CA1275437C - Secondary battery using non-aqueous solvent - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

There is disclosed a secondary battery using a non-aqueous solvent which comprises using a carbonaceous material obtained by carbonating an organic compound and having a pseudographite structure of a hydrogen/carbon ratio being 0.15 or less, a d002 being 3.37 .ANG. to 3.75 .ANG. and a Lc being 8 .ANG. to 150 .ANG. as a negativeelectrode. The battery has a large electric density, less in self discharging and excellent in preservability.

Description

~7~4;37 The present invention relates to a secondary battery using a non-aqueous solvent, more particularly to a secondary battery using a non-aqueous solv~nt which is prone to self-discharge, has good charge/discharge cycle characteristics and has excellent storability.

In recent years, as a secondary battery which is compact and lightweight and has high energy density, those which use a type of a conductive polymer as a negative electrode material and the negative electrode is combined with an electrolyte solution an alkali metal ion such as lithium ion, and sodium ion have attracted attention. This type of secondary battery is doping/undoping or intercalating/deintercalating the aforesaid metal ion electrochemically to the negative electrode and this doping/undoping phenomenon, etc. are utiliæed as a charge/discharge step. Thus, it has an advantage that, the problem of a secondary battery which employs a conventional alkali metal piece as the negative electrode, namely internal shorly of due to precipitation of the alkaline metal dendritely during the discharge and substantial deterioration of 5~

charge/discharge efficiency can be eliminated.

As this kind of secondary battery, there has been known one, for example, in which a negative electrode comprising a polyacetylene and a lithium ion are combined as dis-closed in Japanese Provisional Patent Publication No.
136469/1981. Further, as a conductive polymer which is usable for a neqative electrode material, there may be mentioned, in addition to the above polyacetylene, a linear high molecular compound having a conjugated double bond such as a poly(p-phenylene), a polypyrrol, a poly-thienylene, a polyaniline, a poly(p-phenylenesulfide), a poly(p-phenyleneoxide) and the like.

Since these conductive polymer is lightweight and a poten-tial for doping/undoping an alkali metal ion such as lithium ion, etc. to said polymer is substantially similar as a charge/discharge potential in case that the alkali metal is employed as a negative electrode, it has an advantage that an energy density per unit weight is high when it has used in a secondary battery. However, the aforesaid conductive polymer is unstable at a state of doping the alkali metal ion, that is, a charged state, and since it reacts with a solvent or decomposes itself, there are problems that a self-discharge becomes remark-ably great as well as a cycle characteristic will be deteriorated.

On the other hand, there has been reported a secondary battery in which a graphite having a structure of spread-ing conjugated double bonds quadratically is used as a carbonaceous material and a graphite interlayer compound which is intercalated by electrochemically reducing an alkali metal ion is employed as a negative electrode active substance. However, in such a secondary battery, since an alkali metal-graphite interlayer compound formed ;437 by charging is chemically unstable and it reacts with solvent in accordance with destruction of a graphite structure, there are disadvantages that its storability is bad and deterioration of charge/discharge efficiency as well as lowering of cycle characteristics will be occurred.

Further, there has been reported a secondary battery in which, as the carbonaceous material for constituting a negative electrode, those obtained by carbonizing an organic high molecular compound such as a phenol resin, a polyacrylonitrile, a cellulose and the like have been used. For example. in Japanese Provisi~nal Patent Publication No. 2098~4/1983, a secondary battery using as a negative electrode a carbonaceous material obtained by heat treating an aromatic condensed polymer, which has an atomic ratio of hydrogen/carbon being in th~ range of 0.15 to 0.33 has been disclosed.

Such a secondary battery has high output power as compared with a secondary battery using the conventional conductive polymer or a graphite as a negative electrode. However, it is the actual circumstances that there is not yet improved at all in the point that the negative electrode reacts with an electrolytic solvent ~ irreversibly during charged state so that an increase of self-¦ discharge and a deterioration of cycle characteristics will be caused.

As stated above, there remains a problem that a negative electrode material which utilizes a dope/undope or an intercalate/deintercalate phenomenon of an alkali metal lon is used in a battery, in all cases, a self-discharge increases and a cycle lifetime is short.

The present invention obviates such conventional problems and provides a secondary battery using a non-aqueous solvent which is less in self-discharge, good in charge/discharge cycle characterlstics and excellent in storability.

~ 7S~7 The present inventors have carried out earnest investigations by focusing the development of a negative electrode material for the secondary battery using a non-aqueous solvent. As results, they have found that by constituting a negative electrode with a carbonaceous material which satisfies various conditions mentioned below simultaneously, a secondary battery using a non-aqueous solven-t having excellent characteristics can be obtained.

