JPH09147856A - Nonaqueous secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous secondary battery which is excellent in a charging- discharging cycle characteristic and by which high discharging voltage and high capacity can be realized by forming a negative electrode material of the battery out of an amorphous oxide mainly composed of Sn, Ge and Si. SOLUTION: A nonaqueous secondary battery is formed of a positive electrode material, a negative electrode material, nonaqueous electrolyte containing lithium salt or the like. In this secondary battery, the negative electrode material is formed of an amorphous oxide mainly composed of Sn, Ge and Si. For example, an amorphous oxide expressed by a formula: SnGea Sib M<1> c M<2> d Oe is used as this negative electrode material. In the formula, M<1> is at least one or more kinds of elements selected from Al, Pb, As, P and B, and M<2> is at least one or more kinds of elements selected from a first group element, second and third group elements and a halogen element in a periodic table. (a) represents the number of 0.001 to 2, and (b) represents the number of 0.001 to 1, and (c) represented the number of 0.2 to 2, and (d) represents the number of 0.01 to 1, and (e) represents the number of 1.3 to 11. In this nonaqueous secondary battery, a protective layer is arranged in a negative electrode and a positive electrode according to its necessity.

Description

[Detailed description of the invention]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous secondary battery with improved discharge capacity, charge-discharge characteristics such as charge-discharge cycle life, and improved safety.
The present invention relates to a non-aqueous secondary battery that is an amorphous oxide containing n, Ge and Si elements.

[0002]

2. Description of the Related Art Lithium metal and lithium alloys are typical negative electrode materials for non-aqueous secondary batteries. The dendritic metal itself is highly active and poses a risk of ignition. On the other hand, baked carbonaceous materials capable of intercalating and deintercalating lithium have recently come into practical use. The disadvantage of this carbonaceous material is that it itself is conductive, so lithium metal may deposit on the carbonaceous material during overcharging or rapid charging, eventually resulting in the deposition of dendrite metal. It will be. In order to avoid this, the charger is devised and the amount of positive electrode active material is reduced to prevent overcharging, but the latter method limits the amount of active material. Therefore, the discharge capacity is also limited. In addition, since the carbonaceous material has a relatively low density, the discharge capacity is limited in the double sense that the capacity per volume is low.

[0003] On the other hand, as a negative electrode material other than lithium metal, a lithium alloy, or a carbonaceous material, lithium is absorbed and used.
TiS ₂ , LiTiS ₂ (U.S. Pat. No. 3,983,476), transition metal oxides of rutile structure, such as WO ₂ (U.S. Pat. No. 4,198,47), which can be released
6) Spinel compounds such as Li _x Fe(Fe ₂ )O ₄ (JP-A-58-220362), electrochemically synthesized lithium compounds of Fe ₂ O ₃ (U.S. Pat. No. 4,46
4,447), a lithium compound of Fe ₂ O ₃
-112,070), _{Nb2O5 (} JP-B-62-59,
412, JP-A-2-824, 47), iron oxide, FeO,
_{Fe2O3 , Fe3O4} , cobalt oxide, _CoO , Co
₂ O ₃ , Co ₃ O ₄ (JP-A-3-291862, JP-A-6
-231765), amorphous V ₂ O ₅ (Japanese Unexamined Patent Publication No. 4-
223061), lithium-inserted low oxidation number metal oxides Li _x MO (M is Mn, Ti, Zn; JP-A-6-17);
6758), and the use of transition metal oxides in which the basic structure of the crystal is changed by inserting lithium ions as a negative electrode material (European Patent No. 0567149). Since all of these compounds have high redox potentials, 3 V
A non-aqueous secondary battery with a class high discharge potential and high capacity has not been realized.

[0004] An example using a negative electrode material mainly composed of divalent silicon (JP-A-6-325765, European Patent 058217
3, No. 0615296), but it has a drawback that the cycle life is extremely short. Examples of applying SnO and compounds based on SnO to negative electrode materials include JP-A-6-275268 and JP-A-6-338325.
In either case, it was impossible to obtain a cycle life that could be put to practical use.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to obtain a highly safe non-aqueous secondary battery which has improved charge-discharge cycle characteristics and which can realize a high discharge voltage and a high capacity.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to provide a non-aqueous secondary battery comprising a positive electrode material, a negative electrode material, and a non-aqueous electrolyte containing a lithium salt, the negative electrode material being Sn, Ge and Si.
can be achieved by a non-aqueous secondary battery characterized by comprising an amorphous oxide mainly composed of

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will now be described.
and a non-aqueous secondary battery comprising an amorphous oxide mainly composed of Si. 2. The negative electrode material has the general formula (1) SnGe _a Si _b M ¹ _c M ² _d O _e (1) (wherein M ¹ is at least one selected from Al, Pb, As, P, B Element M ² is at least one element selected from Group 1 elements, Group 2 elements, Group 3 elements, and halogen elements of the periodic table, a is a number of 0.001 or more and 1 or less, b is 0.001 or more 2 The following numbers, where c is a number of 0.2 or more and 2 or less, d is a number of 0.01 or more and 1 or less, and e is a number of 1, 3 or more and 11 or less. 2. The non-aqueous secondary battery according to 1 above, characterized in that: 3. The negative electrode material is represented by the general formula (2) SnGe _a Si _b M ³ _c M ⁴ _d O _e ( ² ) (wherein M3 is at least one element selected from Al, P and B; ^M4 is Li, K, Na, Rb, Cs,
At least one or more elements selected from Ca, Mg, Ba, Sc, Y and F; a is a number between 0.001 and 1. b is a number between 0.001 and 2; c represents a number from 0.2 to 2, d represents a number from 0.01 to 1, and e represents a number from 1, 3 to 11. 3. The non-aqueous secondary battery as described in 1 or 2 above, which is an amorphous oxide represented by 4. The non-aqueous secondary battery as described in any one of 1 to 3 above, wherein the negative electrode and/or the positive electrode have at least one protective layer. 5. The non-aqueous secondary battery as described in any one of 1 to 4 above, wherein the protective layer has substantially no electrical conductivity. 6. The non-aqueous secondary battery as described in any one of 1 to 5 above, wherein the particles contained in the protective layer are inorganic chalcogenite particles. 7. The non-aqueous secondary as described in 1 to 6 above, wherein the inorganic chalcogenite particles as described in 6 above contain at least one oxide of sodium, potassium, magnesium, calcium, strontium, zirconium, aluminum and silicon. battery. 8. The inorganic oxide according to 7 above is alumina, silicon dioxide,
8. The non-aqueous secondary battery according to any one of 1 to 7 above, which is made of zirconia. 9. The non-aqueous secondary battery as described in any one of 1 to 8 above, wherein the protective layer has a thickness of 1 μm or more and 40 μm or less. 10. The non-aqueous secondary battery as described in any one of 1 to 9 above, wherein the protective layer is formed on both the positive electrode and the negative electrode. 11. The non-aqueous secondary battery as described in any one of 1 to 10 above, wherein the protective layer is formed on the negative electrode. 12. The non-aqueous secondary battery as described in any one of 1 to 11 above, wherein the protective layer is formed on the positive electrode.

[0008] The technology of the present invention will be described in detail below. In the present invention, an amorphous oxide mainly composed of Sn, Ge and Si is used as a negative electrode material. Sn and Ge are present in amorphous solids, change their valences as they absorb and release lithium ions, and contribute to charging and discharging as functional elements. As a functional element, Sn alone exhibits excellent performance, but the coexistence of Ge can further improve the charge-discharge cyclability in particular. In addition, although Si is also present in the amorphous solid, it acts as an amorphous forming element and can realize even better charge-discharge cyclability. Among them, general formula (1) SnGe _a Si _b M ¹ _c M ² _d O _e (1) (wherein M ¹ is at least one element selected from Al, Pb, As, P and B, M ² is at least one element selected from the group 1 elements, group 2 elements, group 3 elements and halogen elements of the periodic table, a is a number of 0.001 or more and 1 or less, b is a number of 0.001 or more and 2 or less, c is a number of 0.2 or more and 2 or less, d is a number of 0.01 or more and 1 or less, and e is a number of 1, 3 or more and 11 or less.). Furthermore, the negative electrode material has the general formula (2) SnGe _a Si _b M ³ _c M ⁴ _d O _e ( ² ) (wherein M3 is at least one element selected from Al, P and B; ^M4 is Li, K, Na, Rb, Cs,
At least one or more elements selected from Ca, Mg, Ba, Sc, Y and F; a is a number between 0.001 and 1. b is a number between 0.001 and 2; c represents a number from 0.2 to 2, d represents a number from 0.01 to 1, and e represents a number from 1, 3 to 11. ) is particularly preferred.

In general formulas (1) and (2), the amount (a) of Ge is 0.001 or more and 1 or less with respect to Sn. It is preferably 0.002 or more and 0.7 or less, more preferably 0.01 or more and 0.5 or less. If it is less than this, the Ge coexistence effect will not appear, and if it is more than this, the charge/discharge efficiency will deteriorate. In the present invention, Si element is used as an amorphous forming element. By using Si, it is possible to obtain a stable amorphous material having a network structure, and to improve the charge-discharge cyclability. In the present invention, M ¹ and M ² in the general formulas (1) and (2) are further used. Using these elements makes it easier to obtain an amorphous oxide. Among others, Si and M ¹ and M ² in general formulas (1) and (2) are used in common to facilitate amorphization. M1 is at least ^one element selected from Al, Pb, As, P, and B from Groups 13 to 15 of the periodic table, and M2 is a Group 1 element, a Group ² element, and a Group 3 element of the periodic table. It is at least one element selected from elements and halogen elements. Among them, Al, P and B are preferable as M ¹ . M ² is Li, Na, K, Rb, Cs, M
g, Ba, Sc, Y, and F are preferred, and K, Rb, Cs, and Mg are more preferred, and the coexistence of these M ¹ and M ² makes it easier to obtain an amorphous oxide. Thus, a non-aqueous secondary battery exhibiting even better charge-discharge cyclability can be obtained. General formulas (1) and (2)
The amount (b) of Si is 0.001 or more and 2 or less, preferably 0.005 or more and 1.5 or less, more preferably 0.01 or more and 1.3 or less with respect to Sn. If it is less than this, the coexistence effect of Si will not appear, and if it is more than this, the concentrations of the functional elements Sn and Ge in the amorphous solid will decrease, causing a decrease in the discharge capacity of the non-aqueous secondary battery. It is not preferable. general formula (1),
In (2), the amount (c) of M ¹ is 0.2 or more and 2 or less, preferably 0.3 or more and 1.5 or less, more preferably 0.4 or more and 1.3 or less, relative to Sn. If it is less than this, it will be difficult to make it amorphous, and if it is more than this, the concentrations of the functional elements Sn and Ge in the amorphous solid will decrease, causing a decrease in the discharge capacity of the non-aqueous secondary battery. I don't like it. In general formulas (1) and (2), the amount (d) of M ² used is 0.01 or more and 1 or less, preferably 0.01.
03 or more and 0.8 or less, more preferably 0.05
0.5 or less. If it is smaller than this, the addition effect will be small, and if it is larger than this, S, which is a functional element
The concentration of n and Ge in the amorphous solid is reduced, which causes a decrease in the discharge capacity of the non-aqueous secondary battery, which is not preferable.

The method for synthesizing the amorphous composite oxide in the present invention can be either a calcination method or a solution method, but the calcination method is particularly preferred. The firing method will be described in detail. A Sn compound, a Ge compound, a Si compound, and/or ^an M1 compound and an ^M2 compound may be mixed and fired.

Examples of Sn compounds include SnO, Sn
₂ O ₃ , Sn ₃ O ₄ , stannous hydroxide, stannous acid, stannous oxalate, stannous phosphate, orthostannic acid, metastannic acid, parastannic acid, stannous fluoride, stannous chloride Examples include tin, stannous bromide, stannous iodide, tin selenide, tin telluride, stannous pyrophosphate, tin phosphide, and stannous sulfide. Examples of Ge compounds include alkoxy germanium compounds such as GeO ₂ , GeO, germanium tetrachloride, germanium tetrabromide, germanium tetramethoxide and germanium tetraethoxide. Examples of Si compounds include alkoxy silicon compounds such as SiO ₂ , SiO, silicon tetrachloride, silicon tetrabromide, silicon tetramethoxide and silicon tetraethoxide.
Examples of Al compounds include aluminum oxide (α-alumina, β-alumina), aluminum silicate, aluminum tri-iso-propoxide, aluminum tellurite, aluminum chloride, aluminum boride, aluminum phosphide, aluminum phosphate, lactic acid. Aluminum, aluminum borate, aluminum sulfide, aluminum sulfate, aluminum boride and the like can be mentioned. Examples of Pb compounds include PbO ₂ , PbO, P
_b2O3 , _{Pb3O4 , PbCl2} , lead chlorate, lead perchlorate, lead nitrate, lead carbonate, lead formate, lead acetate, lead tetraacetate, lead tartrate, lead _diethoxide , lead di(isopropoxide ) etc. can be mentioned. Examples of P compounds include phosphorus pentoxide, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride, phosphorus tribromide, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, stannous pyrophosphate, boron phosphate, and the like. can be mentioned. Examples of B compounds include boron sesquioxide, boron trichloride, boron tribromide, boron carbide,
boric acid, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, boron phosphide, boron phosphate and the like. Examples of As compounds include arsenic trioxide, arsenic trichloride, and arsenic tribromide.

