JPH0424831B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel secondary battery, and more particularly to a small and lightweight secondary battery. [Prior Art] In recent years, electronic devices have become smaller and lighter, and there is a great demand for batteries that serve as power sources to be smaller and lighter. In the field of primary batteries, small and lightweight batteries such as lithium batteries have already been put into practical use, but because these are primary batteries, they cannot be used repeatedly, and their fields of application have been limited. On the other hand, in the field of secondary batteries, lead batteries and nickel-cadmium batteries have conventionally been used, but both have major problems in terms of miniaturization and weight reduction. From this point of view, non-aqueous secondary batteries have attracted much attention, but have not yet been put into practical use. One of the reasons for this is that no electrode active material used in the secondary battery has been found that satisfies practical physical properties such as cyclability and self-discharge characteristics. On the other hand, a new group of electrode active materials that utilize the intercalation or doping phenomenon of layered compounds, which are essentially different reaction types from conventional nickel-cadmium batteries, lead batteries, etc., are attracting attention. Such new electrode active materials do not cause complex chemical reactions during electrochemical reactions during charging and discharging, and are therefore expected to have extremely excellent charge-discharge cycle performance. For example, chalcogenite compounds having a layered structure are attracting attention as an example of utilizing intercalation of layered compounds. For example, Li _x TiS ₂ , Li _x
Although chalcogenite compounds such as MoS ₃ have relatively good cyclability, their electromotive force is low.
Even when Li metal is used for the negative electrode, the practical discharge voltage is around 2V at most, which is not satisfactory in terms of high electromotive force, which is one of the characteristics of non-aqueous batteries. On the other hand, it also has a layered structure.
Metal oxide compounds such as Li _x V ₂ O ₅ , Li _x V ₆ O ₁₃ , Li _x CoO ₂ , and Li _x NiO ₂ are attracting attention because of their high electromotive force. However, these metal oxide compounds have inferior performance in terms of cycleability, utilization rate, that is, the ratio that can actually be used for charging and discharging, and furthermore, in terms of overvoltage during charging and discharging, so they have not yet been put into practical use. Not yet. In particular, it is disclosed in Japanese Patent Application Laid-open No. 55-136131.
Secondary battery positive electrodes such as Li _x CoO ₂ and Li _x NiO ₂ have an electromotive force of 4V or more when Li metal is used as the negative electrode.
Moreover, the theoretical energy density (per positive electrode active material)
Although it has an amazing value of 1100 Whr/Kg or more, the proportion that can actually be used for charging and discharging is low, and the energy density obtained is far from the theoretical value. US Pat. No. 4,497,726 states that the positive electrode,
It has been shown that a metal oxide compound represented by the general formula Li _x M _y M′ _z O _22-o Fn is used. but,
Even with this, the above-mentioned problems have not been sufficiently solved. On the other hand, as an example of an electrode active material that utilizes a doping phenomenon, a new type of secondary battery that uses a conductive polymer as an electrode material, for example,
It is described in Publication No. 136469. however,
Secondary batteries using such conductive polymers also have unresolved problems such as instability, ie, low cycleability, and large self-discharge, and have not yet been put into practical use. In addition, JP-A-58-35881, JP-A-59-173979, and JP-A-59-207568 propose the use of high surface area carbon materials such as activated carbon as electrode materials. A unique phenomenon has been found in such electrode materials, which is different from the doping phenomenon and is thought to be caused by the formation of an electric double layer based on the high surface area of the electrode materials, and it is said that they exhibit excellent performance especially when used in positive electrodes.
In addition, some documents describe that such high surface area carbon materials can be used as negative electrodes, but when such high surface area carbon materials are used as negative electrodes, there are major drawbacks in cycle characteristics and self-discharge characteristics, and the utilization rate is low. , that is, the ratio of electrons (or counter cations) that can reversibly enter and exit per carbon atom is extremely low, usually less than 0.05.
0.01 to 0.02, which means that when used as a negative electrode of a secondary battery, both weight and volume become extremely large, which is a major drawback in practical use. In addition, Japanese Patent Application Laid-Open No. 58-209864 describes carbides of phenolic fibers with a hydrogen atom/carbon atom ratio of 0.33 to
It is described that carbonaceous materials in the range of 0.15 are used as electrode materials. It is said that it exhibits excellent characteristics when it is mainly p-doped with anions and used as a positive electrode material, and it is also described that it can be n-doped with cations and used as a negative electrode material. However, such materials also have their n-
When the doped material is used as a negative electrode, the cycleability,
In addition to having a major drawback in self-discharge characteristics, the utilization rate was also extremely low, which was a major drawback in practical use. Furthermore, it has been known for a long time that graphite intercalation compounds can be used as secondary battery electrode materials.
It is known to use a graphite intercalation compound incorporating anions such as Br, ClO ₄ and BF ₄ ions as a positive electrode. On the other hand, it is naturally possible to use a graphite intercalation compound incorporating cations such as Li ions as a negative electrode, and in fact, for example,
The publication describes the use of a graphite intercalation compound incorporating cations as a negative electrode. However, graphite intercalation compounds incorporating such cations are extremely unstable, and have particularly high reactivity with electrolytes, as reported in the Journal of Electrochemistry by ANDey and others.・Society (Journal of Electrochemical Society) vol117
No. 2P. 222-224 1970", it is clear that when graphite or graphite, which can form intercalation compounds, is used as a negative electrode, it lacks stability as a battery such as self-discharge, and the above-mentioned utilization rate was extremely low and could not be put to practical use. British Published Patent No. 2150741 states that as an electrode for a secondary battery, the surface area is 0.1 m ² /g to 50 m ² /g.
It has been shown that carbonaceous materials are suitable, and JP-A-58-93176 also shows that a fired polymer body is used for both the positive electrode and the negative electrode, or for either one of the positive electrode and the negative electrode. The density of the polymer fired body is 1.8
It has been shown that g/cm ³ or less is preferable. but,
Even with these methods, the above-mentioned problems have not been sufficiently solved. [Problems to be solved by the invention] As mentioned above, the new group of electrode active materials that utilize intercalation or doping have not yet achieved the originally expected performance from a practical standpoint. This is the current situation. [Means and effects for solving the problems] The present invention solves the above-mentioned problems and provides a high-performance, high-energy-density, compact, lightweight secondary battery with excellent battery performance, particularly cyclability and self-discharge characteristics. It was done in order to The first invention is a secondary battery having a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte, characterized in that the following is used as an active material of the positive electrode and the following is used as an active material of the negative electrode. It provides secondary batteries. : Non-carbonaceous material. :BET method specific surface area A (m ² /g) is 0.1<A<100
and the crystal thickness Lc in X-ray diffraction
(Å) and true density ρ (g/cm ³ ) under the condition 1.80<ρ
＜2.18, 15＜Lc and 120ρ−227＜Lc＜120ρ−
Carbonaceous materials that meet 189. In the first invention, the non-carbonaceous material used as the active material of the positive electrode has a layered structure and has the general formula A _x M _y N _z O ₂ (where A is at least one selected from alkali metals). Yes, M is a transition metal, N is Al, In,
represents at least one kind selected from the group of Sn,
x, y, z are respectively 0.05≦x≦1.10, 0.85≦y≦
Represents the number 1.00, 0.001≦z≦0.10. ) is optimal. Further, the second invention provides a secondary battery having a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte, characterized in that the following is used as an active material of the positive electrode. It is. : has a layered structure and has the general formula A _x M _y N _z O ₂ (where A is at least one selected from alkali metals, M is a transition metal, and N is Al, In,
represents at least one kind selected from the group of Sn,
x, y, z are respectively 0.05≦x≦1.10, 0.85≦y≦
Represents the number 1.00, 0.001≦z≦0.10. ) complex oxide. The novel layered composite metal oxide of the present invention has the general formula
A _x M _y N _z O ₂ , where A is at least one selected from alkali metals, such as Li,
These are Na and K, with Li being preferred among them. The value of x varies depending on the charging state and discharging state, and its range is
0.05≦x≦1.10. In other words, charging causes de-intercalation of A ions, and the value of x decreases, and in a fully charged state, the value of x becomes
reaches 0.05. In addition, intercalation of A ions occurs due to discharge, and the value of x increases,