ThuS the present invention provides in a secondary battery using a non-aqueous solvent comprising a positive electrode capable of recharging, an el~ctrolytic solution of an electrolyte in a non-aqueous solvent and a negative electrode capable of recharging, the improvement wherein said negative electrode comprises a carbonaceous material obtained by the carbonization o~ at least one of a compound selected from the group consisting of an organic high molecular compound, a condensed polycyclic hydrocarbon compound and polycycllc heterocyclic ~ompound, and having a pseudographite structure of an atomic ratio of hydrogen/carbon being not more than 0.15, the spacing of (002) planes as determined by x-ray wide-angle diffraction belng 3 . 37 A
to 3.75 A and the crystallite size in the direction of c axis being 8 A to 150 A.

Fig. 1 is a longitudinal sectional view showing one example of the non-aqueous solvent secondary battery of the present invention; aDd Figs. 2 to 4 are drawings showing chargeJdischarge curve of the 3~ batteries.

In the secondary battery using a non-aqueous solvent of the present invention, as a starting material for obtaining a carbonaceous material which constitutes a negative electrode, can be used at least one compound selected from the group consisting ~75~37 of an organic high molecular compound, a condensed polycyclic hydrocarbon compound and polycyclic heterocyclic compound.

As the organic high molecular compound, there may be employed any of organic high molecular compound of, for example, a linear novolac resin; a cellulose resin; a phenol resin; an acrylic resin such as a polyacrylonitrile, a poly(~ -halogenacrylonitrile), etc.; a halogenated vinyl resln such as a polyvinyl chloride, a polyvinylidene chloride, a polychlorinated vinyl chloride, etc.; a polyamideimide resin; a polyamide resin;
a conjugated resin such as a polyacetylene, a poly(p-phenylene), etc. Of these compounds, the linear novolac resin is particularly preferred.

Condensed polycyclic hydrocarbon compounds are such that at least two monocyclic hydrocarbon compounds consisting of a three or more membered ring are condensed together or derivatives of such condensed products. Specific examples of the condensed polycyclic hydrocarbon compounds may be mentioned, for example, naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chresene, naphthacene, picene, perylene, pentaphene, pentacene and the like, and the derivatives thereof may include carboxylic acid, carbocyclic acid anhydride or carboxylic acid amide of the above compounds. Further, various kinds of pitches mainly comprising mixtures of the above respective compounds.

Polycyclic heterocyclic compounds are such that at least two monocyclic heterocyclic compounds consisting of a three-or more membered ring are condensed together or at least one such monocyclic heterocyclic compound is condensed with at least one monocyclic hydrocarbon compound consisting of a three- or more membered ring and derivatives of such condensed products.
Specific examples of the polycyclic heterocyclic compounds may be mentioned, for example, indole, isoindole, quinoline, isoquinoline, quinoxaline, phthalazine, carbazole, acridine, phenazine, phenanthridine and the like, and the derivatives s~

thereof may include carboxylic acid, carbocyclic acid anhydride or carboxylic acid amide of the above compounds. Further, 1,2,4,5-tetracarboxylic acid of benzene, its dianhydride or its diimide may also b~ used.

The carbonaceous materials of the present invention are those obtained by carbonizing the above mentioned respective compound and have a pseudographite structure satisfying the following conditions simultaneously.

That is, in the first place, an atomic ratio of hydrogen/carbon measured by an elemental analysis is not more than 0.15, preferably not more than 0.10, more preferably not more than 0.07.

In the second place, a spacing (doo2) of (002) plane measured by X-ray wide angle diffraction is 3.37 A to 3.75 A, preferably 3.39 A to 3.75 A, more preferably 3.41 A to 3.70 A.
In the thlrd place, a crystallite size in the direction of c axis, Lc, measured by the same X-ray wide angle diffraction is 8 o e~ ~ o e, A to 150 A, preferably 8 A to 100 A, more preferably 10 A to 70 I A.

I

~75~37 While the carbonaceous material of the present invention can be obtained by carbonizing the above-mentioned respec-tive compounds, the procedures of the carbonization are considered as described below in the case of the condensed polycyclic hydrocarbon compound as the starting material.
That is, when a thermal energy greater than the dissocia-tion energy necessary to break the bond between the skele-tal carbon and an adjacent hydrogen atom or a substituent is provided by heating, carbon radicals are formed pre-dominantly by homolytic cleavage. A chain of carbonradicals is cyclized to provide a higher molecular weight and the polycyclic aromatic planes are developed so that the process of carboniæation successively occurs. In the initial stage of carbonization, for example, benzene rings are bound together one-dimensionally to form a one-dimen-sional graphite structure. Subsequently, the benzene rings start to bind with one another two-dimensionally, and gradually expanding polycyclic aromatic planes begin to stack in layers to form a two-dimensional graphite structure.