Examples of the compounds of Groups 1 to 3 of the periodic table include oxides, hydroxides, halides, salts of organic acids such as acetic acid and oxalic acid, and salts of inorganic acids such as hydrochloric acid and phosphoric acid. be able to. Examples of Mg compounds include magnesium chloride, magnesium acetate, magnesium oxide, magnesium oxalate, magnesium hydroxide, magnesium stannate, magnesium pyrophosphate, magnesium fluoride, magnesium borofluoride, and magnesium phosphate. Examples of F compounds include tin fluoride, magnesium fluoride, aluminum fluoride, zinc fluoride,
Various fluorine compounds such as indium fluoride, fluorosilicate, germanium fluoride, iron fluoride, and titanium fluoride are used.

[0013] As the sintering conditions, the heating rate is
It is preferable that the temperature is 5 ° C. or higher and 200 ° C. or lower per minute, and
More preferably, the temperature is 7°C or higher and 200°C or lower. particularly good
Preferably, it is 10 ° C. or higher and 200 ° C. or lower, and the firing temperature
is 1500°C or less, and 500°C or more and 1500°C
° C. or less, more preferably 600
° C. or higher and 1500 ° C. or lower, particularly preferably 700 ° C.
above 1500°C and below. 100 hours as firing time
1 hour or more and 100 hours or less
preferably, more preferably 1 hour or more and 70 hours or less
1 hour or more and 20 hours or less is particularly preferable.
be. , the temperature drop rate is 2 ° C. per minute or more 10 ⁷ ℃ or less
more preferably 5°C or higher and 10⁷ ℃
or less, and particularly preferably 10° C. or more and 10⁷ below °C
be.

[0014] The rate of temperature increase in the present invention means a rate from "50% of the firing temperature (indicated in °C)" to "80% of the firing temperature (indicated in °C)".
%”, and the temperature drop rate in the present invention is “80% of the firing temperature (° C. display)”.
to 50% of the firing temperature (indicated in °C). The temperature may be lowered by cooling in the kiln, or by removing the kiln from the kiln and putting it in water for cooling. In addition, the gun method and Hamm described on page 217 of Ceramics Processing (Gihodo Publishing 1987)
er-Anvil method, slap method, gas atomization method,
Plasma spray method, centrifugal quenching method, melt drag
A super quenching method such as a method can also be used. Alternatively, the single roller method or twin roller method described on page 172 of New Glass Handbook (Maruzen 1991) may be used for cooling. In the case of a material that melts during firing, the fired material may be continuously taken out while the raw material is supplied during firing. In the case of a material that melts during firing, it is preferable to stir the melt.

The firing gas atmosphere is preferably an atmosphere having an oxygen content of 5% by volume or less, more preferably an inert gas atmosphere. Examples of inert gases include nitrogen, argon, helium, krypton and xenon. The most preferred inert gas is pure argon.

The average particle size of the compounds represented by the present invention is preferably 0.1-60 µm. Well-known grinders and classifiers are used to obtain the desired particle size. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a whirling jet mill and a sieve are used. At the time of pulverization, wet pulverization in which water or an organic solvent such as methanol is allowed to coexist can also be carried out as necessary. In order to obtain the desired particle size, it is preferable to carry out classification. The classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Both dry and wet classification can be used.

[0017] The negative electrode material used in the present invention is predominantly amorphous when assembled into a battery. The term “mainly amorphous” as used herein means that the 2θ value is 20° by the X-ray diffraction method using CuKα rays.
It has a broad scattering band with an apex at 40° from , and may have crystalline diffraction lines. preferably 2
The strongest intensity among the crystalline diffraction lines seen at the θ value of 40° or more and 70° or less is 500 of the diffraction line intensity at the peak of the broad scattering band seen at the 2θ value of 20° or more and 40° or less.
times or less, more preferably 100
times or less, particularly preferably 5 times or less, and most preferably do not have a crystalline diffraction line. In the present invention, particularly excellent effects can be obtained by
It is to use an amorphous compound containing Sn, Ge and Si and in which Sn has a valence of 2 as the negative electrode active material. The valence of Sn can be determined by chemical titration. For example Physics and Chemistry of Glasses V
8 No. 4 (1967), page 165. It can also be determined from the Knight shift of Sn by solid-state nuclear magnetic resonance (NMR) measurement.
For example, metal Sn (0-valent Sn) is S
For n(CH ₃ ) ₄ , a peak appears in an extremely low magnetic field at around 7000 ppm, whereas for SnO (= divalent) it is around 100 ppm and for SnO ₂ (= tetravalent) -600.
Appears around ppm. Thus, when the ligands have the same ligand, the Knight shift largely depends on the valence of Sn, which is the central metal, so the valence can be determined from the peak position obtained by ¹¹⁹ Sn-NMR measurement. The valence of Ge may be tetravalent or divalent, or both tetravalent and divalent may coexist. The valence of Si may be tetravalent or divalent, or may coexist with tetravalent and divalent, but tetravalent is preferred from the viewpoint of charge-discharge cycle performance.

Specific examples of the negative electrode material used in the present invention are as follows.
Although shown below, the present invention is not limited to these.
stomach. As a compound in which Ge is tetravalent, SnGe_0.001Si
P._0.1B._0.1K._0.5O._{3, 65}, SnGe_0.001Si_0.1P.
_0.45B._0.45Mg_{0, 1}K._0.1O._3.152, SnGe_{0, 005}S.
i_0.8P._0.1B._0.1Mg_0.5K._0.5O._3.76, SnGe
_{0, 01}Si_0.7P._0.2K.₀. ₀₁O._2.925, SnGe_{0, 01}Si
_0.8P._0.1B._0.1K._0.1O._3.07, SnGe_0.001Si
_2.0P._0.1B._0.1Mg_0.1O._{5, 402}, SnGe_0.01Si
_1.5P._0.2K._0.1O. _{4, 57}, SnGe_0.01Si_1.7B._0.2
Mg_0.1O._{4, 82} SnGe_0.1Si_0.6B._0.2Al_0.1Mg_0.1O._{2, 95} SnGe_0,1Si_0,5B._0,3Al_0,1Mg_0,1O._2.9 SnGe_0,1Si_0,4B._0,4Al_0,1Mg_0,1O._2,85 SnGe_0.1Si_0.3B._0.5Al_0.1Mg_0.1O._2.8

SnGe_{0, 02}Si_0.7P._0.3K.
_0.1O._3.24, SnGe_{0, 02}Si_0.7P._0.15B._0.15K._0.1
O._3.09, SnGe_{0, 02}Si_0.6P._0.4K._0.1O._4.209,
SnGe_{0, 02}Si_0.4P._0.2B._{0. 2}O._2.64, SnGe
_{0, 02}Si_0.5P._0.5K._0.1O._{3, 34}, SnGe_{0, 02}Si
_0.5P. _0.25B._0.25K._0.1O._{3, 09}, SnGe_{0, 02}Si_0.4
P._0.6K._0.1O._3.3, SnGe _{0, 02}Si_0.4P._0.3B.
_0.3K._0.1Mg_0.2O._3.29, SnGe_{0, 02}Si_0.3P.
_0.7K._0.1O._3.44, SnGe_{0, 02}Si_0.3P._0.5B._0.2
K._0.1O._3.24, SnGe_{0, 02}Si_0.3P._0.4B._0.3K.
_0.1O._3.14, SnGe_0.1Si_0.5B._0.3P._0.2Al₀.
₁O._3.2, SnGe_0.1Si_0.4B._0.3P._0.2Al_0.1
O.₃ , SnGe_0.1Si_0.3B._0.3P._0.2Al_0.1O.
_2.8, SnGe_0.1Si_0.2B._0.3P._0.2Al_0.1O.
_2.6, SnGe_0.1Si_0.6B._0.3P._0.2Al_0.1O.
_3.4, SnGe_0.1Si_0.7B._0.3P._0.2Al_0.1O.
_3.6, SnGe_0.1Si_0.8B._0.3P._0.2Al_0.1O.
_3.8, SnGe_0.1Si_0.9B._0.3P._0.2Al_0.1O.
_4.0,

SnGe_{0, 05}Si_0.3P._0.3B._0.4K._0.1
O._3.1, SnGe_{0, 05}Si_0.2P._0.8K._0.1O._{3, 55}, S
nGe_{0, 05}Si_0.2P._0.6B._0.2K._0.1O._{3, 85}, SnG
e_{0, 05}Si_0.2P._0.4B._0.4K._0.1O._4.15, SnGe
_{0, 05}Si_0.2P._0.2B._0.6K._0.1O._{2, 95}, SnGe_{0, 05}
Si_0.2P._0.4B._0.4K._0.1Mg_0.1O._3.25, SnGe
_{0, 05}Si_0.2P._0.6B._0.2Mg_0.1K._0.1O._{3, 45}, Sn
Ge_{0, 05}Si_0.2P._0.3B. _0.5Mg_0.1K._0.1O._3.3,

SnGe_{0, 05}Si_0.1P._0.6B._0.3Mg
_0.1K._0.1O._4.0, SnGe_{0, 05}Si_0.2P._0.45B._0.45
K._0.2O._{3, 4}, SnGe_{0, 05}Si_0.1P._0.45B._0.45Mg
_0.1K._0.1O._{3, 34,}SnGe_{0, 05}Si_0.2P._0.45B._0.45
K._0.1Mg_{0. 1}Al_0.05O._{3, 525,}SnGe_{0, 05}Si
_0.1P._0.4B._0.5Mg_0.1K._0.1O._3.2, SnGe_{0, 05}
Si_0.01P._0.6B._0.4K._0.1O._{3, 27}, SnGe_{0, 05}Si
_0.02P._{0. 6}B._0.4Mg_0.1K._0.1O._{3, 39,}SnGe_{0, 05}
Si_0.05P._0.6B._0.4Cs_0.1O. _{3, 35}, SnGe_{0, 05}S.
i_0.1P._0.5B._0.5K._0.1O._{3, 35}, SnGe_{0, 05}Si
_{0.00 1}P._0.5B._0.5Mg_0.1K._0.1O._{3, 252}, SnGe
_{0, 05}Si_0.005P._0.5B._0.5Al_0.1K._0.1O._{3, 31}, S
nGe_{0, 05}Si_0.1P._0.5B._0.5Mg_0.01O._{3, 301}, S
nGe_{0, 05}Si_0.01P._0.5B._0.5Al_0.05Mg_0.1K.
_0.1O._{3, 345}, SnGe _{0, 05}Si_0.1P._0.5B._0.5Cs
_0.1O._{3, 305},

_{SnGe 0,05} Si _0.1 P _0.5 B _0.5 Cs
_{0.05K0.05O3,35 , SnGe0,05Si0.1P0.5B0.5 _ _ _ _
K0.5Cs0.5O3,8 , SnGe0,05Si0.05P0.4B _ _ _
0.6K0.1O3.0 , SnGe0,05Si0.1P0.4B0.6 _ _ _ _
K0.1Mg0.1O3,35 , SnGe0,05Si0.1P0.4B _ _ _
0.6K0.1Al0.02O3,28 , SnGe0,05Si0.1P _ _ _
0.4B0.6Cs0.1O3,25 , SnGe0,05Si0.1P _ _ _
0.4} B _0.6 K _0.2 O _3,26 SnGe _0,05 Si _0.2 P _{0.4
B0.6Rb0.1O3,45 , SnGe0,05Si0.05P0.3B _ _ _
0.7K0.1Mg0.1O3,15 , SnGe0,05Si0.1P _ _ _
0.1B0.9K0.2Mg0.1O3.0 , SnGe0,05Si _ _ _
0.005P0.1B0.9Mg0.4O3,11 , SnGe0,05Si _ _ _
0.3P1.1K0.1O4.5 , SnGe0,05Si0.1P0.7 _ _ _ _
B0.4K0.1Mg0.1O3,8 , SnGe0,05Si0.1P _ _ _
0.6} B _0.5 K _0.1 Mg _0.1 O _3,8 , _{SnGe 0,05} Si
_{0.3P0.5B0.6Cs0.1O3,9 , SnGe0,05Si _ _ _
0.2P0.4B0.7K0.2O3,65 , SnGe0,05Si0.2 _ _ _ _
P0.4B0.7K0.1Mg0.1O3,7 , SnGe0,05Si _ _ _
0.2P1.2K0.1Mg0.1O4,65 , SnGe0,05Si _ _ _
0.002P0.6B0.6K0.1Mg0.1O3 , 654 , _ _}