In a fully discharged state, the value of x reaches 1.10. Further, M represents a transition metal, and among them, Ni and Co are preferable. The value of y does not change due to charging and discharging, but is in the range of 0.85≦y≦1.00. y value is 0.85
If it is less than 1.00 or more than 1.00, the performance as an active material for a secondary battery is not sufficient, that is, the cycleability deteriorates, and phenomena such as an increase in overvoltage occur, which is not preferable. N is at least one selected from the group of Al, In, and Sn, with Sn being preferred among them. In the novel active material for secondary batteries of the present invention, the function of N is extremely important, and it exhibits extremely excellent cycle performance, particularly in deep charge and deep discharge cycles. The value of z does not change due to charging and discharging, but is in the range of 0.001≦z≦0.10, preferably in the range of 0.005≦z≦0.075. The value of z is 0.001
If it is less than 10%, the effect of N is not sufficiently exhibited, the cycleability during deep charging and deep discharging described above is low, and the overvoltage during deep charging increases significantly, which is not preferable. Furthermore, if the value of z exceeds 0.10, the hygroscopicity becomes too strong, making it difficult to handle, and the basic properties as an active material for a secondary battery are impaired, which is not preferable. In order to produce the novel composite oxide for secondary battery active material of the present invention, oxides, hydroxides, carbonates, nitrates, organic acid salts, etc. of each of the metals A, M, and N are mixed. After that, it is obtained by firing in air or under an oxygen atmosphere at a temperature range of 600°C to 950°C, preferably 700°C to 900°C. A firing time of about 5 to 48 hours is usually sufficient.
A _x M _y N _z O ₂ obtained by this method is in a discharge state as a secondary battery positive electrode, that is, the value of x is usually 0.90.
~1.10 is obtained. The thus obtained A _x M _y N _z O ₂ undergoes a de-intercalation reaction due to charging and discharging as described above.
and due to the intercalation reaction, the value of x is
It fluctuates within the range of 0.05≦x≦1.10. This reaction can be represented by the formula A _x ′M _y N _z O ₂ charging/discharging A _x ″M _y N _z O ₂ + (x′-x″) A + (x′-x″) e. (Here, x' represents the value of x before charging, and x'' represents the value of x after charging.) The above-mentioned utilization rate is calculated by the following formula: utilization rate = x'-x''/y + z x 100 (%) The novel active material for non-aqueous secondary batteries of the present invention is characterized by a high utilization rate, that is, deep charging,
It has extremely stable cyclability against discharge. The novel composite oxide for secondary battery active material of the present invention has a very noble potential of 3.9 to 4.5V with respect to Li standard potential, and is especially useful when used as a positive electrode of a non-aqueous secondary battery. Demonstrates excellent performance. On the other hand, the carbonaceous material used in the present invention is described below.
BET method specific surface area A (m ² /g) is larger than 0.1,
Must be less than 100. preferably greater than 0.1 and less than 50, more preferably greater than 0.1 and less than 25
The range is less than or equal to If it is less than 0.1m ² /g, the surface area is too small;
This is not preferable because it makes it difficult for the electrochemical reaction to proceed smoothly on the electrode surface. Further, when the specific surface area is 100 m ² /g or more, it is not preferable because the characteristics deteriorate in terms of cycle life characteristics, self-discharge characteristics, current efficiency characteristics, etc. It is presumed that this phenomenon is due to the excessively large surface area, which causes various side reactions on the electrode surface, which adversely affects battery performance. In addition, the crystal thickness Lc (Å) in X-ray diffraction described below
and true density ρ (g/cm ³ ) under the following conditions, i.e. 1.80
＜ρ＜2.18, 15＜Lc and 120ρ−227＜Lc＜120ρ−
Must be in the range 189. preferably 1.80
＜ρ＜2.18, 15＜Lc and 120ρ−227＜Lc＜120ρ−
196, more preferably 1.96<ρ<2.16, 15<Lc and 120ρ−227<Lc<120ρ−196. In the present invention, when using the n-doped carbonaceous material as a stable electrode active material, the above-mentioned
Crystal thickness Lc (Å) and true density ρ in line diffraction
The value of (g/cm ³ ) is extremely important. That is, the value of ρ is 1.80 or less or the value of Lc is 15 or
If it is less than 120ρ-227, it means that the carbonaceous material is not sufficiently carbonized, that is, the carbon crystal growth is not progressing, and there are a large number of amorphous parts.
Moreover, for this reason, the surface area of carbonaceous materials falling within this range inevitably increases during the carbonization process, and the value of the BET method specific surface area deviates from the range of the present invention.
The n-doped form of such a carbonaceous material is extremely unstable and has a low doping amount, so that it cannot substantially exist stably as an n-doped form and cannot be used as a battery active material. On the other hand, the value of ρ is 2.18 or more or the value of Lc is 120ρ−
If the value exceeds 189, the carbonization of the carbonaceous material has progressed too much. That is, it means that it has a structure similar to graphite or graphite in which carbon is highly crystallized. In addition to true density ρ (g/cm ³ ), crystal thickness Lc (Å), and BET method specific surface area A (m ² /g), parameters that indicate the structure of such carbonaceous materials include, for example, X Interlayer spacing d ₀₀₂ (Å) in line diffraction
can be mentioned. The value of the interplanar spacing d ₀₀₂ (Å) decreases with the progress of crystallization, and although it is not particularly limited, carbonaceous materials having a value of less than 3.43 Å, and even less than 3.46 Å, are excluded from the range defined by the present invention. Deviate. On the other hand, the value of the intensity ratio R (I1360cm ^-1 /I1580cm ^-1 ) in the Raman spectrum is also a parameter indicating the structure of the carbonaceous material, and this intensity ratio R decreases as crystallization progresses, and there are no particular limitations. No, but less than 0.6 or more than 2.5, even 0.7
Carbonaceous materials having values in the range of less than or greater than 2.5 deviate from the range defined by the present invention. As mentioned above, graphite and graphite have a regular layered structure, and carbon materials with such a structure form interlayer compounds with various ions as guests, especially anions such as ClO ₄ and BF ₄ . P with ion
This type of intercalation compound has a high potential, and attempts have been made for a long time to use it as a secondary battery positive electrode. For such purposes, it is an essential condition that intercalation compounds can be easily formed. For example, as described in JP-A-60-36315, the Raman intensity ratio R (I1360
cm ^-1 /I1580cm ^-1 ) should be as small as possible, i.e.
It was essential that the value of ρ and the value of Lc be as large as possible. The present inventors discovered an unexpected fact in the process of various studies on incorporating cations such as Li ions instead of anions into carbonaceous materials from a different perspective. That is, it has been found that when incorporating cations such as Li ions, the carbonaceous material has better properties if it has a certain degree of disordered structure. In other words, the value of ρ is 2.18 or more, or the value of Lc is
When a carbonaceous material having a value of 120ρ-189 or more is used, as mentioned above, graphite-like behavior occurs, the cycle life characteristics and self-discharge characteristics are poor, and furthermore, the utilization rate is extremely low and extremely In such a case, it may not substantially function as a secondary battery, which is not preferable. Carbonaceous materials satisfying the conditions of the present invention can be obtained, for example, by thermal decomposition or calcination carbonization of various organic compounds. In this case, thermal history temperature conditions are important; as mentioned above, if the thermal history temperature is too low, carbonization will not be sufficient, and not only will the electrical conductivity be low, but the carbonaceous material, which is the condition of the present invention, will not be obtained. . The lower temperature limit varies slightly depending on the item, but
The temperature is usually 600°C or higher, preferably 800°C or higher. Even more important is the upper limit of thermal history temperature, which is carried out in normal graphite, graphite and carbon fiber manufacturing.
Heat treatment at temperatures close to 3000°C causes crystal growth to proceed too much, significantly impairing the function of the secondary battery. The preferred range is 2400°C or less, preferably 1800°C or less, and even more preferably 1400°C or less. In such heat treatment conditions, the heating rate, cooling rate, heat treatment time, etc. can be arbitrarily selected depending on the purpose. In addition, after heat treatment in a relatively low temperature range,
A method of raising the temperature to a predetermined temperature is also adopted. An example of a carbonaceous material that satisfies the condition range of the present invention is a vapor grown carbon fiber. The vapor grown carbon fiber is disclosed in, for example, Japanese Patent Application Laid-open No. 1983-
As described in Publication No. 207823, benzene, methane,
It is a carbon material obtained by subjecting a carbon source compound such as carbon monoxide to gas phase thermal decomposition (for example, at a temperature of 600°C to 1500°C) in the presence of a transition metal catalyst, etc., and is obtained by a known method similar to this. Refers to everything that can be applied to the fibers, such as ceramics, graphite substrates, carbon fibers, etc.
Carbon black, ceramic particles, etc. )