With further progress of carbonization, more benzene rings are bound two-dimensionally and adequately expanded poly-cyclic aromatic planes stack one on another in an orderly manner to form the ordinary graphite. In accordance with the present invention, all structures that lead to the final graphite are collectively referred to as the pseudo-graphite structure.

The pseudographite structure in accordance with the pre-sent invention can be determined quantitatively by using an X-ray wide angle diffraction. The ordinary graphite shows a sharp diffraction peak corresponding to a (002) plane at about 20 = 26.
A one-dimensional graphite formed in the initial stage of carbonization of the present invention shows no diffrac-~75~37 tion peak corresponding to the (002) plane or shows a verybroad and its intensity is low.

Then, the polycyclic aromatic planes is developed two-dimensionally to some extent and begin to stack one after another, the diffraction peak corresponding to the (002) plane gradually becomes sharp and its intensity increases.

The pseudographite structure which characterizes the carbonaceous material of the present invention is such that the spacing of (002) planes, doo2, is at least 3.37 A
and the crystallite size in the direction of c axis, Lc, is not more than 150 A. Preferably, doo2 is at least 3.40 A and not more than 3.75 A, whereas Lc is at least 7.0 A
and not more than 150 A. The case where no diffraction peak corresponding to the (002) plane is observed at all is also included in the present invention.

When the carbonaceous material to be used is not satisfied any one of the above three inevitable requirements, that is, the atomic ratio of hydrogen/carbon is 0.15 or more, the spacing doo2 of the (002) plane measured by the X-ray wide angle diffraction is not more than 3.37 A or the crystallite size in the direction of c axis, Lc, measured by the same exceeds 150 A, in the secondary battery using the carbonaceous material as the negative electrode, dis-advantages that over voltage of charge/discharge at the negative electrode side becomes large, a gas is generated from the electrode at the charging, storability of the battery at the charged state is bad and charge/discharge cycle characteristics are deteriorated are caused.

In the carbonaceous material to be used in the present invention, the following conditions may desirably be satisfied in addition to the above three conditions. That is, in the pseudographite structure determined quantita-tively by using the X-ray wicle angle diffraction, a cry-stallite size in the direction of a axis La is preferably lo A or more, more preferably 15 A or more and 150 A or less, particularly preferably 19 A or more and 70 A or less. Further, a distance aO t= 2dllo) twice the spacing dllo of the (110) planes measured by the X-ray wide angle difEraction is preferably 2.38 A or more and 2.47 A or less, more preferably 2.39 A or more and 2.46 A or less.
Moreover, at least one of the signals have an inter-peak line width (~Hpp) obtained by first differential absorp-tion curve of the electron spin resonance spectrum (mea-sured at 23 C) of preferably 20 gauss or more, or no signals have an inter-peak line width (~Hpp) of not more than 20 gauss. More preferably, at least one of the signals have an inter-peak line width (~Hpp) obtained by first differential absorption curve of the electron spin resonance spectrum (measured at 23 C) of preferably 50 gauss or more, or no signals have an inter-peak line width (~Hpp) of not more than 50 gauss.
i The above carbonaceous material is specified by the atomic ratio of hydrogen/carbon obtained by the elemental analy-i sis, but a small proportion of other atoms such as a ! nitrogen, oxygen, halogen may be present.
In the present invention, the carbonaceous material consti-tuting the negative electrode can be obtained by carbona-ting the aforesaid compounds, more specifically by sinter-ing under vacuum or through an inert gas (N2, Ar, etc.).
30 Since the carbonating temperature is closely related to the above atomic ratio of hydrogen/carbon, it is required to set the atomic ratio to not more than 0.15. The carbo-nating temperature is different depending on the kinds of the compounds to be used as a starting material but usual-ly 500 to 3,000 C is preferred.

i' ~i~75437 Of the aforesaid compounds, with respect to polyacrylonit-rile, pitch, etc., it is preferred to carry out9 prior to carbonization, the flame resistant treatment or the infus-ible treatment at 200 to 400 C by heating under active atmosphere such as an air.

Further, after completion of the carbonization step, the obtained carbonaceous material may be activated by heating the carbonaceous material under oxidative gaseous atmos-phere such as vapor, carbon dioxide, etc. whereby a speci-fic surface area thereof can be increased.

The positive electrode material of the non-a~ueous solvent secondary battery in accordance with the present invention is not particularly limited and there may be mentioned, for example, a metallic chalcogen compound which release or capture an alkali metal cation such as lithium ion, etc.
accompanying charge/discharge reaction, and a carbonaceous material having specific hydrogen/carbon atomic ratio as mentioned in the above negative electrode.