SnGe _0,1 Si _0.3 P _0.9 K
_{0.1O4.1 , SnGe0 , 1Si0.3P0.7B0.2K0.1 _ _
Mg0.1O3,9 , SnGe0,1Si0.2P0.6B0.3M _ _ _
g0.1K0.1O3,7 , SnGe0,1Si0.2P0.45B _ _ _
0.45K0.1O3,45 , SnGe0,1Si0.4P0.45B0.45K0.2O3,9 , Sn _ _ _ _
Ge0,1Si0.1P0.45B0.45Mg0.1K0.1O3,35 , SnGe0,1Si0.2P0.45B0.45K0.1Mg0.1Al _ _ _ _ _ _ _ _ _ _
0.05O3,625SnGe0,1Si0.2P0.4B0.5Mg _ _ _ _ _ _
0.1} K _0.1 O _3,5 , SnGe _0,1 Si _0.1 PK _0.1 Mg
_{0.2O4,25 , SnGe0,1Si0.2P0.6B0.4K0.1 _ _ _ _
O3,75 , SnGe0,1Si0.1P0.6B0.4Mg0.1K _ _ _
0.1O3,65 , SnGe0,1Si0.2P0.6B0.4Cs0.1O3,75 , S _ _ _
nGe0,1Si0.1P0.5B0.5K0.1O3,45 , _ _ _ _}

SnGe_{0, 1}Si_0.1P._0.5B._0.5Mg
_0.1K._0.1O._{3, 55}, SnGe_{0, 1}Si_0.3P._0.5B._0.5
Al_0.1K._0.1O._3.0, SnGe_{0, 1}Si_0.2P._0.5B.
_0.5Ba_0.05K._0.1O._{2, 7}, SnGe_{0, 1}Si_0.05P.
_0.5B._0.5Pb_0.05K._0.1O._{2, 4}, SnGe_{0, 1}Si
_0.1P._0.5B._0.5Mg_0.05K._0.15O._{3, 525}, SnGe
_{0, 1}Si_0.3P._0.5B._0.5Mg_0.2K._0.05O._4.025, SnGe_{0, 1}Si_0.1P._0.5B._0.5Mg_0.01O._{3, 401},
SnGe_{0, 1}Si_0.05P._0.5B._0.5Al_0.05Mg_0.1K.
_0.1O._{3, 425}, SnGe _{0, 1}Si_0.1P._0.5B._0.5Cs
_0.1O._{3, 405}, SnGe_{0, 1}Si_0.5P._0.5B._0.5Mg
_0.1Li_0.1O._{4, 35}, SnGe_{0, 1}Si_0.3P._0.5B.
_0.5Na_0.1O._{3, 805}, SnGe_{0, 1}Si_0.1P._0.5B.
_0.5Rb_0.O._{3, 405}, SnGe_{0, 1}Si_0.2P._0.5B.
_0.5K._0.1Ca_0.05O._{3, 675}, SnGe_{0, 1}Si_0.01P.
_0.5B._0.5Mg_0.1K._0.1F._0.1O._{3, 27}, SnGe_{0, 1}
Si_0.02P._0.5B._0.5K._0.1Sc_0.02O._{3, 32}, SnGe
_{0, 1}Si_0.2P._0.5B._{0. Five}Mg_0.1K._0.1Y._0.01O.
_{3, 765},

SnGe_{0, 1}Si_0.2P._0.5B._0.5Cs
_0.05K._0.05O._{3, 65}, SnGe_{0, 1}Si_0.1P._0.5B._0.5
Mg_0.1K._0.4Cs_0.4O._{3, 9}, SnGe_{0, 1}Si_0.1P.
_0.5B._0.5K._0.5Cs_0.5O._{3, 9}, SnGe_{0, 1}Si
_0.3P._0.4B._{0. 6}K._0.1O._{3, 75}, SnGe_{0, 1}Si_0.1
P._0.4B._0.6K._0.1Mg_0.1O._{3, 45}, SnGe_{0, 1}Si
_0.1P._0.4B._0.6K._0.1Al_0.02O._{3, 38}SnGe_{0, 1}S.
i_0.1P._0.4B._0.6Cs_0.1O._{3, 35}, SnGe_{0, 1}Si
_0.1P._0.4B._0.6K._0.2O._{3, 36}, SnGe_{0, 1}Si_0.1
P._0.4B._0.6Rb_0.1O._{3, 35}, SnGe_{0, 1}Si_0.3P.
_0.3B._0.7K._0.1Mg_0.1O._{2, 75}, SnGe_{0, 1}Si
_0.2P._0.3B._0.7K.₀.₁₅Mg_0.05O._{2, 325}, SnGe
_{0, 1}Si_0.1P._0.3B._0.7Cs_0.1O._{2, 25}, SnGe
_{0, 1}Si_0.04P._0.1B._0.9K._0.2Mg_0.1O._{2, 98}, Sn
Ge_{0, 1}Si_0.1P._0.1B._0.9Mg_0.4O._{3, 4}, SnG
e_{0, 1}Si_0.4P._1.1K._0.1O._4.8, SnGe_{0, 1}Si
_0.3P._0.7B._0.4K._0.1Mg_0.1O._4.3, SnGe_{0, 1}
Si_0.2P._0.6B._{0 .Five}K._0.1Mg_0.1O._4.1, SnGe
_{0, 1}Si_0.1P._0.5B._0.6K._0.1Al_0.02O._{3, 63} SnGe_{0, 1}Si_0.1P._0.5B._0.6K._0.1Ba_0.05O.
_{3, 65}, SnGe_{0, 1}Si_0.1P._0.5B._0.6Cs_0.05O.
_{3, 535}, SnGe_{0, 1}Si_0.05P._0.5B._0.6Cs_0.1O.
_{3, 5}, SnGe_{0, 1}Si_0.05P._0.5B._0.6Cs_0.05K.
_0.05O._{3, 5}, SnGe_{0, 1}Si_0.05P._0.4B._0.7K._0.2
O._{3, 45}, SnGe_{0, 1}Si_0.5P._1.2K._0.1Mg_0.1O.
_{5, 35}, SnGe_{0, 1}Si_0.2P._0.6B._0.6K._0.1Mg
_0.1O._4.15, SnGe_{0, 1}Si_0.7P._1.5K._0.2Mg
_0.1O._6.55,

SnGe _0,2 Si _0.3 P _0.7 B _0.2 K _{0.1
Mg0.1O4.1 , SnGe0,2Si0.3P0.6B0.3M _ _ _
g0.1K0.1O4.1 , SnGe0,2Si0.2P0.45B _ _ _
0.45K0.1O3,65 , SnGe0,2Si0.2P0.45B0.45K0.2O3,7 , Sn _ _ _ _
Ge0,2Si0.3P0.45B0.45Mg0.1K0.1O3,95 , SnGe0,2Si0.1P0.45B0.45K0.1Mg0.1Al _ _ _ _ _ _ _ _ _ _
0.05O3,525 , SnGe0,2Si0.1P0.4B0.5Mg0.1K0.1O _ _ _ _ _
3,5 , SnGe0,2Si0.5PK0.1Mg0.2O5,25 , _ _
SnGe0,2Si0.2P0.6B0.4K0.1O3,95 , Sn _ _ _
Ge0,2Si0.1P0.6B0.4Mg0.1K0.1O3,85 , SnGe0,2Si0.2P0.6B0.4Cs0.1O3,95 , S _ _ _ _ _ _ _ _
nGe0,2Si0.3P0.5B0.5K0.1O4.05 , _ _ _ _}

SnGe _0,2 Si _0.1 P _0.5 B _0.5 Mg
_0.1 K _0.1 O _3,75 SnGe _0,2 Si _0.05 P _0.5 B _{0.5
Al0.1K0.1O3,7SnGe0,2Si0.2P0.5B0.5Mg0.05K0.15O _ _ _ _ _ _ _ _
3,925 , SnGe0,2Si0.1P0.5B0.5Mg0.01O _ _ _
3,601 , SnGe0,2Si0.1P0.5B0.5Al0.05M _ _ _
g0.1K0.1O3,825 , SnGe0,2Si0.05P0.5B _ _ _
0.5Cs0.1O3,505 , SnGe0,2Si0.1P0.5B _ _ _
0.5Cs0.05K0.05O3,65 , SnGe0,2Si0.1P _ _ _
0.5B0.5K0.5Cs0.5O4.1 , SnGe0,2Si _ _ _
0.05} P _0.4 B _0.6 K _0.1 O _3,45 SnGe _0,2 Si _{0.2
P0.4B0.6K0.1Mg0.1O3,85 , SnGe0,2Si _ _ _
0.1P0.4B0.6K0.1Al0.02O3,58 , SnGe0,2 _ _ _ _
Si0.2P0.4B0.6Cs0.1O3,75 , SnGe0,2S _ _ _
i0.1P0.4B0.6K0.2O3,56 , SnGe0,2Si _ _ _
0.3P0.4B0.6Rb0.1O3,95 , SnGe0,2Si _ _ _
0.3} P _0.3 B _0.7 K _0.1 Mg _0.1 O _2,95 SnGe _{0,2
Si0.2P0.1B0.9K0.2Mg0.1O3,5SnGe0,2Si0.4P0.1B0.9Mg0.4O4.2 , _ _ _ _ _ _ _ _ _ _}

SnGe _0,2 Si _0.5 P _1.1 K
_{0.1O5,2 , SnGe0,2Si0.4P0.7B0.4K0.1 _ _ _ _
Mg0.1O4.1 , SnGe0,2Si0.2P0.6B0.5K _ _ _
0.1} Mg _0.1 O _3,7 , SnGe _0,2 Si _0.05 P _0.5 B
_{0.6Cs0.05O3,635 , SnGe0,2Si0.002P0.5 _ _ _
B0.6Cs0.1O3,604 , SnGe0,2Si0.01P0.4 _ _ _
B0.7K0.2O3,57 , SnGe0,2Si0.05P0.4B _ _ _
0.7K0.1Mg0.1O3,7 , SnGe0,2Si0.6P _ _ _
1.2K0.1Mg0.1O5.75 , SnGe0,2Si0.005P _ _ _
0.6B0.6K0.1Mg0.1O3,96 , _ _ _}

SnGe _0,5 Si _0.3 P _0.7 B _0.8 K _{0.2
Mg0.2O5,85 , SnGe0,6Si0.7P0.8B0.8C _ _ _
s0.1O6.85 , SnGe0,7Si1.0P1.8K _ _
0.2O9 , SnGe0,8Si1.2P0.9B0.9K0.2M _ _ _ _
g0.4O6,7 , SnGe1Si0.8P1B1Cs0.1O _ _ _ _
8.65 , SnGe1Si1.2P0.4As0.1B0.1K0.1 _ _ _ _}
Mg _0.1 O _6.85

SnGe _0.1 Si _1.7 O _4.6 , SnGe
_{0.3Si2.0O5,6 , SnGe0.5Si1.5O5 , SnG _
e0.8Si1.2O4.0 , SnGeSi2O7 , SnGe
1.3} Si _1.8 O _7.2 , SnGeSiO ₅ and the like.

