Abstract: A precursor glass for a positive electrode material for a lithium ion secondary battery, characterized in that, as a glass composition, Li20 is contained in a percentage by mole of 20%. 50%, P2〇5 20%~40%, Fe203 0%~40%, Μη02 0%~60%, 〇2〇50.1%~2.40/0, and in terms of molar ratio, he 〇3 + ]^ 11〇2/2) /P2〇5^〇.85 ° III, English abstract: A precursor glass for an anode material of a lithium ionic secondary cell is characterized in containing 20 mole% to 50 mole% of Li20,20 mole % to 40 mole% of P2O5, 〇mole% to 40 mole% of Fe203, 0 mole% to 60 mole% of 201226354 ^^^?46243 Chinese manual without scribe correction This revision date: February 23, 1曰Μη02, and 0.1 mole% to 2.4 mole% of Nb2〇5, and (Fe2〇3 + Mn02/2 ) /P2O5 ^ 0.85 based on mole ratio. 201226354 40992pitl Revision date: February 23, 2011 is the 10014ffi43 No. Chinese manual, no marking correction. 7. Patent application scope: 1. Precursor glass for positive electrode material for ion secondary battery, characterized in that: as a glass composition, Li2〇2〇%~ 50 is included as a percentage of moles. %, P2〇5 20°/. ~40%, pe2〇3 〇%~4〇%, Mn〇2 〇%~6〇%, Nb205 0.1〇/〇~2.4〇/〇, and in terms of molar ratio, (Fe2〇3 + Mn〇2 /2) /P2O5 — 〇·85 〇〇 2. The precursor glass for a positive electrode material for a lithium ion secondary battery according to claim 1, wherein 'in terms of a percentage of moles, more than 2% to 2 4% of Si〇2 + V2〇5 + Β2〇 3 + Ge02 + Al2〇3 + Ga203 + Sb203 + Bi2〇3 0 3. The precursor glass for a positive electrode material for a lithium ion secondary battery according to claim 1, wherein Moh + Mn02/2 ) g〇.5. • The positive electrode of the ionization secondary battery described in the scope of the patent scope of the patent application is as follows: pre-service glass, towel, Molex, %(10)%, and domain Ll2〇/ (Fe2〇3 + Mn〇2 /2) (9) 85. Rotor secondary battery positive (4) miscellaneous glass, its special I is broken, containing Li2〇20%~ Nh Ο n〇/5 2〇/〇^4〇% 'Fe2〇3 〇%-% by mole percentage 40% ^ Μη02 0%-60°/〇' 〇 5(10)~2·4%, and called ear series, (10) / suction (four). The f-branch is in the ionic-under-battery cathode material for crystallized glass, which is 3〇%^p; 〇: 2^ 2〇5α1%~2.4%, and (efn〇/°~40° pure 0%~60%) , mound CFe203 + Mn02/2) / Ρ 205 ^ 〇 · 85. 23 201226354 40992pifl Revision date: January 23, 2011 is No. 100146243 Chinese manual without scribe correction. 7. The crystallized glass for lithium material as described in claim 6 of the patent application, wherein Eight ^ _ human battery positive thirsty _v2 〇 5 + B two Gf0 = f two f containing. Have. . /. ~ + Bi2〇3. ^Al2〇3 + Ga2〇3 + Sb2〇3 8· Crystallized glass for lithium ion two materials as described in claim 6, wherein, in terms of molar ratio, L 丄〇+ Μη02/2) ^ 0.5. 2〇3 9. For the towel, please use the crystallized glass for the positive electrode material of the rotor secondary battery described in item 6, wherein the molar ratio is Li2Q/P2 palpitations, and/or Li2〇/ ( Fe203 + Mn02/2) g〇.85. The surname λΛ〇 is a crystallized glass for the positive electrode material of the ion secondary battery, and the temple f is: as a glass composition, containing Li2〇20%~50%, P2〇5 2G%~4G%, Fe2 in terms of percentage of moles 〇3 G%~4G%, Mn〇2 〇%~6〇〇/〇, Nb2〇5〇%~2.4%, and secret/(10)(4)(1). The crystallized glass for a positive electrode material for an ion secondary battery according to any one of claims 6 to 1, wherein iMnxFeyMi-(x+y)P〇4 crystal +=made From at least one of Nb, Τι, V, Cr, c〇, and Ni), as the main, crystal 0. As described in the scope of the patent range, the sub-secondary battery is positively used for crystallized glass. Among them, the content of the above-mentioned Yuhe and the example p〇4 day is 50 wt% or more. 〇13· A method for producing a positive electrode material for a chain ion secondary battery, comprising: 24 201226354 40992pifl No. 100146243 Chinese manual without a slash correction This correction period: 1〇i year February 23 is made of glass Containing Li20 20%~50%, P2〇5 20%~40%, Fe203 0%~40%, Μη02 0%~60%, Nb205 〇.1〇/0~2.4%, and Mo a step of adjusting the raw material powder by means of (Fe203 + Mn02/2) / Ρ 2 〇 5 ^ 0.85, a step of melting the raw material powder to obtain molten glass, and quenching the molten glass to obtain a precursor The steps of the glass. 14. The method for producing a positive electrode material for a lithium ion secondary battery according to claim 13, which further comprises the step of subjecting the precursor glass to thermal crystallization to obtain crystallized glass. ',,, 25 201226354 40992pifl For the Chinese manual No. 100146243, there is no slash correction. Revision date: February 23, 1st, 2011. IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: No 0