First, specific examples of the metallic chalcogen com-pounds to be used as the constituting material of the positive electrode of the present invention may include oxides such as Cr3O8, V2O5, V~O13, 2 3 3 etc.; sulfides such as TiS2, V2S5, MoS2, MoS3, CuS, Fe 25Vo 75S2~ Cr0 25V0 7sS2~ Cro.5vo.5 2~ 0.1 2 etc.; phosphine-sul'ur compounds such as NiPS3, FePS3, etc.; and selenium compounds such as VSe2, NbSe3, etc., among them, TiS2, MoS2 and V2O5 are particularly pre-ferred.

To use such metallic chalcogen compounds as the positive electrode is preferred in the point of obtaining a second-ary battery having large capacity and high reliability.

On the other hand, a carbonaceous material to be used as ~75437 the constituting material of the positive el~ctrode isthe same as the carbonaceous material constituting the above negative electrode and one obtained by carbonization of at least one compounds selected from the group consist~
ing of an organic high molecular compound, a condensed polycyclic hydrocarbon compound and a polycyclic hetero-cyclic compound, and has an atomic ratio of hydrogen/-carbon being 0.10 or more and 0.70 or less, preferably 0.10 or more and 0.60 or less, more preferably 0.10 or more and 0.50 or less. When the atomic ratio of hydrogen/-carbon deviates the above range, over voltage of the charge/discharge at the positive electrode side becomes large and stable charge/discharge cyclic could not be realized with low charge efficiency of the charge/dis-charge whereby deterioration of the battery characteristicsmay be caused according to circumstances.

When these carbonaceous material is used as the positive electrode material, it is preferred that the atomic ratio of hydrogen/carbon of the carbonaceous material constitut-ing the positive electrode is set greater than those of - the carbonaceous material constituting the negative elect-j rode ~rom the point of heightening the battery character-istics much more.
Moreover, these carbonaceous materials are preferred those having pseudographite structure satisfying the conditions as mentioned below. That is, the carbonaceous material to be used in the positive electrode is firstly the spacing of (002) planes, doo2, measured by the X-ray wide angle diffraction is preferably at least 3.42 A, more preferably at least 3.44 A, particularly preferably at least 3.46 A.
Further, the crystallite size in the direction of c axis, Lc, is not more than 70 A, more preferably not more than 50 A, particularly preferably not more than 30 A, and the crystallite size in the direction of a axisr La, is not ~7';437 more than 70 A, more preferably not more than 50 A, parti-cularly preferably not more than 30 A. Moreover, a dis-tance aO (= 2dllo) twice the spacing dllo of the (110) planes measured by the X-ray wide angle diffraction is preferably not more than 2.45 A, more preferably 2.37 A or more and 2.43 A or less.

Furthermore, the carbonaceous materials to be used in the positive electrode have preferably at least one of the signals having an inter-peakline width (aHpp) obtained by first differential absorption curve of the electron spin resonance spectrum (measured at 23 C) of 7 gauss or more, or no signals having an inter-peak line width (~Hpp) of not more than 7 gauss. More preferably, they have at least one of the signals having an inter-peak line width (aHpp) obtained by first differential absorption curve of the electron spin resonance spectrum (measured at 23 C) of preferably 10 gauss or more, or no signals having an inter-peak line width (aHpp) of not more than 10 gauss.
Also, the carbonaceous material constituting the positive electrode can be obtained in the same manner as in the carbonaceous materials for the negative electrode by carbonating the aforesaid compounds, that is by by sinter-ing them. The carbonating temperature at this time maypreferably be set, for example, at 300 to 2,000 C.

When the positive electrode comprising these carbonaceous material and the negative electrode comprising the afore-said materials for the negative electrode are combinedlyused, a secondary battery having good battery performances can be obtained without carrying out the preliminary ope-ration of discharging or charging the positive electrode or the negative electrode previously.

In the present invention, as the materials for the posi-~l~75437 tive electrode, in addition to the above metallic chalco-gen compounds and the carbonaceous materials, a conductive polymer doped or dedoped an electrolytic anion accompany-ing with the charge/discharge reaction can also be used.
As the conductive polymer, there may be mentioned high molecular compounds having linear conjugated double bonds such as polyacetylene, poly(p-phenylene), polypyrrole, polythienylene, polyaniline, poly(p-phenylenesulfide), poly(p-phenyleneoxide) and the like.
Further, in the non-aqueous secondary battery of the present invention, as the electrolyte, those dissolved an electrolytic salt in a non-aqueous solvent can be used.
As the non-aqueous solvent, there may be used propylene carbonate, ethylene carbonate, dimethoxyethane, ~-butyro-lactone, tetrahydrofuran, 2-methyltetrahydrofuran, sulfo-rane, 1,3-dioxorane and the like, and they may be used alone or in combination of 2 or more. On the other hand, as the electrolytic salts, those obtained by optionally 20 combining an anion such as CQO4 , PF6 , BF4 , CF3SO3 , AsF6 , etc. and an alkali metal cation such as Li , Na , K+, etc. can be used. As the cation, in addition to the above alkali metal cation, cation species of quaternary amines such as N(CH3)4 , N(C2H5)4 , N(n-C3H7)4 , etc- may be used.