As a compound in which Ge is divalent, SnG
_{e0,02Si0.7P0.3K0.1O3.14 , SnGe0,02Si _ _ _
1.0} P _0.15 B _0.15 K _0.1 O _3,59 SnGe _0,02 Si _{0.5
P0.4K0.1O4,99 , SnGe0,02Si0.5P0.2B0.2O2,64 , SnGe _ _ _
0,02Si0.5P0.5K0.1O3,24 , SnGe0,02Si0.4 _ _ _ _
P0.25B0.25K0.1O2.7 , SnGe0,02Si0.4 _ _ _
P0.6K0.1O3.2 , SnGe0,02Si0.3P0.3B _ _ _
0.3K0.1Mg0.2O2,99 , SnGe0,02Si0.2P _ _ _
0.7K0.1O3.14 , SnGe0,02Si0.3P0.5B0.2 _ _ _ _
K0.1O3.14 , SnGe0,02Si0.3P0.4B0.3K _ _ _
0.1 O3.04} ,

_{SnGe 0,05} Si _0.2 P _0.3 B _0.4 K _{0.1
O2,8 , SnGe0,05Si0.3P0.8K0.1O3,65 , S _
nGe0,05Si0.4P0.6B0.2K0.1O4.15 , SnG _ _ _
e0,05Si0.4P0.4B0.4K0.1O3.25 , SnGe _ _ _
0,05 Si0.3P0.2B0.6K0.1O3.05 , SnGe0,05 _ _ _
Si0.2P0.4B0.4K0.1Mg0.1O3.15SnGe0,05Si0.5P0.6B0.2Mg0.1K0.1O _ _ _ _ _ _ _ _ _ _ _
3,95SnGe0,05Si0.4P0.3B0.5Mg0.1K0.1O _ _ _ _ _ _
3.6} ,

_{SnGe 0,05} Si _0.2 P _0.6 B _0.3 Mg
_{0.1K0.1O4.1 , SnGe0,05Si0.2P0.45B0.45 _ _ _ _
K0.2O3.3SnGe0,05Si0.3P0.45B0.45Mg0.1K0.1O _ _ _ _ _ _ _
3, 64, SnGe 0,05} Si _0.1 P _0.45 B _0.45 K _0.1 Mg _0.1 Al
_{0.05O3,225 SnGe0,05Si0.1P0.4B0.5Mg0.1K0.1O _ _ _ _ _ _
3.1 SnGe0,05Si0.2P0.6B0.4K0.1O3,45 , Sn _ _ _
Ge0,05Si0.1P0.6B0.4Mg0.1K0.1O3,35 , SnGe0,05Si0.05P0.6B0.4Cs0.1O3,15 , S _ _ _ _ _ _ _ _
nGe0,05Si0.1P0.5B0.5K0.1O3,25 , SnG _ _ _
e0,05Si0.1P0.5B0.5Mg0.1K0.1O3,35 , S _ _ _ _
nGe0,05Si0.05P0.5B0.5Al0.1K _ _ _ _
0.1O3,9 , SnGe0,05Si0.1P0.5B0.5Mg _ _ _
0.01O3,201 , SnGe0,05Si0.00P0.5B0.5Al _ _ _
0.05} Mg _0.1 K _0.1 O _3,227 , _{SnGe 0,05} Si _{0.005
P0.5B0.5Cs0.1O3 , 015 _}

_{SnGe 0,05} Si _0.1 P _0.5 B _0.5 Cs
_{0.05K0.05O3,25 SnGe0,05Si0.2P0.5B0.5 _ _ _ _ _
K0.5Cs0.5O3,9 , SnGe0,05Si0.1P0.4B _ _ _
0.6K0.1O3.0 , SnGe0,05Si0.1P0.4B0.6 _ _ _ _
K0.1Mg0.1O3,25 , SnGe0,05Si0.05P0.4B _ _ _
0.6K0.1Al0.02O3.08SnGe0,05Si0.05P0.4B0.6Cs0.1O3.05 , SnGe0,05Si0.2P0.4B0.6K0.2O3.36 , Sn _ _ _ _ _ _ _ _ _ _ _
Ge0,05Si0.1P0.4B0.6Rb0.1O2,56 , SnG _ _ _
e0,05Si0.1P0.3B0.7K0.1Mg0.1O2,55 , S _ _ _ _
nGe0,05Si0.1P0.1B0.9K0.2Mg _ _ _ _
0.1O2,9 , SnGe0,05Si0.2P0.1B0.9Mg _ _ _
0.4O3,4 , SnGe0,05Si0.5P1.1K _ _
0.1O4,8 SnGe0,05Si0.2P0.7B0.4K0.1 _ _ _ _ _
Mg0.1O3,9 , SnGe0,05Si0.1P0.6B0.5K _ _ _
0.1} Mg _0.1 O _3,7 , _{SnGe 0,05} Si _0.05 P _0.5 B
_{0.6Cs0.1O3,3 , SnGe0,05Si0.05P0.4B _ _ _
0.7} K _0.2 O _3,25 SnGe _0,05 Si _0.1 P _0.4 B _{0.7
K0.1Mg0.1O3,4SnGe0,05Si0.8P1.2K0.1Mg0.1O5.75 , S _ _ _ _ _ _
nGe0,05Si0.01P0.6B0.6K0.1Mg _ _ _ _
0.1 O3,57} ,

SnGe _0,1 Si _1.0 P _0.9 K
_{0.1O5,4 , SnGe0,1Si0.6P0.7B0.2K0.1 _ _ _ _
Mg0.1O4.4 , SnGe0,1Si0.4P0.6B0.3M _ _ _
g0.1K0.1O4.0 , SnGe0,1Si0.3P0.45B _ _ _
0.45K0.1O3,65 , SnGe0,1Si0.3P0.45B0.45K0.2O3,6 , Sn _ _ _ _
Ge0,1Si0.2P0.45B0.45Mg0.1K0.1O3,45 , SnGe0,1Si0.1P0.45B0.45K0.1Mg0.1Al _ _ _ _ _ _ _ _ _ _
0.05O3,325SnGe0,1Si0.2P0.4B0.5Mg0.1K0.1O _ _ _ _ _ _ _
3,4 , SnGe0,1Si0.5PK0.1Mg0.2O5,05 , _ _
SnGe0,1Si0.3P0.6B0.4K0.1O3,85 , Sn _ _ _
Ge0,1Si0.1P0.6B0.4Mg0.1K0.1O3,55 , SnGe0,1Si0.1P0.6B0.4Cs0.1O3,25 , S _ _ _ _ _ _ _ _
nGe0,1Si0.2P0.5B0.5K0.1O3,55 , _ _ _ _}

SnGe _0,1 Si _0.05 P _0.5 B _0.5 Mg
_0.1 K _0.1 O _3,35 SnGe _0,1 Si _0.1 P _0.5 B _{0.5
Al0.1K0.1O2,5 , SnGe0,1Si0.2P0.5B _ _ _
0.5Ba0.05K0.1O2,6 , SnGe0,1Si0.3P _ _ _
0.5B0.5Pb0.05K0.1O3.4 , SnGe0,1Si _ _ _
0.1P0.5B0.5Mg0.05K0.15O3,425 , SnGe _ _ _
0 , 1Si0.05P0.5B0.5Mg0.2K0.05O3 , 425 , SnGe0 , 1Si0.3P0.5B0.5Mg0.01O3 , 701 , _
SnGe0,1Si0.05P0.5B0.5Al0.05Mg0.1K _ _ _ _ _
0.1O3,425 , SnGe0,1Si0.001P0.5B0.5C _ _ _
s0.1O3,107 , SnGe0,1Si0.3P0.5B0.5M _ _ _
g0.1Li0.1O3,85 , SnGe0,1Si0.5P0.5B _ _ _
0.5Na0.1O4,105 , SnGe0,1Si0.2P0.5B _ _ _
0.5Rb0.1O3,505 , SnGe0,1Si0.1P0.5B _ _ _
0.5K0.1Ca0.05O3,375 , SnGe0,1Si0.02P _ _ _
0.5} B _0.5 Mg _0.1 K _0.1 F _0.1 O 3,19 _{SnGe 0,1
Si0.1P0.5B0.5K0.1Sc0.02O3,38 , SnGe _ _ _
0} , 1 Si _0.05 P _0.5 B _0.5 Mg _0.1 K _0.1 Y _0.01 O
3, ₃₆₅ ,

SnGe _0,1 Si _0.1 P _0.5 B _0.5 Cs
_0.05 K _0.05 O _3,25 SnGe _0,1 Si _0.2 P _0.5 B _{0.5
Mg0.1K0.4Cs0.4O3,8 , SnGe0,1Si0.05 _ _ _
P0.5B0.5K0.5Cs0.5O3,65 , SnGe0,1Si _ _ _
0.05} P _0.4 B _0.6 K _0.1 O _3,10 , SnGe _0,1 Si _{0.05
P0.4B0.6K0.1Mg0.1O3,20 , SnGe0,1Si _ _ _
0.2P0.4B0.6K0.1Al0.02O3,28SnGe0,1Si0.1P0.4B0.6Cs0.1O3,25 , S _ _ _ _ _ _ _ _ _
nGe0,1Si0.1P0.4B0.6K0.2O3,16 , SnG _ _ _
e0,1Si0.3P0.4B0.6Rb0.1O3,35 , SnGe _ _ _
0,1Si0.2P0.3B0.7K0.1Mg0.1O2,2.5 , S _ _ _ _
nGe0,1Si0.2P0.3B0.7K0.15Mg0.05O _ _ _ _ _
2,225 , SnGe0,1Si0.05P0.3B0.7Cs0.1O _ _ _
2.0 , SnGe0,1Si0.4P0.1B0.9K0.2Mg _ _ _
0.1O3.2 , SnGe0 , 1Si0.5P0.1B0.9Mg _
0.4O3,6 , SnGe0,1Si0.7P1.1K0.1O4.0 , SnGe0,1Si0.2P0.7B0.4K0.1Mg0.1O _ _ _ _ _ _ _ _
3,8 , SnGe0,1Si0.02P0.6B0.5K0.1Mg _ _ _
0.1O3,64 , SnGe0,1Si0.005P0.5B0.6K _ _ _
0.1Al0.02O3,335SnGe0,1Si0.05P0.5B _ _ _ _ _
0.6K0.1Ba0.05O3,40 SnGe0,1Si0.002P _ _ _ _
0.5} B _0.6 Cs _0.05 O _3,237 , SnGe _0,1 Si _{0.001
P0.5B0.6Cs0.1O3,301 , SnGe0,1Si _ _
0.005P0.5B0.6Cs0.05K0.05O3,305 , SnGe _ _ _
0,1Si0.2P0.4B0.7K0.2O3,45 , SnGe0,1 _ _ _ _
Si0.1P0.4B0.7K0.1Mg0.1O3,45 , SnGe _ _ _
0} , 1 Si _0.4 P _1.2 K _0.1 Mg _0.1 O _4,65 , SnGe
₀ , 1 Si _0.01 P _0.6 B _0.6 K _0.1 Mg _0.1 O _3,66 , Sn
_{Ge0,1Si1.2P1.5K0.2Mg0.1O6.25 , _ _ _ _}

SnGe _0,2 Si _0.5 P _0.7 B _0.2 K _{0.1
Mg0.1O3,9 , SnGe0,2Si0.4P0.6B0.3M _ _ _
g0.1K0.1O3,8 , SnGe0,2Si0.3P0.45B _ _ _
0.45K0.1O3,45 , SnGe0,2Si0.4P0.45B0.45K0.2O3,6 , Sn _ _ _ _
Ge0,2Si0.1P0.45B0.45Mg0.1K0.1O3,35 , SnGe0,2Si0.2P0.45B0.45K0.1Mg0.1Al _ _ _ _ _ _ _ _ _ _
0.05O3,525 SnGe0,2Si0.1P0.4B0.5Mg0.1K0.1O _ _ _ _ _ _
3,3 , SnGe0,2Si0.4PK0.1Mg0.2O4,55 , _ _
SnGe0,2Si0.3P0.6B0.4K0.1O3,75 , Sn _ _ _
Ge0,2Si0.05P0.6B0.4Mg0.1K0.1O3,60 , SnGe0,2Si0.2P0.6B0.4Cs0.1O3,65 , S _ _ _ _ _ _ _ _
nGe0,2Si0.2P0.5B0.5K0.1O3,55 , _ _ _ _}

SnGe _0,2 Si _0.1 P _0.5 B _0.5 Mg
_0.1 K _0.1 O _3,55 SnGe _0,2 Si _0.2 P _0.5 B _{0.5
Al0.1K0.1O3,7 , SnGe0,2Si0.002P0.5 _ _ _
B0.5Mg0.05K0.15O3,427 , SnGe0,2Si0.01 _ _ _
P0.5B0.5Mg0.01O3,311 , SnGe0,2Si0.01 _ _ _
P0.5B0.5Al0.05Mg0.1K0.1O3,535 , SnG _ _ _
e0,2Si0.1P0.5B0.5Cs0.1O3,405 , SnG _ _ _
e0,2Si0.2P0.5B0.5Cs0.05K0.05O3,55 , S _ _ _ _
nGe0,2Si0.3P0.5B0.5K0.5Cs _ _ _ _
0.5O4.1 , SnGe0,2Si0.1P0.4B0.6K0.1 _ _ _ _
O3,35SnGe0,2Si0.2P0.4B0.6K0.1Mg0.1O _ _ _ _ _ _
3,55 , SnGe0,2Si0.2P0.4B0.6K0.1Al _ _ _
0.02O3,48SnGe0,2Si0.1P0.4B0.6Cs0.1O3,35 , S _ _ _ _ _
nGe0,2Si0.05P0.4B0.6K0.2O3,31 , SnG _ _ _
e0,2Si0.2P0.4B0.6Rb0.1O3,45 , SnGe _ _ _
0} , 2 Si _0.3 P _0.3 B _0.7 K _0.1 Mg _0.1 O _3.15 , Sn
_{Ge0,2Si0.5P0.1B0.9K0.2Mg0.1O3,5SnGe0,2Si0.3P0.1B0.9Mg0.4O3,6 , _ _ _ _ _ _ _ _ _ _ _}

SnGe _0,2 Si _2.0 P _1.1 K
_{0.1O6,1 , SnGe0,2Si0.7P0.7B0.4K0.1 _ _ _ _
Mg0.1O4.5 , SnGe0,2Si0.002P0.6B0.5 _ _ _
K0.1Mg0.1O3,802 , SnGe0,2Si0.01P0.5 _ _ _
B0.6Cs0.05O3,445 , SnGe0,2Si0.1P0.5 _ _ _
B0.6Cs0.1O3,6 , SnGe0,2Si0.1P0.4B _ _ _
0.7K0.2O3,55 , SnGe0,2Si0.3P0.4B0.7 _ _ _ _
K0.1Mg0.1O3,8 , SnGe0,2Si0.8P1.2K _ _ _
0.1Mg0.1O5.25 , SnGe0,2Si0.005P0.6B _ _ _
0.6} K _0.1 Mg _0.1 O 3, ₂₅₅ , etc. can be mentioned.