There are known methods such as generating it in the gas phase and generating it in the gas phase. Fibrous,
That is, it is obtained as carbon fiber, but in the present invention, it may be used as it is in the form of fibers, or it may be used in the form of pulverized powder. It is a well-known fact that such vapor-grown carbon fibers are a typical example of graphitizable carbon. That is, it has the characteristic of being extremely easily converted into graphite graphite by heat treatment. Such heat treatment is usually performed at a temperature of 2400°C or higher. Various characteristics of the graphitized vapor-grown carbon fiber thus obtained as a graphite material with an extremely well-organized crystal structure have already been reported. It is known that an intercalation compound is very easily formed with an anion such as Br, as described in 2007, and that a temperature difference battery can be made by using an intercalation compound with such anion for the positive and negative electrodes. However, such battery systems usually have extremely low electromotive force and are not suitable for practical use. On the other hand, as mentioned above, graphite and graphite have a regular layered structure, and carbon materials with such a structure form interlayer compounds with various ions as guests, especially ClO ₄ , BF ₄ etc. Intercalation compounds with anions have a high potential, and attempts have been made for a long time to use them as positive electrodes for secondary batteries.
For such purposes, it is essential that intercalation compounds be easily formed, and for example, as described in JP-A-60-36315, a graphite structure of graphite heat-treated at nearly 3000° C. is an essential condition. From a different perspective, the present inventors have found that Li, rather than anions, is added to carbonaceous materials.
An unexpected fact was discovered in the process of examining various n-doped bodies into which cations such as ions were incorporated. That is, it has been found that when incorporating cations such as Li ions, the carbonaceous material has better properties if it is not subjected to excessive thermal history. That is, the vapor-grown carbon fiber used in the present invention has a maximum thermal history temperature of 2400°C, including the manufacturing process.
C. or less, preferably 2000.degree. C. or less, especially 1400.degree. C. or less is suitably used. If the temperature exceeds 2400°C, the properties of the n-doped product will be adversely affected, which is not preferable. Another example is a pitch-based carbonaceous material. Examples of pitches used in the present invention include petroleum pitch, asphalt pitch, coal tar pitch, crude oil cracking pitch, petroleum sludge pitch, etc., which are obtained by thermal decomposition of petroleum and coal, and pitch obtained by thermal decomposition of high molecular weight polymers. Pitch obtained by thermal decomposition of an organic low-molecular compound such as tetrabenzophenazine and the like can be mentioned. Thermal history temperature conditions are important in order to obtain a pitch-based calcined carbide that satisfies the conditions of the present invention, and as mentioned above, a thermal history at a high temperature gives a fired carbide that is too crystallized and has the characteristics of an n-doped body. becomes significantly worse. The thermal history temperature condition is preferably 2400°C or less, preferably 1800°C or less, and even more preferably 1400°C or less. In addition, the lower temperature limit is at least the temperature at which the fired carbide begins to exhibit properties such as electrical conductivity.
The preferred range is 600°C or higher, more preferably 800°C or higher. Specific examples of such pitch-based calcined carbides are as follows:
Examples include needle coke. A further example of the carbonaceous material used in the present invention is a fired carbide of a polymer containing acrylonitrile as a main component. In order to obtain a calcined carbide of a polymer whose main component is acrylonitrile that satisfies the conditions of the present invention, thermal history temperature conditions are important. The properties of the n-doped product are significantly deteriorated.
The thermal history temperature condition is 2400℃ or less, preferably
The preferred range is 1800°C or lower, more preferably 1400°C or lower. In addition, the lower temperature limit is at least the temperature at which the fired carbide begins to exhibit properties such as electrical conductivity.
The preferred range is 600°C or higher, more preferably 800°C or higher. The carbonaceous material of the present invention differs from ordinary graphite and graphite in that it does not have a layered structure that can form interlayer compounds, and this is useful for X-ray analysis, Raman analysis, true density measurement, etc. It is clear from the results. In fact, the carbonaceous material in the condition range of the present invention does not take in anions such as ClO ₄ , BF ₄ , Br, etc., which are very likely to form intercalation compounds with graphite and graphite, or does not take them in very easily. Also, as in the example of the above-mentioned Japanese Patent Application Laid-Open No. 58-35881,
Unlike the formation of an electric double layer on the surface, which is a type of capacitor behavior, seen in high surface area carbon materials such as activated carbon, in the case of the present invention, there is no correlation between surface area and battery performance; on the contrary, the surface area is large. However, there is a fact that it becomes negative in terms of performance such as current efficiency and self-discharge. This fact is different from the phenomenon found in conventionally known carbon materials, and when used as a secondary battery active material, it exhibits the following characteristics. It has a cycle life characteristic of at least 100 times or more, sometimes 300 times or more, and even 500 times or more. In addition, the current efficiency during charging and discharging is at least
Over 90%, in some cases over 95%, and even over 98%. The self-discharge rate is at least 30%/month or less, sometimes 20%/month or less, and even 10%/month or less. Furthermore, one of the characteristics of the carbonaceous material that satisfies the conditions of the present invention is that it has a very high utilization rate. The utilization rate as used in the present invention means the ratio of electrons (or counter cations) that can reversibly go in and out per carbon atom, and is defined by the following formula. Utilization rate = Charge/discharge electricity amount (Ahr unit)/w (g unit)/12×26.8 Here, w is the weight of the carbonaceous material used (g unit)
represents. In the present invention, the utilization rate is at least 0.08 or more,
Furthermore, it reaches 0.15 or more, making it possible to store a large amount of electricity with a small weight and volume. The n-doped carbonaceous material of the present invention exhibits excellent performance when used as a secondary battery active material, and particularly exhibits even more excellent performance when used as a negative electrode active material. Next, a secondary battery using the active material of the present invention will be described. When manufacturing an electrode using the active material for a secondary battery of the present invention, the active material can be used in various shapes. That is, the active material can be used in any form such as a film, fiber, or powder depending on the purpose, but especially when used in powder form, the active material can be formed into any form such as a sheet. A common method for molding is to mix the active material with a powdered binder such as Teflon powder or polyethylene powder, and then compression mold the mixture. A more preferable method is to form an electrode active material using an organic polymer dissolved and/or dispersed in a solvent as a binder. Although non-aqueous batteries have conventionally been superior in terms of performance such as high energy density, small size and light weight, they have disadvantages in output characteristics compared to aqueous batteries, so they have not been widely used. Particularly in the field of secondary batteries, where output characteristics are required, this drawback is one of the factors preventing practical use. The reason why non-aqueous batteries have inferior output characteristics is that aqueous electrolytes have high ionic conductivity, which usually has a value on the order of 10 ^-1 Ω ^-1 cm ^-1 , whereas non-aqueous batteries usually have a high ionic conductivity.
This is due to its low ionic conductivity of 10 ^-2 to 10 ^-4 Ω ^-1 cm ^-1 . One possible way to solve this problem is to increase the area of the electrode, that is, to use a thin film or a large-area electrode. The above method is a particularly preferred method for obtaining such thin film, large area electrodes. When using such an organic polymer as a binder, there is a method in which an electrode active material is dispersed in a binder solution in which the organic polymer is dissolved in a solvent and used as a coating liquid, or a water emulsion dispersion of the organic polymer is used. Examples include a method in which a liquid in which an electrode active material is dispersed is used as a coating liquid, and a method in which a solution and/or dispersion of the organic polymer is applied to a preformed electrode active material. The amount of binder used is not particularly limited, but is usually 0.1 to 20 parts by weight per 100 parts by weight of the electrode active material.
Preferably it is in the range of 0.5 to 10 parts by weight. The organic polymer used here is not particularly limited, but if the organic polymer is
When the dielectric constant at 1 kHz has a value of 4.5 or more, particularly favorable results are brought about, and the battery exhibits particularly excellent characteristics in terms of cycleability, overvoltage, and the like. Examples of organic polymers that meet these conditions include acrylonitrile, methacrylonitrile, vinyl fluoride, vinylidene fluoride, chloroprene,