When the metallic chalcogen compound is used as the active substance in the positive electrode and carbonaceous materials as the negative electrode of the secondary battery, either one of the positive electrode and the negative electrode or both of the positive and negative electrodes may preferably be doped an alkali metal cation such as Li+ and the like.

In case where doping is previously carried out with res-pect to the positive electrode, a battery in the dis-1~5~37 charged state can be realized, while doping in the nega-tive electrode provides a battery in the charged state.
When the doping is carried out in both of the positive and negative electrodes, a battery in any state between dis-charged and charged by changing the ratio of dopingamounts to the respective electrodes can be manufactured.

The capacity of the battery is determined by the total amounts of an alkali metal to be doped in the positive and/or negative electrodes.

When the carbonaceous material of the present invention is used in the negative electrode, the alkali metal is doped in a film~like or a strip-like carbonaceous material or is doped in moldings prepared by mixing a powder of the carbonaceous material and a powder state adhesive such as polytetrafluoroethylene, polyethylene, etc. and kneading, and then by molding under heating.

As the method for doping the alkali metal cation in the electrodes previously, there may be mentioned, for exam-; ple, the electrochemical method, the chemical method and the physical method.

More specifically, as the electrochemical method, there may include a method in which the carbonaceous material of the present invention is used as the positive electrode, an alkali metal M is used as the negative electrode and an electrolyte obtained by dissolving an alkali metal salt such as MC~04, MPF6, MBF4, MAsF6, MA~CQ4, MC~, MBr, MI and the like (where M is anyone of Li, Na, K, Rb and Cs) in an organic solvent such as propylene carbonate, 1,2-dimethoxy-ehtane, ~-butyrolactone, dioxolan, ethylene carbonate,

2-methyltetrahydrofuran and the like is interposed between the electrodes to continue therebetween or a current is passed therethrough. As the chemical method, there may be ~ ~7~437 mentioned the method in which the carbonaceous material according to the present invention is dipped in an organic solvent solution such as ether, aliphatic hydrocarbon, etc.l dissolved an alkylated alkali metal therein. Fur-ther, as the physical method, there may be mentioned themethod in which the carbonaceous material according to the present invention is exposed to vapor of an alkali metal.
Of these methods, preferred are the electrochemical method and the chemical method and more preferred is the electro-chemical method.

When the alkali metal is doped in the positive electrode,i.e., in the metallic chalcogen compound which is the discharged state of the battery, the same methods as in the above carbonaceous material can also be applied.

In this case, when the metallic chalcogen compound elec-trode is used as the positive electrode, a negative poten-tial is applied to the electrode and a positive potential is applied to the opposite electrode.

As the opposite electrode material, there may be mention-ed, for example, an inert metal such as platlnum, etc., and an alkali metal such as lithium, etc., but the use of lithium is particularly desired.

When the non-aqueous solvent secondary battery is consti-tuted by the above material, the positive electrode and the negative electrode are laminated opposite to each other lying a separator between them and/or interposed a separator between them and a non-aqueous solvent contain-ing an electrolyte. Each electrode has a plate-like structure in general, hut the structure where one elec-trode is made a cylindrical shape and the other electrode is inserted therein may be employed. Further, the struc-ture where the positive electrode and the negative elec-~ ~754~
~ 16 -trode are made opposite to each other through a separator and spirally wound to form a spiral structure may also be employed.

Further, it is a desirable embodiment that the electroly-tic solution is impregnated in a separator such as a non woven, a woven, an open cell cellular foaming material and a porous plastic sheet and the separator is interposed between both of the electrodes.
In the non-aqueous secondary battery constituted by the negative electrode, the positive electrode and the ele-ctrolyte comprising the aforesaid each materials, it is confirmed that an electrochemically oxidation/reduction reactlon in accordance with the dope/undope of the alkali metal ion is occurred at the charge/discharge and the battery has been less self-discharge and has good cycle characteristics.

In the secondary battery using a non-aqueous solvent of the present invention, a discharging capacity of the positive electrode should preferably be set l.l-fold or more to that of the negative electrode, more preferably l.l-fold to 3-fold, and most preferably 1.5-fold to 2-fold.

That is, for example, in case of using V2O5 as the posi-tive electrode active substance, by repeating dope/undope of lithium to the V2O5, reversibility of dope/undope of lithium to the V2O5 will be gradually impaired when the doping is carried out in an amount of 2/3 or more to the maximum amount capable of being doped the lithium to the V2O5 so that deterioration of the battery capacity accom-panied by proceeding of cycles will be remarkable.