In the present invention, by using the above-described compounds as negative electrode materials, it is possible to obtain a non-aqueous secondary battery with excellent charge-discharge cycle characteristics, high discharge voltage, and high capacity.

Various compounds can be contained in the negative electrode active material of the present invention. For example, transition metals (Sc, Ti, V,
Cr, Co, Ni, Cu, Zn, Y, Zr, Nb, M
o, Tc, Ru, Rh, Pd, Ag, Cd, lanthanide metals (Hf, Ta, W, Re, Os, Ir, Pt,
Au, Hg) and also dopants such as various compounds (eg, Sb, In, Nb compounds) that increase electronic conductivity. The amount of compound to be added is preferably 0 to 20 mol %. As shown in the examples, by using the negative electrode material of the present invention, it is possible to obtain a non-aqueous secondary battery with high capacity and excellent cyclability.

However, these high-capacity batteries
Abnormal current flows due to an external short circuit caused by improper use such as forced discharge, and accidents such as a significant rise in internal temperature, ejection of contents, and bursting of the battery can may occur. In order to prevent these problems, efforts have been made to incorporate a safety valve, a current shielding element such as a PTC, and the like, but the problem of heat generation has not been solved essentially. In the present invention, it is preferable to provide at least one protective layer on the negative electrode and/or the positive electrode in order to improve safety.

In the present invention, the protective layer is composed of at least one layer, and may be composed of multiple layers of the same type or different types. These protective layers are substantially electronically non-conducting, ie insulating layers. When the protective layer is formed from multiple layers, at least the outermost layer is insulating.
The thickness of the protective layer is preferably 1 μm or more and 40 μm or less, more preferably 2 μm or more and 30 μm or less. Furthermore, it is desirable that the protective layer containing these particles does not melt at 300° C. or less and does not form a new film. These protective layers preferably contain insulating organic or inorganic particles. These particles are preferably 0.1 μm or more and 20 μm or less, more preferably 0.2 μm or more and 15 μm or less.

Preferable organic particles are crosslinked latex or fluororesin powder, have a glass transition point of 250° C. or higher and 350° C. or lower, and preferably do not decompose or form a film. More preferred is Teflon powder. Examples of inorganic particles include carbides, silicides, nitrides, sulfides, and oxides of metals and nonmetallic elements. SiC among carbides, silicides and nitrides,
Aluminum nitride, BN, and BP are preferred because of their high insulating properties and chemical stability, and SiC using BeO, Be, and BN as a sintering aid is particularly preferred. Among chalcogenides, oxides are preferred, and oxides that are difficult to oxidize or reduce are preferred. These oxides include Al ₂ O
₃ , _As4O6 , _{B2O3 ,} BaO, _BeO , CaO,
_Li2O , _K2O , _{Na2O , In2O3} , MgO, S
_b2O5 , _SiO2 , _SrO and _ZrO4 .
Among these, Al ₂ O ₃ , BaO, BeO, Ca
O, _K2O , _Na2O , MgO, _SiO2 , SrO, Z
_rO4 is particularly preferred. Preferred compounds as composite oxides include mullite (3Al ₂ O ₃ .2SiO ₂ ),
Forsterite ₍ 2MgO.SiO2) _, cordierite _{( 2MgO.2Al2O3.5SiO2} ) and the like can be mentioned.

These inorganic compound particles are adjusted to a particle size of 0.1 μm or more and 20 μm or less, particularly preferably 0.2 μm or more and 15 μm or less. The content of particles used in the present invention is 1 to
80 g/m ² , preferably 2 to 40 g/m ² . The protective layer is formed using the substantially non-conductive electrically insulating particles and a binder. As the binder, the binder used when forming the electrode mixture described later can be used. The ratio of the non-conductive particles to the binder is preferably 40% by weight or more and 96% by weight or less, more preferably 50% by weight or more and 92% by weight or less, based on the total weight of both.

The protective layer may be applied to either the positive electrode or the negative electrode, or may be applied to both the positive electrode and the negative electrode. again,
When the positive electrode and the negative electrode are formed by coating the mixture on both sides of the current collector, the protective layer may be coated on both sides, or may be coated on only one side. However, separate
Either one of the positive electrode and the negative electrode, which face each other through a terminator, must be coated.

[0048] The coating method of the protective layer may be a sequential method in which a mixture containing a material capable of reversibly absorbing and desorbing lithium is coated on the current collector and then the protective layer is sequentially coated. A simultaneous coating method in which the agent layer and the protective layer are coated at the same time may be used.

[0049] Hereinafter, using the negative electrode material of the present invention, a non-aqueous
Details other materials and manufacturing methods for making secondary batteries
be. The oxide positive electrode active material or negative electrode used in the present invention
The surface of the electrode material is different from the positive electrode active material and negative electrode material used.
can be coated with an oxide having the chemical formula this
Surface oxides are compounds that dissolve in both acid and alkali
Oxides containing are preferred. Metals with even higher electronic conductivity
Oxides are preferred. For example, PbO₂ , Fe ₂ O.₃ , S
nO₂ , In₂ O.₃ , ZnO, etc. or their oxidation
dopants (e.g. gold with different valences in oxides)
genus, halogen elements, etc.) are preferably included. Special
preferably SiO₂ , SnO₂ , Fe₂ O.₃ , Zn
O, PbO₂ is. Gold used for these surface treatments
The amount of the group oxide is 0.00 per the positive electrode active material/negative electrode material.
1 to 10% by weight is preferred, and 0.2 to 5% by weight is particularly preferred.
Preferably, 0.3-3% by weight is most preferred. Also, this
In addition, it is possible to modify the surfaces of positive electrode active materials and negative electrode materials.
can. For example, the surface of a metal oxide can be treated with an esterification agent.
treatment, treatment with a chelating agent, conductive polymer, polyethylene
Treatment with ren oxide or the like can be mentioned.

The positive electrode active material used in the present invention may be a transition metal oxide capable of reversibly intercalating and deintercalating lithium ions, but lithium-containing transition metal oxides are particularly preferred.
Preferred lithium-containing transition metal oxide positive electrode active materials used in the present invention include lithium-containing Ti, V, Cr,
Oxides containing Mn, Fe, Co, Ni, Cu, Mo, and W can be mentioned. In addition, alkali metals other than lithium (elements of IA and IIA of the periodic table), and/or Al, G
a, In, Ge, Sn, Pb, Sb, Bi, Si, P,
B etc. may be mixed. Mixing amount is 0 for transition metal
~30 mol% is preferred. As a more preferable lithium-containing transition metal oxide positive electrode active material used in the present invention,
Lithium compounds/transition metal compounds (where transition metals are Ti, V, Cr, Mn, Fe, Co, Ni, Mo,
at least one selected from W) has a total molar ratio of 0.
It is preferable to synthesize by mixing so that the ratio is 3 to 2.2. Particularly preferred lithium-containing transition metal oxide positive electrode active materials used in the present invention include lithium compounds/transition metal compounds (where the transition metals are V, Cr, Mn,
At least one selected from Fe, Co, and Ni) are preferably mixed and synthesized so that the total molar ratio is 0.3 to 2.2. A particularly preferable lithium-containing transition metal oxide positive electrode active material used in the present invention is Lix Q
Oy (where Q is primarily, at least one of which is C
o, transition metals including Mn, Ni, V, Fe), x=0.
02 to 1.2, y=1.4 to 3). Q is Al, Ga, In, G
e, Sn, Pb, Sb, Bi, Si, P, B, etc. may be mixed. The mixing amount is 0 to 30 mol% with respect to the transition metal
is preferred.

Li _x CoO is the most preferable lithium-containing transition metal oxide positive electrode active material used in the present invention.
_{2 , LixNiO2 , LixMnO2 , LixCogN
i1 - gO2 , LixMn2O4 , LixCofV1 - f}
Oz (where x = _0.02-1.2 , g = 0.1-0.
9, f = 0.9 to 0.98, z = 2.01 to 2.3). Li _x CoO is the most preferable lithium-containing transition metal oxide positive electrode active material used in the present invention.
_{2 , LixNiO2 , LixMnO2 , LixCogN
i1 - gO2 , LixMn2O4 , LixCofV1 - fO
z} (where x=0.02-1.2, g=0.1-0.
9, f = 0.9 to 0.98, z = 2.02 to 2.3). Here, the above x value is a value before charging/discharging is started, and increases/decreases due to charging/discharging.

[0052] The positive electrode active material can be synthesized by a method of mixing a lithium compound and a transition metal compound and baking them, or by a solution reaction, but the baking method is particularly preferred. The firing temperature used in the present invention may be a temperature at which a part of the mixed compound used in the present invention decomposes and melts.
50 to 2000°C is preferred, especially 350 to 1500°C
is preferred. It is preferable to calcine at 250 to 900° C. during firing. The firing time is preferably 1 to 72 hours, more preferably 2 to 20 hours. Moreover, the method of mixing the raw materials may be either a dry method or a wet method. In addition, after firing 20
Annealing may be performed at 0°C to 900°C. The firing gas atmosphere is not particularly limited, and can be either an oxidizing atmosphere or a reducing atmosphere. For example, in the air, or gas adjusted to an arbitrary ratio of oxygen concentration, or hydrogen, carbon monoxide,
Nitrogen, argon, helium, krypton, xenon, carbon dioxide and the like.

In synthesizing the positive electrode active material of the present invention, as a method of chemically inserting lithium ions into the transition metal oxide, synthesis is carried out by reacting lithium metal, a lithium alloy, or butyllithium with the transition metal oxide. A method is preferred. Although the average particle size of the positive electrode active material used in the present invention is not particularly limited, it is preferably 0.1 to 50 µm.
Although the specific surface area is not particularly limited, it is 0.00 by the BET method.
01 to 50 m ² /g is preferred. Further, when 5 g of the positive electrode active material is dissolved in 100 ml of distilled water, the pH of the supernatant is preferably 7 or more and 12 or less. Well-known grinders and classifiers are used to obtain the desired particle size. For example, a mortar, a ball mill, a vibrating ball mill, a vibrating mill, a satellite ball mill, a planetary ball mill, a whirling jet mill, a sieve, and the like are used. The positive electrode active material obtained by firing may be washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent before use.

Negative electrode material and positive electrode active material used in the present invention
is based on Sn, Ge and Si
Amorphous oxide and Li_xCOO₂ , Li_xNiO₂ , Li
_xCo_gNi_1-gO.₂ , Li_xMnO₂ , Li_xMn₂
O._Four , or Li_xCo_fV. _1-fO._z(where x=0.
02-1.2, g=0.1-0.9, f=0.9-0.
98, z = 2.02 to 2.3).
Preferably, the amorphous oxide represented by the general formula (1) and Li
_xCOO₂ , Li_xNiO₂ , Li_xCo_gNi_1-gO.
₂ , Li_xMnO₂ , Li_xMn₂ O._Four , or Li_x
Co_fV._1-fO. _z(where x=0.02-1.2, g=
0.1-0.9, f=0.9-0.98, z=2.02
to 2.3), more preferably one
The amorphous oxide represented by the general formula (2) and Li_xCOO₂ ,
Li_xNiO₂ , Li_xCo_gNi_1-gO.₂ , Li_xM.
nO₂ , Li_xMn₂ O._Four , or Li_xCo_fV._1-f
O. _z(where x=0.02-1.2, g=0.1-0.
9, f = 0.9-0.98, z = 2.02-2.3)
In these cases, high discharge voltage, high capacity
It is possible to obtain a non-aqueous secondary battery with excellent charge-discharge cycle characteristics with a large amount.
can be done.