Examples include polymers or copolymers such as vinylidene chloride, nitrocellulose, cyanoethylcellulose, polysulfide rubber, and the like. When manufacturing an electrode using this method, the coating solution is applied onto a base material and dried to form the electrode. At this time, if necessary, it may be molded together with the current collector material, or alternatively, a current collector such as aluminum foil or copper foil may be used as the base material. The binder, conductive aid, and other additives such as thickeners, dispersants, fillers, adhesion aids, etc. may be added to the battery electrode manufactured using the active material of the present invention. It refers to a material containing at least 25% by weight of the active material of the present invention. Examples of the conductive aid include metal powder, conductive metal oxide powder, and carbon. Particularly, the addition of such a conductive auxiliary agent has a remarkable effect when A _x M _y N _z O ₂ of the present invention is used. Among them, carbon gives preferable results, and is usually used in an amount of 1 to 100 parts by weight of A _x M _y N _z O ₂
Addition of 30 parts by weight produces a significant overvoltage reduction effect and exhibits excellent cycle characteristics. The carbon referred to herein requires properties that are completely different from those of the carbonaceous material defined in the present invention, and does not necessarily mean a specified carbon. Examples of such carbon include graphite and carbon black. As a particularly preferable combination, when carbon having an average particle size of 0.1 to 10 μm and carbon having an average particle size of 0.01 to 0.08 μm are used as a mixture, particularly excellent effects can be obtained. As mentioned above, the active material of the present invention: A _x M _y N _z O ₂ exhibits particularly excellent performance when used as a positive electrode. The negative electrode used at this time is not particularly limited, but may include a light metal such as Li or Na or an alloy negative electrode thereof,
Metal oxide negative electrodes such as Li _x Fe ₂ O ₃ , Li _x Fe ₃ O ₄ , Li _x WO ₂ , conductive polymer negative electrodes such as polyacetylene and poly-p-phenylene, vapor grown carbon fibers, and pitch-based negative electrodes. Examples include carbonaceous material negative electrodes such as carbon and polyacrylonitrile carbon fibers. On the other hand, the active material of the present invention exhibits particularly excellent performance when used as a negative electrode as described above. The positive electrode used at this time is not particularly limited, but examples include TiS ₂ , TiS ₃ , MoS ₃ , FeS ₂ ,
Li _(1-x) MnO ₂ , Li _(1-x) CoO ₂ , Li _(1-x) NiO ₂ , V ₂ O ₅ ,
Examples include V ₆ O ₁₃ . As a particularly preferred combination, the most preferred is a combination in which the active material of the present invention: A _x M _y N _z O ₂ is used as a positive electrode, and the active material of the present invention is used as a negative electrode. Basic components for assembling the non-aqueous secondary battery of the present invention include an electrode using the active material of the present invention, a separator, and a non-aqueous electrolyte. The separator is not particularly limited, but
Examples include woven fabrics, non-woven fabrics, glass woven fabrics, synthetic resin microporous membranes, etc. As mentioned above, when using thin films and large-area electrodes, synthetic resin microporous membranes disclosed in JP-A-58-59072, for example, can be used. Porous membranes, particularly microporous polyolefin membranes, are preferred in terms of thickness, strength, and membrane resistance. The electrolyte of the non-aqueous electrolyte is not particularly limited, but examples include LiClO ₄ , LiBF ₄ , LiAsF ₆ ,
_CF3SO3Li , _{LiPF6 ,} LiI, _LiAlCl4 , _NaClO4 ,
NaBF ₄ , NaI, (n-Bu) ₄ N ClO ₄ , (n-
Bu) _{4NBF4 , KPF6} , etc. In addition, examples of organic solvents used in the electrolytic solution include ethers, ketones, lactones, nitriles, amines, amides, sulfur compounds, chlorinated hydrocarbons, esters, carbonates, nitro compounds, and phosphorus. Acid ester compounds, sulfolane compounds, etc. can be used, and among these, ethers, ketones, nitriles, chlorinated hydrocarbons, carbonates, and sulfolane compounds are preferred. More preferred are cyclic carbonates. Representative examples of these include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, anisole, monoglyme, acetonitrile, propionitrile, 4-methyl-2-pentanone, butyronitrile, valeronitrile, benzonitrile, 1,2- Dichloroethane, γ-butyrolactone, dimethoxyethane, methylformate, propylene carbonate, ethylene carbonate, vinylene carbonate, dimethylformamide, dimethylsulfoxide, dimethylthioformamide, sulfolane, 3-methyl-sulfolane, trimethyl phosphate, triethyl phosphate, and these Examples include mixed solvents of
It is not necessarily limited to these. Furthermore, if necessary, the battery is constructed using parts such as a current collector, a terminal, and an insulating plate. The structure of the battery is not particularly limited, but may include a paper type battery with a positive electrode, a negative electrode, and if necessary a separator in a single layer or multiple layers, a stacked battery, or a positive electrode, a negative electrode, and if necessary, a separator. For example, a cylindrical battery formed by winding a separator into a roll can be cited. [Effects of the Invention] The battery of the present invention is small and lightweight, has particularly excellent cycle characteristics and self-discharge characteristics, and is extremely useful as a power source for small electronic devices, electric vehicles, power storage, and the like. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. The BET method specific surface area (hereinafter referred to as "BET surface area") was measured by a nitrogen adsorption method using a BET surface area measuring device P-700 manufactured by Shibata Kagaku Kikai Kogyo Co., Ltd. In addition, X-ray diffraction was performed according to the "Japan Society for the Promotion of Science Law." The true density was measured using a sample of powder obtained by pulverizing a carbonaceous material in an agate mortar so as to pass through a 150-mesh standard sieve, and by a float-sink method using a mixed solution of bromoform and carbon tetrachloride at 25°C. For samples with a true density distribution, the measured value was the value at which about 50% of the total powder particles settled. The relative dielectric constant was measured under the following conditions. (Measurement temperature) 25℃ (Measurement frequency) 1kHz (Sample shape) 0.5mm thick sheet (Measurement device)
TR-10C type dielectric volume measuring instrument (manufactured by Ando Electric Co., Ltd.) Example 1 Anthracene oil was added at room temperature under an Ar atmosphere.
The temperature was raised at a rate of °C/min, and the mixture was fired and carbonized at 1200 °C for 1 hour.
The BET surface area, Lc ₍₀₀₂₎ obtained from X-ray diffraction, and true density of this carbonaceous material are 60 m ² /g and 25, respectively.
Å, 2.01 g/cm ³ . 1 part by weight of powder with an average particle size of 2 μm obtained by ball-milling this sample was mixed with 2.5 parts by weight of a methyl ethyl ketone solution (2 wt% concentration) of nitrile rubber (relative dielectric constant 17.3) to prepare a coating liquid.
A film with a thickness of 75 μm was formed on a 1 cm×5 cm surface of a 10 μm copper foil. This was sandwiched between SUS nets and used as the negative electrode of the battery shown in FIG. On the other hand, 1.05 moles of lithium carbonate, cobalt oxide
1.90 mol, 0.084 mol of stannic oxide are mixed, 650
After 5 hours of calcining at .degree. C., the mixture was calcined in air at 850.degree. C. for 12 hours to obtain a composite oxide having a composition of Li _1.03 Co _0.95 Sn _0.042 O ₂ . After pulverizing this composite oxide to an average size of 3 μm using a ball mill, 0.1 part by weight of acetylene black and 1 part by weight of a dimethylformamide solution (concentration 2 wt%) of polyacrylonitrile (relative dielectric constant 5.59) were added to 1 part by weight of the composite oxide. After mixing, the mixture was applied to one side of a 1 cm x 5 cm piece of 15 μm aluminum foil to a thickness of 100 μm. This is sandwiched between SUS nets and used as the positive electrode.
The battery was evaluated using a 0.6 molar LiClO ₄ propylene carbonate solution as the electrolyte. Polyethylene microporous membrane as a separator
35 μm was used. After charging at a constant current of 2 mA for 50 minutes, an open terminal voltage of 3.9 V was obtained. As a result of this charging, the ratio of Li ions incorporated per carbon atom, ie, the utilization rate, was 0.12. After that, the battery was similarly discharged to 2.7V at a constant current of 2mA. The charging voltage and discharging voltage at this time are as shown in Figure 2,
Overvoltage was extremely low at 0.04V. After that, charge/discharge cycles with a constant current of 2 mA (charging end voltage 3.95 V,
The final discharge voltage was 2.7V). The changes in current efficiency and utilization factor with cycles are shown in Figure 3-A.
The energy density (per negative electrode active material) at the 5th cycle was 911 Whr/Kg. Furthermore, the self-discharge rate of this battery when left at 25°C for 720 hours was 15%. Examples 2 to 6, Comparative Examples 1 to 5 Using carbonaceous materials obtained by calcination carbonization or heat treatment of the raw materials shown in Table 1 under the treatment conditions also shown in Table 1, the same method as in Example 1 was carried out. I conducted a battery evaluation. In this test, the current efficiency and the rate of Li ions reversibly incorporated per carbon atom, ie, the utilization rate, were as shown in Table 1. Also obtained from BET surface area and X-ray diffraction
Lc ₍₀₀₂₎ indicates true density. Further, for Comparative Example 2, changes in current efficiency and utilization rate in a long-term cycle are shown in FIG. 3-B. The energy density (per negative electrode active material) at the 5th cycle was 288 Whr/Kg. Incidentally, the self-discharge of the battery in Comparative Example 2 after being left for 720 hours (25° C.) was 85%.