~754~7 By the reason as stated above, when the battery constitu-tion using the metallic chalcogen compound as the positive electrode and the carbonaceous material in accordance with the present invention as the negative electrode is employ-ed, it is preferred that the capacity of the positiveelectrode is set l.l-fold or more to that of the negative electrode to enlarge a space (residual capacity) capable of accepting a lithium ion at discharging.

When the capacity of the positive electrode is set 1.1-fold or more to that of the negative electrode, the capa-city of the battery is regulated by the capacity of the negative electrode. Therefore, it is not preferred to remarkably enlarge the capacity of the positive electrode to that of the negative electrode since high capacity characteristics which are possessed of the battery of the present constitution will be lost, and thus, the discharg-ing capacity of the positive electrode is set within the above range.
In the present invention, each measurements of the ele- -mental analysis, X-ray wide angle diffraction and electLon spin resonance spectrum are carried out following the methods as described below.
[Elemental analysis]

A sample is dried in vacuum at 120 C for about 15 hoursO
Then, the sample is transferred onto a hot plate in a dry box and dried in vacuum at 100 C for 1 hour. A portion of the dried sample is put into an aluminum cup in an argon atmosphere, and the carbon content is determined from the weight of CO2 gas evolved as a result of com-bustion whereas the hydrogen content is determined from the weight of H2O also evolved by combustion. In the ~L~75~37 Examples of the present invention that follow, an ele-mental analyzer of Perkin-Elmer Model 240 C was used.

[X-ray wide angle diffraction]

(1) doo2, the spacing of (002) planes, and dllo, the spacing of (110) planes:

A powder of carbonaceous material (flaky carbonaceous material is reduced to a powder in an agate mortar) is packed into a sample cell together with about 15 wt % of the powder of an internal standard substance, a hiyh-purity silicon powder of the standard grade for X-ray analysis.
A wide-angle X-ray reflection diffractometer scan is obtained with monochromatic CuK~ radiation from a graphite monochrometer. Instead of making corrections associated with the Lorentz factor, polarization factor, absorption factor and atomic scattering factor, the following simple and convenient method is used. Draw a baseline for the scan curves corresponding to diffractions at (002) and (110) Planes. Plot the substantial intensities as calcu-lated from the baseline, obtaining corrected curves for (002) and (110) planes. Draw an angular axis at a height which is two-thirds of the height of the peak in each curve and obtain the midpoint of the line defined by the two points where a line parallel to that angular axis intersects the scan curve. Correct the angle of the midpoint by the internal standard to obtain a value twice the angle of diffraction. Substitute this value and the wavelength of CuK~ radiation,~ , into the following two eguations of Bragg's law to obtain doo2 and dllo:

002 2 i [A~;

~7S14~7 dll0 = ~ [A~
wherein ~: 1.54]~ A
~, 9': the angle of diffraction corresponding to doo2 or dll0' (2) Crystallite size in c and a axes, Lc and La:

Ohtain the half-width ~ at a point hdlf the height of the peak in each of the corrected scan curves prepared in (1), and substitute this value into the following equations:

Lc = - - tA];
~-cosQ
K-~ O
La = [A]
~ cos~ ' Various values may be taken for the shape factor K, but in the present invention, K = 0.90 is used. For the meanings of ~, ~ and ~', the same as the previous paragraph.

~Line width between peaks in the first differential of the absorption spectrum of electron spin resonance: ~Hpp3 The first differential of the absorption spectrum of electron spin resonance was measured with JEOL JES-FE lX
ESR spectrometer in the X-band. A powder of carbonaceous material ~flaky carbonaceous material is reduced to a powder in an agate mortar~ is put into a capillary tube (ID: 1 mm) which is placed in an ESR tube ~OD: 5 mm). The radiofrequency magnetic field is modulated by an amount of 6.3 gauss. All the procedures above are followed within air at 23 C. The value of the line width between peaks 1~75437 in the first differential of the absorption spectrum ~Hpp) is determined by comparison to a standard sample Mn ~MgO.

EXAMPLES

Examples 1 to 11 (1) Preparation of the carbonaceous material In a reactor were put 108 g of ortho-cresol, 32 g of para-formaldehyde and 240 g of ethylcellosolve with 10 g of sulfuric acid, and the mixture was reacted at 115 C for 4 hours under stirring. After completion of the reaction, the mixture was neutralized by adding 17 g of NaHCO3 and 30 g of water. Then, under stirring with high speed, the reaction mixture was poured into 2 liters of water and precipitated products were collected by filtration to obtain 115 g of linear high molecular weight novolac resin. The number average molecular weight of the resin was measured by applying the vapor pressure method (in methylethyl ketone, at 40 C) to obtain 2600.