The equivalent of lithium insertion into the negative electrode material of the present invention is 3 to 10 equivalents, and the ratio of lithium to the positive electrode active material is determined according to this equivalent. It is preferable to multiply the usage ratio based on this equivalent weight by a factor of 0.5 to 2 times. If the lithium supply source is other than the positive electrode active material (eg, lithium metal, alloys, butyllithium, etc.), the amount of the positive electrode active material used is determined according to the lithium release equivalent of the negative electrode material. Also in this case, it is preferable to multiply the usage ratio based on this equivalent by a factor of 0.5 to 2 times. _SnGeSiO5 of the said compound example is mentioned as an example, and it demonstrates. When A equivalent of lithium is inserted (charged) into this compound, it becomes Li _A SnGeSiO ₅ , and when B equivalent of lithium is released (discharged) from this compound, Li _AB SnGeSi
becomes _O5 . Charging and discharging are performed between them according to the formula (4), and this is repeated. _SnGeSiO5- >LiA _SnGeSiO5 (formula- ₃ ) (discharge) LiA _{SnGeSiO5 LiAB SnGeSiO5 (} formula-4) (charge)

Examples of negative electrode materials that can be used in conjunction with the present invention include lithium metal and lithium alloys (Al, Al
-Mn, Al-Mg, Al-Sn, Al-In, Al-
Cd, etc.) and baked carbonaceous compounds capable of intercalating and deintercalating lithium ions or lithium metal. The purpose of using the lithium metal or lithium alloy in combination is to insert lithium into the negative electrode material used in the present invention in the battery, and does not utilize the dissolution/precipitation reaction of lithium metal or the like as a battery reaction.

Conductive agents, binders, fillers, and the like can be added to the electrode mixture. The conductive agent can be any electronically conductive material that does not undergo chemical changes in the constructed battery. Generally, natural graphite (flaky graphite, flaky graphite, earthy graphite, etc.), artificial graphite, carbon black, acetylene black, Ketjen black, carbon fibers and metals (copper, nickel, aluminum, silver (JP-A-63) -1
48,554)) powder, metal fibers, or conductive materials such as polyphenylene derivatives (JP-A-59-20,971) can be contained singly or as a mixture thereof. A combination of graphite and acetylene black is particularly preferred. The amount to be added is preferably 1 to 50% by weight, particularly preferably 2 to 30% by weight. For carbon and graphite, 2 to
15% by weight is particularly preferred.

Binders are generally starch, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, regenerated cellulose, diacetyl cellulose, polyvinyl chloride, polyvinylpyrrolidone,
Tetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, polybutadiene, fluororubber,
Polysaccharides such as polyethylene oxide, thermoplastic resins, polymers having rubber elasticity, and the like are used singly or as a mixture thereof. Moreover, when using a compound containing a functional group that reacts with lithium, such as a polysaccharide, it is preferable to deactivate the functional group by adding a compound such as an isocyanate group. The amount of the binder added is preferably 1 to 50% by weight, particularly 2 to 30% by weight.
is preferred. The filler can be any fibrous material that does not chemically change in the constructed battery. Ordinarily, olefinic polymers such as polypropylene and polyethylene, and fibers such as glass and carbon are used. The amount of filler added is not particularly limited, but 0
~30% by weight is preferred.

In using the negative electrode material of the present invention in a non-aqueous secondary battery system, a water-dispersed mixture paste containing the compound of the present invention is coated on a current collector, dried, and the water-dispersed mixture paste is applied to a current collector. is preferably 5 or more and less than 10, more preferably 6 or more and less than 9. Further, it is preferable to keep the temperature of the water-dispersed paste at 5° C. or more and less than 80° C., and to apply the paste onto the current collector within 7 days after preparation of the paste.

As an electrolyte, propylene is used as an organic solvent.
Lencarbonate, ethylene carbonate, butylene carbonate
carbonate, dimethyl carbonate, diethyl carbonate
gamma-butyrolactone, 1,2-dimethoxyethane
tetrahydrofuran, 2-methyltetrahydrofuran
dimethylsulfoxide, 1,3-dioxolane,
formamide, dimethylformamide, dioxolane,
Acetonitrile, Nitromethane, Methyl formate, Methyl acetate
mol, methyl propionate, ethyl propionate, phosphoric acid
triester (JP-A-60-23,973), trimetto
oxymethane (JP-A-61-4170), dioxolane
Derivatives (JP-A-62-15,771, JP-A-62-22,3
72, 62-108, 474), sulfolane
62-31, 959), 3-methyl-2-oxazolidi
non (JP-A-62-44,961), propylene carbon
Nate derivatives (JP-A-62-290,069, JP-A-62-
290,071), tetrahydrofuran derivatives
63-32, 872), diethyl ether (JP-A-63
-62,166), 1,3-propanesultone (JP-A-62,166),
63-102, 173) of aprotic organic solvents such as
Dissolves in a solvent mixed with at least one or more
Lithium salts, e.g. LiClO_Four , LiBF _Four , Li
PF₆ , LiCF₃ SO₃ , LiCF₃ CO₂ , LiA
sF₆ , LiSbF₆ , LiB_TenCl_Ten(JP-A-57-
74,974), lower aliphatic carboxylate lithium
1985-41,773), LiAlCl_Four , LiCl,
LiBr, LiI (JP-A-60-247,265),
Roroboran lithium (JP-A-61-165,957),
Lithium tetraphenylborate (JP-A-61-214,37
6) is composed of one or more salts such as in
also propylene carbonate or ethylene carbonate
and 1,2-dimethoxyethane and/or diethyl
LiCF in the mixture of carbonate₃SO₃, LiClO
_Four , LiBF_Four and/or LiPF₆ electrolysis containing
Quality is preferred. The amount of these electrolytes added to the battery is
Although not particularly limited, the amount of the positive electrode active material and the negative electrode material and the battery
The required amount can be used depending on the size of the supporting electrolysis
The concentration of electrolyte is 0.2-3 mol per liter of electrolyte.
preferable.

In addition to the electrolytic solution, the following solid electrolytes are also used.
can be used. Inorganic solid electrolytes are used as solid electrolytes.
They are divided into electrolytes and organic solid electrolytes. For inorganic solid electrolyte
Li nitrides, halides, oxyacids, etc. are often
Are known. Among them, Li₃ N, LiI, Li_Five N.
I₂ , Li₃ N-LiI-LiOH, LiSiO_Four , L
iSiO_Four -LiI-LiOH (JP-A-49-81,8
99), xLi₃ PO _Four -(1-x) Li_Four SiO_Four
(JP-A-59-60,866), Li₂ SiS₃(Unexamined
60-501,731), phosphorus sulfide compounds (JP-A-6
2-82,665) are effective. organic solid electrolyte
In the case of polyethylene oxide derivatives or containing such derivatives
Polymer (JP-A-63-135,447), polypropylene
a renoxide derivative or a polymer containing said derivative, ion
A polymer containing a dissociative group (JP-A-62-254, 30
2, 62-254, 303, 63-193, 95
4), a polymer containing an ionic dissociation group and the aprotic
A mixture of electrolytes (U.S. Pat. No. 4,792,504, ibid.)
4,830,939, JP-A-62-22375, JP-A-6
2-22,376, 63-22,375, 63-2
2,776, JP-A-1-95,117), phosphoric acid ester
A polymer (JP-A-61-256573) is effective.
be. In addition, polyacrylonitrile is added to the electrolyte
There is also a method (JP-A-62-278774). Also, no
A method of using both a machine and an organic solid electrolyte (Japanese Patent Application Laid-Open No. 60-1,
768) are also known.

It is also known to add the following compounds to the electrolyte for the purpose of improving discharge and charge/discharge characteristics. For example, pyridine (JP-A-49-108, 52
5), triethyl phosphite (JP-A-47-4, 3
76), triethanolamine (JP-A-52-72, 4
25), cyclic ethers (JP-A-57-152, 68)
4), ethylenediamine (JP-A-58-87, 77)
7), n-glyme (JP-A-58-87778), hexaphosphate triamide (JP-A-58-87779),
Nitrobenzene derivatives (JP-A-58-214,28
1) Sulfur (JP-A-59-8280), quinone imine dye (JP-A-59-68184), N-substituted oxazolidinone and N,N'-substituted imidazolidinone (JP-A-5
9-154,778), ethylene glycol dialkyl ether (JP-A-59-205,167), quaternary ammonium salt (JP-A-60-30,065), polyethylene glycol (JP-A-60-41). , 773), pyrrole (JP-A-60-79,677), 2-methoxyethanol-
(JP-A-60-89075), AlCl ₃ (JP-A-61-88466), conductive polymer-electrode active material monomer (JP-A-61-161673), triethylene phosphor Amide (JP-A-61-208,758), trialkylphosphine (JP-A-62-80,976), morpholine (JP-A-62-80,977), aryl compound having a carbonyl group (JP-A-62) Showa 62-86, 67
3) Hexamethylphosphoric triamide and 4-alkylmorpholine (JP-A-62-217,575), bicyclic tertiary amine (JP-A-62-217,578), oil (JP-A-62) -287,580), quaternary phosphonium salts (JP-A-63-121,268), and tertiary sulfonium salts (JP-A-63-121,269).

In order to make the electrolyte nonflammable, the electrolyte may contain a halogen-containing solvent such as carbon tetrachloride or ethylene trifluorochloride. (JP-A-48-36,
632) In addition, carbon dioxide gas can be contained in the electrolytic solution in order to make it suitable for high-temperature storage (Japanese Laid-Open Patent Publication No. 59-1
34,567). Also, the mixture of the positive electrode and the negative electrode can contain an electrolytic solution or an electrolyte. For example, the ion conductive polymer and nitromethane (JP-A-48-3
6,633), electrolytic solution (JP-A-57-124,870)
It is known to include

As the separator used in the present invention, a material having high ion permeability, a predetermined mechanical strength, and insulating microporous or gaps is used. Furthermore, in order to improve safety, it is necessary to have a function of closing the gap at 80° C. or higher to increase the resistance and cut off the current. The closing temperature of these gaps is 90° C. or more and 180° C. or less. Although the method of creating the gap varies depending on the material, any known method may be used. In the case of porous films, the pore shape is usually circular or elliptical and the size is from 0.05 μm to 30 μm, preferably from 0.1 μm to 20 μm. Furthermore, the pores may be rod-shaped or amorphous, as in the case of making by drawing or phase separation. In the case of cloth, the gaps are voids between fibers and depend on how the woven and nonwoven fabrics are made. The ratio of these gaps, that is, the porosity is 20% to 90%, preferably 35% to 80%.

The separator of the present invention has a thickness of 5 μm or more and 10
0 μm or less, more preferably 10 μm or more and 80 μm or less, microporous films, woven fabrics, non-woven fabrics, and the like.
The separator of the present invention contains at least two ethylene components
0% by weight is preferred, and 30% is particularly preferred
It includes the above. Components other than ethylene include propylene, butene, hexene, ethylene fluoride, vinyl chloride, vinyl acetate and acetalized vinyl alcohol, with propylene fluoride being particularly preferred.

The microporous film is preferably made of polyethylene, ethylene-propylene copolymer or ethylene-butene copolymer. Further, a material made by mixing and dissolving polyethylene, polypropylene polyethylene and polytetrafluoroethylene is also preferable. Non-woven fabrics and woven fabrics have a thread diameter of 0, 1 μm to 5 μm, and are made of polyethylene, ethylene-propylene copolymer, ethylene-butene 1 copolymer, ethylene-methylbutene copolymer, ethylene-methylpentene copolymer, polypropylene, Those made of polytetrafluoroethylene fibers are preferred.

[0067] These separators may be of a single material or of a composite material. In particular, a laminate of two or more types of microporous films with different pore sizes, porosity, pore closing temperature, etc., composites of materials with different forms, such as microporous films and nonwoven fabrics, microporous films and woven fabrics, and nonwoven fabrics and paper. is particularly preferred. The separator of the present invention may contain indefinite fibers such as glass fibers and carbon fibers, and inorganic particles such as silicon dioxide, zeolite, alumina and talc. Further, the voids and surfaces may be treated with a surfactant to make them hydrophilic.