[Table] Example 7, Comparative Example 6 A battery evaluation was carried out in exactly the same manner as in Example 1, except that the binder shown in Table 2 was used as the binder for the negative electrode active material. The end-of-charge voltage and overvoltage at this time are also shown in Table 2.

[Table] Examples 8 to 10 In Example 1, 0.6 molar concentration was used as the electrolyte.
Exactly the same battery evaluation was performed except that the electrolyte shown in Table 3 was used instead of the LiClO ₄ propylene carbonate solution. The results are also shown in Table 3.

[Table] Example 11 1% by weight of biscyclopentadienyl iron was dissolved in benzene to prepare a raw material liquid. Internal diameter 60mm in tube furnace with Kanthal wire heater
A φ alumina furnace core tube was installed horizontally, and both ends were sealed with rubber plugs. An alumina pipe with an inner diameter of 6 mmφ through which the raw material liquid is introduced is passed through one of the plugs.
One end of the pipe is kept at the pre-measured furnace temperature of 510℃.
The outlet was placed at the center of the furnace tube. The other end of the pipe was taken out of the furnace and connected to a metering pump with a rubber tube. The metering pump was designed to pressurize the raw material liquid with an inert gas and send it to the metering pump. Further, a pipe of the same diameter is passed through the rubber stopper on the raw material introduction side, and an inert gas for replacing the inside of the furnace and hydrogen gas as an aid for fiber growth are introduced through the rubber tube. These gases could be switched arbitrarily using valves. On the other hand, an alumina pipe with an inner diameter of 60 mm was installed on the rubber stopper at the other end so that exhaust gas could be discharged through the rubber tube. First, the inside of the furnace was replaced with inert gas, then switched to hydrogen gas, and the temperature at the center of the furnace was raised to 1200°C. At this time, the temperature at the pipe outlet was 500°C. While supplying hydrogen gas at a flow rate of 1000c.c./min,
The raw material liquid was supplied at a rate of 1 c.c./min for about 15 minutes. As a result, 7.1 g of carbon fiber was obtained in the 600-1200°C zone. This carbon fiber has an average diameter of approximately 4μmφ, BET
Surface area, true density, interplanar spacing obtained by X-ray diffraction
d ₀₀₂ and Lc ₍₀₀₂₎ are 9m ² /g and 2.03g/cm ³ , respectively.
They were 3.54 Å and 38 Å. This vapor grown carbon fiber 5
mg was formed into a sheet of 1 cm x 5 cm, which was then sandwiched between SUS nets to form the negative electrode of the battery shown in FIG. On the other hand, a battery evaluation was performed using a 1 cm x 5 cm x 0.1 cm sheet of LiCoO ₂ sandwiched between SUS nets as a positive electrode and a 0.6M propylene carbonate solution of LiClO ₄ as an electrolyte. Note that a polypropylene nonwoven fabric was used as a separator. After charging at a constant current of 2 mA for 50 minutes, an open terminal voltage of 3.9 V was observed. This charging causes carbon 1
The ratio of Li ions incorporated per atom, ie, the utilization rate, was 0.15. After that, charge/discharge cycle with constant current 2mA (end-of-charge voltage 3.95V, end-of-discharge voltage
2.70V). Figure 4-A shows the changes in current efficiency and utilization factor with cycles. The energy density (per negative electrode active material) at the 5th cycle is
It was 1139Whr/Kg. Furthermore, the self-discharge rate of this battery after being left for 720 hours was 7%. Examples 12 to 15, Comparative Examples 7 to 8 The vapor-grown carbon fibers obtained in Example 11 were heat-treated in an Ar atmosphere at the temperatures shown in Table 4 for 30 minutes, and then treated in exactly the same manner as in Example 11. The battery was evaluated through operation. In this test, the current efficiency and Li ions reversibly incorporated per carbon atom, ie, the utilization rate, were as shown in Table 4. At the same time, the BET surface area, true density, and
The Lc ₍₀₀₂₎ values obtained by X-ray diffraction are also shown in Table 4.