After dissolving 2.25 g of this novolac resin and 0.25 g of hexamine in ethanol, the ethanol was evaporated and removed to obtain a mixture of the novolac resin and hexamine. Then, the mixture was put in a glass vessel under nitrosen gas stream, and heat treated at 250 C for 2 hours under nitrogen gas stream.
The thus obtained heat-treated mixture was not dissolved in ethanol but swelled. The swelled heat-treated mixture was carried out the press forming at a temperature of l9Q
C under a pressure of 200 Kg/cm2 to obtain a strip having a width of 2 cm, a length of 5 cm and a thickness of 1 mm.

~7t~ 7 Then, the press forming product was set in an electric furnace and under nitrogen stream carbonization was carried out by e~evating the temperature to 2100 C per elevating speed of 20 C/min. and maintaining the tempera-ture, i.e., at 2100 C for one hour under nitrogen stream.As a result, 80 mg of a strip-like carbonaceous material a having black color was obtained.

Further, in the above steps, by the same conditions as in the above except for changing the carbonization tempera-ture to 1600 C, 1400 C, 1000 C and 800 C, each 80 mg of strip-like carbonaceous materials b, c, d and e was obtained, respectively.

lS Each value of the carbonization temperature ~C] during synthesis, the atomic ratio of hydrogen/carbon measured by elemental analysis, the plane spacing doo2 ~A] of (002) plane and the plane spacing dl1o [~] of (110) plane each measured by the X-ray wide angle diffraction, the crystal-lite size Lc [A] in the direction of c axis and the cry-stallite size La [A] in the direction of a axis, and the line width between peaks of the electron spin resonance spectrum ~Hpp ~gauss] of the carbonaceous materials a to e was summarized in Table 1. In the table, each of the above values with respect to graphite was also shown.

As clearly seen from the table, among the above carbona-ceous materials a to e, a and b are materials for the negative electrode, d and e are materials for the positive electrode, and c is a material usable or both the nega-tive electrode and the positive electrode.

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~ ~754~7 (2) Evaluating tests of the secondary battery performances By using each of the carbonaceous materials obtained by the above, the secondary batteries using a non-aqueous solvent as shown in Fig. 1 were prepared. In Fig. 1, reference numeral 1 represents a negative electrode and it is prepared by press forming 50 mg of each powder of the carbonaceous material as mentioned above to form a pellet having a diameter of 20 mm. 2 is a collector for the negative electrode comprising nickel. A negative elec-trode terminal 4 is e]ectrically connected to the collec-tor 2 for the negative electrode through a spring 3. 5 is a positive electrode which is prepared by press forming 50 mg of each powder of the carbonaceous material as mention-ed above to form a pellet having a diameter of 20 mm, is prepared by mixing and kneading 450 mg of titanium disul-fide tTiS2) with 25 mg of polytetrafluoroethylene and 25 mg of acetylene black and then press forming it to a pellet having a diameter of 20 mm or is prepared by mixing 20 and kneading 450 mg of vanadium pentoxide tV2O5) with 25 mg of polytetrafluoroethylene and 25 mg of acetylene black and then press forming it to a pellet having a diameter of 20 mm. The positive electrode 5 is one which is carried out a preliminary discharging at 2 mA for 10 hours in a propylene carbonate solution containing 1.5 mole/liter of LiCO4. Further, the positive electrode 5 is compressedly adhered to a collector 6 for the positive electrode compris-ing titanium which serves as a positive terminal. Between the negative electrode 1 and the positive electrode 5, a separator 7 comprising non woven fabric of propylene carbonate is provided therethrough and they are all com-pressedly adhered with each other by the spring 3. Refer-ence numerals 8 and 9 are vessels made of Teflon ttrade ~ame, produced by du Pont de Nemours), and inner materials are sealed by an O ring 10. Moreover, 2 ml of a propyl-ene carbonate solution containing 1.5 mole/liter of ~7Cj~37 LiCQO4 as an electrolyte is filled in the separator 7, and the vessels ~ and 9.

Here, by combinedly using the carbonaceous materials a, b, c, d and e shown in Table 1, and TiS2 and V2O5 as the above positive electrode 5 and the negative electrode 1, batteries A, B, C, D, E, F, G, H, I, J and K of the pre-sent invention were prepared and they were evaluated with respect to the following evaluating tests of respective performances.

Comparative examples 1 to 8 In the same manner as in Examples 1 to 11, by combinedly using the carbonaceous materials d and e shown in Table 1, graphite and TiS2 and V2O5 as the above positive electrode 5 and the negative electrode 1, batteries L, M, N, O, P, Q, R and S for comparative purpose were prepared and they were also evaluated with respect to the following evalu-ating tests of respective performances.