As the current collectors for the positive and negative electrodes, any electron conductors that do not undergo chemical changes in the constructed battery may be used. For example, the positive electrode may be made of stainless steel, nickel, aluminum, titanium, carbon, or the like, or the surface of aluminum or stainless steel may be treated with carbon, nickel, titanium, or silver.
Aluminum or an aluminum alloy is particularly preferred. Materials for the negative electrode include stainless steel, nickel,
In addition to copper, titanium, aluminum, and carbon, copper or stainless steel whose surface is treated with carbon, nickel, titanium, or silver, and Al--Cd alloys are used. Copper or a copper alloy is particularly preferred. Oxidizing the surface of these materials is also used. Moreover, it is desirable to make the surface of the current collector rough by surface treatment. As for the shape, in addition to foil, films, sheets, nets, punched materials, laths, porous bodies, foams, molded bodies of fiber groups, and the like are used. The thickness is not particularly limited, but 1
˜500 μm is used.

The shape of the battery can be coin, button, sheet, cylinder, flat, square, or any other shape. When the shape of the battery is a coin or a button, the mixture of positive electrode active material and negative electrode material is mainly used after being compressed into a pellet shape.
The thickness and diameter of the pellet are determined by the size of the battery. When the shape of the battery is a sheet, a cylinder, or a square, the mixture of the positive electrode active material and the negative electrode material is mainly used by being applied (coated) on the current collector, dried, and compressed. A general method can be used for the coating method. for example,
reverse roll method, direct roll method, blade method,
The knife method, extrusion method, curtain method, gravure method, bar method, dip method and squeeze method can be mentioned. Among them, the blade method, the knife method and the extrusion method are preferred. Application is 0.1-1
It is preferably carried out at a speed of 00 m/min. At this time, by selecting the coating method according to the solution properties and drying properties of the mixture, a good surface condition of the coating layer can be obtained. The coating may be applied one side at a time or simultaneously on both sides. Also, the application may be continuous, intermittent, or striped. The thickness, length and width of the coating layer are determined according to the size of the battery, but the thickness of the coating layer on one side is particularly preferably 1 to 2000 µm in the compressed state after drying.

[0070] As a method for drying or dehydrating the pellets or sheets, generally employed methods can be used. In particular, hot air, vacuum, infrared rays, far infrared rays, electron beams and low humidity air are preferably used alone or in combination. The temperature is preferably in the range of 80 to 350°C, especially 10°C.
A range of 0 to 250°C is preferred. The water content is preferably 2000 ppm or less for the entire battery, and preferably 500 ppm or less for each of the positive electrode mixture, the negative electrode mixture and the electrolyte in terms of cycle performance. As a method for pressing pellets or sheets, a commonly used method can be used, but die press method and calendar press method are particularly preferred. Although the press pressure is not particularly limited, it is 0.2 to 3 t/
cm ² is preferred. The press speed of the calendar press method is preferably 0.1 to 50 m/min, and the press temperature is room temperature to 2
00°C is preferred. The ratio of the negative electrode sheet width to the positive electrode sheet is preferably 0.9 to 1.1, particularly preferably 0.95 to 1.0. The content ratio of the positive electrode active material and the negative electrode material varies depending on the type of compound and mixture formulation, so it cannot be limited, but it can be set to an optimum value from the viewpoint of capacity, cyclability, and safety.

[0071] The material mixture sheet and the separator were laminated together.
After combining, the sheets are rolled and folded.
and insert it into the can, electrically connect the can and the sheet, and then electrolyze
A liquid is injected, and a battery can is formed using a sealing plate. this
Sometimes the safety valve can be used as a sealing plate. safety valve
In addition, it is equipped with various conventionally known safety elements.
can be For example, fuses,
A bimetal, a PTC element, or the like is used. Also safe
In addition to the valve, as a countermeasure against the internal pressure rise of the battery can, switch the battery can.
method, gasket crack method or sealing plate turtle
It is possible to use the splitting method or the cutting method with the lead plate.
can. In addition, overcharge and overdischarge countermeasures are incorporated into the charger.
Equipped with a protection circuit or connected independently
good too. In addition, as a countermeasure against overcharging, the battery internal pressure rises.
It can be provided with a method for interrupting the current flow. with this
If the mixture or electrolyte contains a compound that increases internal pressure,
can of compounds used to increase internal pressure
For example, Li₂ CO ₃ , LiHCO₃ , Na₂ CO
₃ , NaHCO₃ , CaCO₃ , MgCO₃ Carbonic acid such as
Examples include salt.

[0072] The can and the lead plate can be made of a metal or alloy having electrical conductivity. For example, metals such as iron, nickel, titanium, chromium, molybdenum, copper and aluminum or alloys thereof are used. cap,
Known methods (eg, DC or AC electric welding, laser welding, ultrasonic welding) can be used for welding cans, sheets, and lead plates. A conventionally known compound or mixture such as asphalt can be used as the sealing agent for sealing.

Applications of the non-aqueous secondary battery of the present invention are not particularly limited. type word processor, pocket word processor, electronic book player, mobile phone, cordless phone handset, pager, handy terminal, mobile fax, mobile copy, mobile printer, headphone stereo, video movie, liquid crystal television, handy cleaner, portable CD, mini disc, Electric shavers, electronic translators, car phones,
Walkie-talkies, power tools, electronic notebooks, calculators, memory cards, tape recorders, radios, backup power supplies, memory cards, and the like. Other consumer products include automobiles, electric vehicles, motors, lighting fixtures, toys,
Game machines, load conditioners, irons, watches, strobes, cameras, medical devices (pacemakers, hearing aids, shoulder massage machines, etc.), etc. Furthermore, it can be used for various military applications and space applications. It can also be combined with a solar cell.

[0074]

EXAMPLES The present invention will be described in more detail below with reference to specific examples, but the present invention is not limited to these examples as long as the gist of the invention is not exceeded.

Synthesis Example-1 Tin pyrophosphate 10.3 g, tin monoxide 6.7 g, diboron trioxide 1.7 g, potassium carbonate 0.69 g, magnesium oxide 0.4 g, germanium dioxide 1.0 g, silicon dioxide 0 .6 g were dry mixed, placed in an alumina crucible and heated to 1100° C. at 15° C./min under argon atmosphere.
After sintering at 1100° C. for 12 hours, the temperature was lowered to room temperature at 10° C./min, taken out from the sintering furnace, and SnGe _0.1 Si
_0.1 B _0.5 P _0.5 Mg _0.1 K _0.1 O _{3.55 was} obtained. The compound was coarsely pulverized and further pulverized with a jet mill to obtain a powder having an average particle size of 7.0 μm (compound 1-1). This is Cu
It has a broad peak with an apex near 28° at the 2θ value in the X-ray diffraction method using Kα rays, and 2
No crystalline diffraction line was observed at a θ value of 40° or more and 70° or less. In the same manner, stoichiometric amounts of raw materials were mixed, fired, and pulverized to synthesize the following compounds.

_{SnGe0.1Si0.5P0.2B0.3Al0.1O3.3 ( 1-2 ) SnGe0.1Si0.5B0.2Mg0.1Al0.1O2.75 ( 1-3 ) SnGe0.1Si0.1B0.5Al0.1OK3 , _ _ _ _ _ _ _ _ 6} (1-4) SnGe _0.1 Si _0.2 P _0.5 B _0.5 Ba _0.05 K _0.1 O ₃ , 3 (1-5) SnGe _0.1 Si _0.2 P _0.5 B _0.5 Pb _0.05 K _0.1 O 3, ₃₅ (1-6) SnGe _{0.1 Si0.05P0.5B0.5Cs0.1O3,26 ( 1-7 ) SnGe0.1Si0.2P0.5B0.5Mg0.01O3,25 ( 1-8 ) SnGe0.1Si0.3P0.5B0.5Mg0.1Li30.1O _ _ _ _ _ _ _ _ _ , 65} (1-9) SnGe _0.1 Si _0.2 P _0.5 B _0.5 Na _0.1 O 3 , 65 (1-10) _{SnGe 0.1} Si _0.1 P _0.5 B _0.5 Rb _0.1 O 3 , 45 (1-11) _{SnGe 0.1} Si _0.2 P _0.5 B _0.5 Ca _0.05 K _0.1 O _3,7 (1-12) SnGe _0.1 Si _0.1 P _0.5 B _0.5 Mg _0.1 K _0.1 F _0.1 O 3, ₃₅ (1-13) _{SnGe 0.1} Si _0.02 P _0.5 B _0.5 Sc K _0.1 O _3,32 (1-14) SnGe _0.1 Si _0.2 P _0.5 B _0.5 Y _0.01 K _0.1 O _3,665 (1-15) SnGe _0.1 Si _0.1 P _0.5 B _0.5 Mg _0.1 K _0.1 Al _0.05 O _3.675 ( _{16 ) SnGe0.2Si0.3P0.1B0.1Mg0.5K0.5O3.15 ( 1-17 ) SnGe0.1Si0.7P0.1B0.1K0.5O3.25 ( 1-18 ) SnGe0.1Si0.4P0.35B _ _ _ _ _ _ _ _ O3.65 ( 1-19 ) SnGe0.1Si0.5P0.6B0.3Mg0.1K _ 0.1} O _4,3 (1-20) SnGe _0.1 Si _0.2 P _0.45 B _0.45 Mg _0.1 K _0.1 O _3,45 (1-21) SnGe _0.2 Si _0.3 P _0.45 B _0.45 Mg _0.1 K _0.1 O _3,95 (1- _{22 ) SnGe0.01Si0.2P0.45B0.45Mg0.1K0.1O2,77 ( 1-23 ) SnGe0.001Si0.3P0.45B0.45Mg0.1K0.1O3.552 ( 1-24 ) SnGe0.01Si0.1K0.1O3.552 ( 1-24 ) SnGe0.4Si0.4P0.5B0.5 _ _ _ Mg0.1K0.1O3,25 ( 1-25 ) SnGe0.02Si0.1P0.45B0.45Mg0.1K0.1O3,29 ( 1-26 ) SnGe0.1Si0.7P0.4As0.1B0.1K0.1Mg4 _ _ _ _ _ _ _ _ _ 15} (1-27) SnGe _0.1 Si _0.01 P _0.4 B _0.6 Mg _0.1 K _0.1 O 3, ₂₇ (1-28) SnGe _0.1 Si _0.1 P _0.4 B _0.6 Cs _0.1 O 3, ₃₅ (1-29) SnGe _0.1 Si _0.5 P _1.0 Mg _0.2 K _0.1 O 4, 95 (1-30) _{SnGe 0.1} Si _0.01 P _0.6 B _0.6 K _0.1 Mg _0.01 O 3, 68 ( _1-31 ) _{SnGe 0.5} Si _0.2 P _0.7 B _0.8 K _0.2 Mg 5, 65 (1-32) _{SnGe 0.8} Si _0.05 P _0.9 B _0.9 K _0.1 Mg _0.1 O 6, 75 (1-33) _{SnGe 1.0} Si _0.001 P _1.0 B _1.0 Cs _0.1 O 7, 052 (1-34) _{SnGe 1.3} Si _0.005 P _1.0 B _1.0 K _0.2 O _8.71 (1-35) SnGeSiO ₅ (1-36) SnGeSi ₂ O ₇ (1-37) SnGe _1.3 Si _1.6 O _6.8 (1-38) SnGe _0.3 Si _2.0 O _6.6 (1 _{-39 ) SnGe0,05Si0.3P0,45B0,45Mg0,1K0,1O3,34 ( _ _ _ 1-40 ) SnGe0,05Si0.2P0,5B0,5Al0,1Mg0,1K0,1O3,425 ( 1-41 ) SnGe0,1Si0.1P0,5B _ _ _ _ 0} , 5 Mg ₀ , 1 K ₀ , 1 O 3, ₃₅ (1-42) SnGe ₀ , 1 Si _0.1 P 0, ₄ B 0, ₆ Cs ₀ , 1 O 3, 25 (1-43) _{SnGe 0, 2Si0.2P0,5B0,5Cs0,05K0,05O3,75 ( 1-44 ) SnGe0,7Si1.0P0,7K0,1O3,74 ( 1-45 _ _ _ _ _} ) SnSi _0.5 B _0.2 Al _0.1 Mg _0.1 O _2.55 (1-46) SnSiO ₃ (1-47) SnGeO ₃ (1-48) These compounds also have a 2θ value of 20 in the X-ray diffraction method using CuKα rays. It had a broad scattering band with an apex at 40° to 40°. However, compound 1-48 was crystalline.