[Table] Example 16 The vapor-grown carbon fiber obtained in Example 11 was pulverized in a ball mill to obtain a pulverized vapor-grown carbon fiber having an average particle size of 4 μm. A mixture of 9 parts by weight of this pulverized material and 1 part by weight of powdered polyethylene was molded on a SUS net at a pressure of 250 kg/cm ² to obtain a sheet-like test piece of 1 cm x 5 cm. A battery test was conducted in exactly the same manner as in Example 1 using this test piece as a negative electrode. The results are shown in Figure 4-B. Example 17 1% by weight of biscyclopentadienyl iron was dissolved in benzene to prepare a raw material liquid. Internal diameter 60mm in tube furnace with Kanthal wire heater
A φ alumina furnace core tube was installed horizontally, and both ends were sealed with rubber plugs. An alumina pipe with an inner diameter of 6 mmφ through which the raw material liquid is introduced is passed through one of the plugs.
One end of the pipe is kept at the pre-measured furnace temperature of 510℃.
The outlet was placed at the center of the furnace tube. The other end of the pipe was taken out of the furnace and connected to a metering pump with a rubber tube. The metering pump was designed to pressurize the raw material liquid with an inert gas and send it to the metering pump. Further, a pipe of the same diameter is passed through the rubber stopper on the raw material introduction side, and an inert gas for replacing the inside of the furnace and hydrogen gas as an aid for fiber growth are introduced through the rubber tube. These gases could be switched arbitrarily using valves. On the other hand, an alumina pipe with an inner diameter of 6 mm was provided on the rubber stopper at the other end so that exhaust gas could be discharged through the rubber tube. First, the inside of the furnace was replaced with inert gas, then switched to hydrogen gas, and the temperature at the center of the furnace was raised to 1200°C. At this time, the temperature at the pipe outlet was 500°C. While supplying hydrogen gas at a flow rate of 2500c.c./min,
The raw material liquid was supplied at a rate of 2.5 cc/min for 3 minutes. As a result, 3.7 g of carbon fiber was obtained in the 600-1200°C zone. This vapor grown carbon fiber has an average diameter of 0.2μm.
φ, BET surface area, true density, and Lc ₍₀₀₂₎ obtained by X-ray diffraction are 16 m ² /g, 2.04 g/cm ³ , and 45, respectively.
It was Å. Using this vapor-grown carbon fiber, battery evaluation was conducted in exactly the same manner as in Example 11. The terminal voltage is
3.9V, the proportion of Li ions taken in,
That is, the utilization rate was 0.14 per carbon atom. or,
The current efficiency was 93%. Comparative Example 9 In Example 16, commercially available graphite powder (Lonza Graphite) was used instead of the vapor grown carbon fiber pulverized material.
KS2.5, manufactured by Lonza, BET N ₂ specific surface area 22m ² /
g, true density 2.25 g/cm ³ , interplanar spacing d ₀₀₂ = 3.36 Å,
Exactly the same procedure was performed except that Lc ₍₀₀₂₎ >1000 Å) was used. I charged it for 1 hour at 2mA constant current, but
Discharge is not possible and Li is reversibly incorporated.
The ion was O. Comparative Example 10 In place of the vapor grown carbon fiber in Example 11,
Commercially available activated carbon fiber (BET N ₂ specific surface area 450m ² /
g, true density 1.70 g/cm ³ , interplanar spacing d ₀₀₂ = 3.60 Å,
Exactly the same procedure was performed except that Lc ₍₀₀₂₎ <10 Å) was used. Figure 4-C shows the changes in current efficiency and utilization rate at this time.
Shown below. The energy density (per negative electrode active material) at the 5th cycle was 288 Whr/Kg. Furthermore, the self-discharge rate of this battery after being left for 720 hours (25°C) was 85%. Example 18 The temperature of an asphalt pitch was raised from room temperature at a rate of 10°C/min under an Ar atmosphere, and after being held at 530°C for 1 hour,
Carbonization was performed at 1150°C for 1 hour. This carbonaceous material
The values of BET surface area, true density, and interplanar spacing d ₀₀₂ and Lc ₍₀₀₂₎ obtained from X-ray diffraction are 47 m ² /g and 2.00, respectively.
g/cm ³ , 3.48 Å, and 26 Å. This sample was ground in a ball mill to obtain a ground product with an average particle size of 1.5 μm.
A battery evaluation was conducted in exactly the same manner except that this pulverized product was used in place of the anthracene oil-fired carbide powder of Example 1. The results are shown in Figure 5-A. Note that the energy density (per negative electrode active material) at the 5th cycle was 1216 Whr/Kg. Furthermore, the self-discharge rate of this battery when left at 25°C for 720 hours was 7%. Examples 19 to 26, Comparative Examples 11 to 14 Using carbonaceous materials obtained by firing and carbonizing the raw material pitch shown in Table 5 under the heat treatment conditions also shown in Table 5, the same battery evaluation as in Example 18 was conducted. I went. In this test, the current efficiency and the rate of Li ions reversibly incorporated per carbon atom, ie, the utilization rate, were as shown in Table 5. Also BET
Surface area, Lc ₍₀₀₂₎ obtained from X-ray diffraction, and true density are shown. Comparative Example 15 In Example 1, commercially available activated carbon (BET surface area 450
m ² /g, true density 1.70g/cm ³ , interplanar spacing d ₀₀₂ = 3.60Å,
Exactly the same procedure was performed except that Lc ₍₀₀₂₎ >10 Å) was used. Changes in current efficiency and utilization rate at this time are shown in Figure 5-B. The energy density (per negative electrode active material) at the 5th cycle was 217 Whr/Kg. Also, the self-discharge rate of this battery when left at 25℃ for 720 hours is 88
It was %.

[Table] Example 27 Petroleum-based raw coke was heated in an Ar atmosphere at a rate of 10°C/min from room temperature, and calcined and carbonized at 1400°C for 0.5 hours. BET surface area, true density,
The values of interplanar spacing d ₀₀₂ and Lc ₍₀₀₂₎ obtained from X-ray diffraction were 16 m ² /g, 2.13 g/cm ³ , 3.46 Å, and 46 Å, respectively. This sample was ground in a ball mill and the average particle size was
A pulverized product of 5 μm was obtained. A battery evaluation was conducted in exactly the same manner except that this pulverized product was used in place of the anthracene oil-fired carbide powder of Example 1. The results are shown in Figure 6-A. The energy density (per negative electrode active material) at the 5th cycle was 911 Whr/Kg. Furthermore, the self-discharge rate of this battery when left at 25°C for 720 hours was 7%. Examples 28-29, Comparative Examples 16-17 Using carbonaceous materials obtained by calcination carbonization or heat treatment of the raw coke shown in Table 6 under the treatment conditions also shown in Table 6, the same process as in Example 27 was carried out. I conducted a battery evaluation. The results are shown in Table 6. together
BET surface area, true density, interplanar spacing d ₀₀₂ and Lc ₍₀₀₂₎ obtained from X-ray diffraction are shown.