Example-1 As a method for preparing a mixture, the negative electrode material was composed of 82% by weight of the compound 1-1 synthesized in Synthesis Example-1, 8% by weight of flake graphite as a conductive agent, and 4% by weight of acetylene black. %, as a binder, pellets (13 mm Φ, 22
mg) was used after drying with a far infrared heater (150°C for 3 hours) in a dry box (dew point -40 to -70°C, dry air). Among positive electrode materials, the positive electrode active material LiCoO ₂
82% by weight, 8% by weight of flake graphite as a conductive agent, 4% by weight of acetylene black as a conductive agent, and 6% by weight of tetrafluoroethylene as a binder. (13 mmΦ, compound A-1
to match the lithium insertion capacity of The charge capacity of LiCoO ₂ was set to 140 mAh/g. ) was used after drying with a far infrared heater (150° C. for 3 hours) in the same dry box as above. As the current collector, a net of SUS316 with a thickness of 80 μm was welded to a coin can for both the positive and negative electrode cans.
LiPF ₆ with a supporting electrolyte of 0.95 mol/L as an electrolyte
and 0.05 mol/L of LiBF ₄ mixed supporting salt (2:8 volume mixture of ethylene carbonate and diethyl carbonate) was used, and 200 μl of the mixture was used. A non-woven fabric was impregnated with the electrolytic solution. Then, a coin-type non-aqueous secondary battery as shown in FIG. 1 was produced in the same dry box as above.

This non-aqueous secondary battery was charged at 0.75 mA/cm ² .
A charge/discharge test was performed in the range of 4.15 to 2.8 V at a constant current density of 1 (all tests started from charging).
The results are shown in Table 1. The abbreviations shown in Table 1 are
(a) negative electrode material of the present invention, (b) first discharge capacity (mAh per 1 g of negative electrode material), (c) average discharge voltage (V),
(d) charge-discharge cyclability (60% of the first discharge capacity
The number of cycles at which the capacity is reached) is shown. Coin-type non-aqueous secondary batteries were produced in the same manner for compounds 1-2 to 1-45 shown in Synthesis Examples, and charge/discharge tests were performed. The results are shown in Table 1. From these results, it can be seen that the negative electrode active material used in the present invention is excellent in charge-discharge cyclability and provides a non-aqueous secondary battery with high discharge voltage and high capacity.

[0079]

[Table 1]

[0080]

[Table 2]

Comparative Example-1 In Example-1, SnO as a reagent and compounds 1-46 to 1-4 synthesized in Synthesis Example 1 were used instead of the negative electrode material 1-A.
A coin-type non-aqueous secondary battery was produced in the same manner as in Example-1 except that No. 8 was used, and a charge/discharge test was performed. Table 1 shows the results of a charge/discharge test on these compounds. From these results, it can be seen that the compounds of the present invention are superior to any of the comparative compounds in charge/discharge cycle characteristics and capacity.

Example-2 Compound 1-1 synthesized in Synthesis Example-1 was used as a negative electrode material, and 88% by weight of compound 1-1 was used, 6% by weight of flake graphite, and polyvinylidene fluoride as a binder were dispersed in water. 4% by weight of the product, 1% by weight of carboxymethyl cellulose and 1% by weight of lithium acetate were added and kneaded using water as a medium to prepare a slurry. The slurry was applied to both sides of a copper foil having a thickness of 18 μm by an extrusion method, dried, compression-molded by a calender press, and cut to a predetermined width and length to prepare a strip-shaped negative electrode sheet. The thickness of the negative electrode sheet was 78 μm. LiCoO ₂ as a positive electrode material
87% by weight, 6% by weight of flake graphite, 3% by weight of acetylene black, and 3% by weight of polytetrafluoroethylene aqueous dispersion and 1% by weight of sodium polyacrylate as binders.
A slurry obtained by adding weight % and kneading with water as a medium was coated on both sides of a 20 μm thick aluminum foil, dried, pressed and cut in the same manner as described above. and thickness 2
A 50 μm strip-shaped positive electrode sheet was produced. nickel at each end of the negative electrode sheet and the positive electrode sheet;
After the aluminum lead plate was spot-welded, it was dehydrated and dried in dry air with a dew point of -40°C or less at 230°C for 30 minutes. Furthermore, the dehydrated and dried positive electrode sheet (8), the microporous polyethylene film separator, the dehydrated and dried negative electrode sheet (9) and the separator (10) were laminated in this order, and spirally wound with a winder.

This wound body was housed in a nickel-plated steel cylindrical battery can (11) with a bottom, which also served as a negative electrode terminal. Further, the same electrolyte as in Example-1 was injected into the battery can. A battery lid (12) having a positive electrode terminal was crimped through a gasket (13) to produce a cylindrical battery. The positive electrode terminal (12) was previously connected to the positive electrode sheet (8), and the battery can (11) was previously connected to the negative electrode sheet (9) by means of lead terminals. FIG. 2 shows a cross section of a cylindrical battery.
(14) is a safety valve. Charge and discharge conditions are 4.1
5 to 2.8 V and 1 mA/cm ² . The results are shown in Table 2. The abbreviations shown in Table 2 are (b), (c),
(d) Both are the same as Example-1. (e) shows the energy density per AA battery. Compounds 1-2, 1-3, 1-4, 1-7, 1-12 synthesized in Synthesis Example-1,
1-16, 1-17, 1-19, 1-21, 1-22,
1-23, 1-24, 1-26, 1-27, 1-30,
1-33, 1-34, 1-36, 1-37, 1-41,
Table 2 shows the results of evaluation in the same manner for 1-44.
shown.

[0084]

[Table 3]

Comparative Example-2 In Example-2, compound 1-1 was used as the negative electrode active material.
instead of SnO, compounds 1-46, 1-47, 1-4
A cylindrical battery was prepared in the same manner as in Example-2 except that No. 8 was used, and a charge/discharge test was performed. The results are shown in Table 2.

Example 3 Compound 1-1 synthesized in Synthesis Example 1 was used as a negative electrode material, and 88% by weight of compound 1-1 was used, 6% by weight of flake graphite, and polyvinylidene fluoride as a binder was dispersed in water. 4% by weight of the product, 1% by weight of carboxymethyl cellulose and 1% by weight of lithium acetate were added and kneaded using water as a medium to prepare a slurry. The slurry was applied to both sides of a copper foil having a thickness of 18 μm by an extrusion method. On top of this, α-Al ₂ O ₃ (average particle diameter 1 μm) 94, 5% by weight, polyvinylidene fluoride 4, 5% by weight, and carboxymethyl cellulose 1% by weight were mixed and kneaded using water as a medium to form a slurry. A protective layer was provided by applying the sintered material. After drying, it was compression-molded by a calender press and cut into a predetermined width and length to prepare a strip-shaped negative electrode sheet. The thickness of the negative electrode sheet was 100 μm. As a positive electrode material, 87% by weight of LiCoO ₂ , 6% by weight of flake graphite,
3% by weight of acetylene black, 3% by weight of polytetrafluoroethylene aqueous dispersion and 1% by weight of sodium polyacrylate as binders were added, and the resulting slurry was kneaded using water as a medium. was applied to both sides of the sample in the same manner as above. On top of this, α-Al
₂ O ₃ (average particle size 1 μm) 94, 5% by weight, polyvinylidene fluoride 4, 5% by weight, carboxymethyl cellulose 1
They were mixed at a weight % ratio, kneaded using water as a medium to form a slurry, and applied to provide a protective layer. After drying, it was compression-molded with a calender press and cut into a predetermined width and length to prepare a belt-shaped positive electrode sheet. The thickness of the positive electrode sheet was 265 μm. A cylindrical battery was produced in the same manner as in Example 2 using these negative electrode sheet and positive electrode sheet.
Ten such batteries were prepared, charged to 4.15 V at 1 mA/cm ² , and stored at 60° C. for 3 weeks. After 3 weeks, the circuit voltage of each battery was measured and the following results were obtained.

[0087] 1, 4, 11V 2, 4, 10V 3, 4, 10V 4, 4, 10V 5, 4, 09V 6, 4, 11V 7, 4, 09V 8, 4, 11V 9, 4, 10V 10, 4, 11V

Example-4 Using the compound 1-2 as a negative electrode material, 10 cylindrical batteries provided with a protective layer in the same manner as in Example-3 were prepared and subjected to the same test as in Example-3. These results are shown below.

[0089] 1, 4, 10V 2, 4, 11V 3, 4, 11V 4, 4, 10V 5, 4, 09V 6, 4, 10V 7, 4, 09V 8, 4, 10V 9, 4, 11V 10, 4, 10V

Comparative Example-3 Using SnO as a negative electrode material, 10 cylindrical batteries (Batteries A-1 to A-10) were prepared in the same manner as in Comparative Example-2.
I did the same test as 3. Further, 10 cylindrical batteries (Batteries B-1 to B-10) provided with a protective layer in the same manner as in Example-3 were prepared using SnO as the negative electrode material, and subjected to the same test as in Example-3. These results are shown below. Battery A-1 1.02 V Battery B-1 4.10 V −2 0.47 V −2 2.38 V −3 0.72 V −3 4.12 V −4 0.92 V −4 4.09 V −5 1.21 V − 5 4.10V -6 0.02V -6 3.22V -7 0.66V -7 4.10V -8 1.01V -8 2.19V -9 0.55V -9 4.11V -10 0.47V - From the result of 10 4.10 V or more, it can be seen that the battery of the present invention clearly has less voltage drop during storage and has stable performance.

Example-5 300 same batteries as in Example-3 were prepared and charged to 4.15V. When we counted the number of batteries with poor charging, we found 0
was individual.

Example-6 300 batteries were prepared in the same manner as in Example-4 and charged to 4.15V. When we counted the number of batteries with poor charging, we found 0
was individual.

COMPARATIVE EXAMPLE-4 300 batteries (Batteries A and B) were produced in the same manner as in Comparative Example-3, and tested in the same manner as in Example-4. As a result, there were 10 defective batteries in A battery, and 10 batteries in B battery.
There were 3 batteries. From the above results, it can be clearly seen that the battery of the present invention is resistant to short-circuiting, has a low rate of defective products, and is safe.

[0094]

INDUSTRIAL APPLICABILITY As in the present invention, when at least one specific amorphous composite oxide mainly composed of Sn and Ge is used as a negative electrode material, high discharge operation voltage, large discharge capacity and excellent charge/discharge are obtained. It is possible to obtain a non-aqueous secondary battery that provides cycle characteristics. By providing a protective layer on the negative electrode and/or the positive electrode, a safe non-aqueous secondary battery can be provided.

[Brief description of the drawing]

FIG. 1 shows a cross-sectional view of a coin-type battery used in Examples.

FIG. 2 shows a cross-sectional view of a cylindrical battery used in Examples.

[Description of symbols]

1 negative electrode sealing plate 2 Negative electrode mixture pellet 3 Separator 4 positive electrode mixture pellet 5 current collector 6 positive electrode case 7 Gasket 8 positive electrode sheet 9 negative electrode sheet 10 Separator 11 battery can 12 Battery lid 13 Gasket 14 safety valve

Claims (4)

[Claims] 1. A non-aqueous secondary battery comprising a positive electrode material, a negative electrode material, a non-aqueous electrolyte containing a lithium salt, and a separator, wherein the negative electrode material is an amorphous oxide mainly composed of Sn, Ge and Si. A non-aqueous secondary battery comprising: 2. The negative electrode material has the general formula (1) SnGe _a Si _b M ¹ _c M ² _d O _e (1) (wherein M ¹ is at least one selected from Al, Pb, As, P and B). one or more elements, M2 is at least one element selected from Group 1 elements, Group ² elements, Group 3 elements, and halogen elements of the periodic table, a is a number of 0.001 or more and 1 or less, b is 0.001 or more; 001 or more and 2 or less, c is a number of 0.2 or more and 2 or less, d is a number of 0.01 or more and 1 or less, and e is a number of 1, 3 or more and 11 or less. 2. The non-aqueous secondary battery according to claim 1, wherein the non-aqueous secondary battery is a substance. 3. The negative electrode material has the general formula (2) SnGe _a Si _b M ³ _c M ⁴ _d O _e (1) (wherein M ³ is at least one element selected from Al, P and B ^.M4 is Li, K, Na, Rb, Cs,
At least one or more elements selected from Ca, Mg, Ba, Sc, Y and F; a is a number between 0.001 and 1. b is a number between 0.001 and 2; c represents a number from 0.2 to 2, d represents a number from 0.01 to 1, and e represents a number from 1, 3 to 11. 3. The non-aqueous secondary battery according to claim 1, wherein the non-aqueous secondary battery is an amorphous oxide represented by ). 4. The non-aqueous secondary battery according to any one of claims 1 to 3, wherein said negative electrode and/or positive electrode has at least one protective layer.