[Table] Example 30 Average particle size of commercially available petroleum-based needle coke (manufactured by Koa Oil Co., Ltd., KOA-SJ Coke) was measured using a ball mill.
It was ground to 10 μm. A battery evaluation was conducted in exactly the same manner, except that this pulverized product was used in place of the anthracene oil-fired carbide powder of Example 1. The results are shown in Figure 6-B. In addition, the BET surface area, true density, and interplanar spacing obtained from X-ray diffraction of this needle coke d ₀₀₂ , Lc ₍₀₀₂₎
are 11m ² /g, 2.13g/cm ³ , 3.44Å, and 52Å, respectively.
It was hot. Examples 31 to 34 Completely similar battery evaluations were performed except that the coke shown in Table 7 was used instead of the petroleum-based needle coke (manufactured by Koa Oil Co., Ltd., KOA-SJ Coke) in Example 30. Results and BET surface area, true density,
Table 7 shows the values of the interplanar spacing d ₀₀₂ and Lc ₍₀₀₂₎ obtained by line diffraction.

[Table] Example 35, Comparative Examples 18 to 24 Battery evaluation was performed in exactly the same manner as in Example 1, except that the carbonaceous materials shown in Table 8 were used instead of the anthracene oil-fired carbide powder. Table 8 shows the results and the values of BET surface area, true density, interplanar spacing d ₀₀₂ and Lc ₍₀₀₂₎ obtained from X-ray diffraction.

[Table] Example 36 1.05 mol of lithium carbonate, 1.90 mol of cobalt oxide, and 0.084 mol of tin oxide were mixed and heated at 650°C for 5 mols.
After calcining for an hour, the mixture was calcined in air at 850°C for 12 hours to obtain a composite oxide having a composition of Li _1.03 Co _0.95 Sn _0.042 O ₂ . After pulverizing this composite oxide to an average size of 3 μm using a ball mill, 1 part by weight of a dimethylformamide solution of polyacrylonitrile (concentration 2 wt%) and 0.2 parts by weight of graphite as a conductive aid are mixed with 1 part by weight of the composite oxide. After that, 15μ
It was applied to one side of 1 cm x 5 cm aluminum foil to a film thickness of 75 μm. The battery shown in FIG. 1 was assembled using this test piece as a positive electrode, lithium metal as a negative electrode, and a 0.6M LiClO ₄ -propylene carbonate solution as an electrolyte. After charging at a constant current of 25 mA (current density 5 mA/cm ² ) for 30 minutes, charging at a constant current of 25 mA
It was discharged to 3.8V. The charging voltage and discharging voltage at this time were as shown in FIG. 7, and the overvoltage was extremely low. Thereafter, a cycle test was conducted under the same charging and discharging conditions, and the charging voltage and discharging voltage at the 500th cycle were as shown in FIG. 8, and showed almost no change. Examples 37-38, Comparative Examples 25-27 The same operations as in Example 36 were carried out except that the amounts of lithium carbonate, cobalt oxide, and stannic oxide were changed to the amounts shown in Table 9, and various composites were prepared. An oxide was obtained. The composition ratios are also shown in Table 9.

[Table] A battery similar to that in Example 1 was assembled using this composite oxide and evaluated. Charging end voltage, open terminal voltage, and overvoltage are shown in Table 10.

[Table] Example 39 The same procedure as in Example 36 was carried out except that 0.041 mol of indium oxide was used instead of 0.082 mol of stannic oxide. Performed a similar battery evaluation,
The measured overvoltages are shown in Table 11. Example 40 The same procedure as in Example 36 was carried out except that 0.042 mol of aluminum oxide was used instead of 0.084 mol of stannic oxide. The battery was evaluated and the measured overvoltages are shown in Table 11. Example 41 The same procedure as in Example 36 was carried out except that 1.90 mol of nickel oxide was used instead of 1.90 mol of cobalt oxide. Similar battery evaluations were conducted and the measured overvoltages are shown in Table 11.

[Table] Example 42, Comparative Example 28 Battery evaluation was performed in exactly the same manner as in Example 36, except that the conductive additive shown in Table 12 was used instead of 0.2 part by weight of graphite. The measured overvoltages are also shown in Table 12.

[Table] Examples 43 to 47, Comparative Examples 29 to 34 Battery evaluation was performed in exactly the same manner as in Example 36, except that the binder solution shown in Table 13 was used instead of the dimethylformamide solution of polyacrylonitrile. The results are shown in Table 13.

【table】

[Table] Example 48 A battery was assembled in exactly the same manner as in Example 36 except that lithium-aluminum alloy was used instead of lithium metal. After charging at a constant current of 10 mA (current density: 2 mA/cm ² ) for 150 minutes (charging end voltage: 3.70 V), discharging was performed at the same constant current to 3.55 V. Overvoltage was extremely low at 0.02V. Example 49 In Example 36, wood alloy (bismuth-tin-lead-cadmium alloy) was used instead of lithium metal.
A battery was assembled in exactly the same manner except that .
After charging at a constant current of 10 mA (current density: 2 mA/cm ² ) for 150 minutes (charging end voltage: 3.75 V), discharging was performed at the same constant current to 3.55 V. Overvoltage is
The voltage was extremely low at 0.02V.

[Brief explanation of drawings]

FIG. 1 is a sectional view of a configuration example of a secondary battery of the present invention,
Figure 2 is a graph showing the relationship between the charging and discharging voltages and the utilization rate when the secondary battery of Example 1 is charged and discharged, and Figures 3 to 7 are graphs showing the current efficiency ( Figure 3-A shows Example 1, Figure 3-B shows Comparative Example 2, Figure 4-A shows Example 11, and Figure 4-B shows Example 1.
16, Figure 4-C is Comparative Example 10, Figure 5-A is Example
18, Figure 5-B is Comparative Example 15, Figure 6-A is Example
27, Figure 6-B is a graph showing the results of Example 30;
Fig. 7 is a graph showing the constant current charging voltage and discharging voltage of the battery of Example 36, and Fig. 8 is a graph showing the charging voltage and discharging voltage at the 500th cycle of charging and discharging the battery of Example 36. be. 1 is a positive electrode, 2 is a negative electrode, 3, 3' is a current collector rod, 4,
4' is SUS net, 5, 5' are external electrode terminals, 6
is a battery case, 7 is a separator, and 8 is an electrolytic solution or solid electrolyte.

Claims (1)

[Claims] 1. A secondary battery having a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte, characterized in that the following is used as an active material for the positive electrode and the following is used as an active material for the negative electrode. secondary battery. : Non-carbonaceous material. :BET method specific surface area A (m ² /g) is 0.1<A<100
and the crystal thickness Lc in X-ray diffraction
(Å) and true density ρ (g/cm ³ ) under the condition 1.80<ρ
＜2.18, 15＜Lc and 120ρ−227＜Lc＜120ρ−
Carbonaceous materials that meet 189. 2. The non-carbonaceous material used as the active material of the positive electrode has a layered structure and has the general formula A _x M _y N _z O ₂ (where A is at least one selected from alkali metals and M is a transition metal). Yes, N is Al, In,
represents at least one kind selected from the group of Sn,
x, y, z are respectively 0.05≦x≦1.10, 0.85≦y≦
Represents the number 1.00, 0.001≦z≦0.10. ) The secondary battery according to claim 1, wherein the secondary battery is a composite oxide represented by: 3. A secondary battery having a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte, characterized in that the following is used as an active material of the positive electrode. : has a layered structure and has the general formula A _x M _y N _z O ₂ (where A is at least one selected from alkali metals, M is a transition metal, and N is Al, In,
represents at least one kind selected from the group of Sn,
x, y, z are respectively 0.05≦x≦1.10, 0.85≦y≦
Represents the number 1.00, 0.001≦z≦0.10. ) complex oxide.