(a) Evaluating test of charge/discharge cycle characteris-tics (i) As to the above respective batteries A to S, charge/-discharge test was carried out under argon gas atmosphere at 25 C upto each 100 cycles. A charging current and a discharging current were all 500 ~A and discharye was started immediately after completion of charging. Closed circuit terminal voltages for charging and discharging processes were set as follows, respectively.

Batteries A to E, L and M:
charging voltage = 3.5 V, discharging terminal voltage = 2.0 V

~75437 Batteries F to H and N to P:
charging voltage = 2.1 V, discharging terminal voltage = 1.0 V
Batteries I to K and Q to S:
charging voltage = 3.0 V, discharging terminal voltage = 2.0 V

Fig. 2 shows charge/discharge curves of the batteries A, D
and L at the fifth cycle. In the Fig., curves Al, Dl and Ll each represent charging curves of the batteries A, D
and L, respectively, and curves A2, D2 and L2 are each represent discharging curves of the same. Further, in Fig. 3, charge/discharge curves of the batteries F, H and O at the fifth cycle are shown, and curves Fl, Hl and l each represent charging curves of the batteries F, H and O, respectively, and curves F2, H2 and 2 are each repre-sent discharging curves of the same. Moreover, in Fig. 4, charge/discharge curves of the batteries I, K and Q at the fifth cycle are shown, and curves Il, Kl and Ql each represent charging curves of the batteries I, K and Q, respectively, and curves I2, K2 and Q2 are each represent discharging curves of the same.

Furthermore, in Table 2, charging capacities, discharging capacities and charge/discharge efficiencies at the fifth cycle and the 100th cycle and a ratio ~%) of discharging capacity at the 100th cycle to the fifth cycle of each of the batteries are shown.

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~L~754;~

(ii) Charge/discharge test was carried out in the same manner as in the above (i) except for changing the charge/discharge cycle number to 50 cycles. In Table 3, charging capacities, discharging capacities and charge/-discharge efficiencies at the tenth cycle and the 50thcycle and a ratio (~) of discharging capacity at the 50th cycle to the tenth cycle of each of the batteries are shown.

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~754~7 (b) Evaluating tests of self-discharge and preservability (i) In the same manner as in the above (a), usual charge/-discharge was carried out upto the ninth cycle and then self-discharge test was carried out at the tenth cycle.
That is, at the tenth cycle, discharge after completion of charging was carried out after preservation at 25 C for 30 days.

In Table 4, charging capacities, discharging capacities and charge/discharge efficiencies at which discharging was immediately carried out at the ninth cycle and at which discharging was carried out at the tenth cycle after preservation for 30 days and a ratio (%) of discharging capacity at the tenth cycle to the ninth cycle of each of the batteries are shown.

43~
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(ii) In the same manner as in the above (i), usual charge/-discharge was carried out upto the forth cycle and then self-discharge test was carried out at the fifth cycle.
That is, at the tenth cycle, discharge after completion of charging was carried out after preservation at 25 C for 30 days.

In Table 5, charying capacities, discharging capacities and charge/discharge efficiencies at which discharging was immediately carried out at the forth cycle and at which discharging was carried out at the fifth cycle after preservation for 30 days and a ratio (%) of discharging capacity at the fifth cycle to the forth cycle of each of the batteries are shown.

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As clearly seen from the description as mentioned above, the secondary battery using a non-aqueous solvent of the present invention using a carbonaceous material having the specific structure for the negative electrode has extreme-ly excellent charge/discharge cycle characteristics ascompared with those used a conventional graphite as the negative electrode material and those used a carbonaceous material deviated from the requirements of the present invention, and is less in self-discharge and excellent in preservability whereby its industrial value is extremely great.

Claims (16)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A secondary battery comprising a positive electrode capable of recharging, an electrolytic solution of an electrolyte in a non-aqueous solvent and a negative electrode capable of recharging, in which said negative electrode comprises a carbonaceous material obtained by the carbonization of at least one of a compound selected from the group consisting of an organic high molecular compound, a condensed polycyclic hydrocarbon compound and polycyclic heterocyclic compound, and having a pseudographite structure of an atomic ratio of hydrogen/carbon being not more than 0.15, a spacing of (002) planes as determined by X-ray wide-angle diffraction being 3.37 .ANG.
to 3.75 .ANG. and a crystallite size in the direction of c axis being 8 .ANG. to 150 .ANG..

2. A secondary battery according to Claim 1, wherein said positive electrode and said negative electrode are laminated through a separator impregnated with the electrolyte.

3. A secondary battery according to Claim 1, wherein said electrolyte is a combination of an alkali metal cation and at least one anion selected from the group consisting of C O4-, PF6-, BF4-, CF3SO3- and AsF6-; or a quaternary amonium salt.

4. A secondary battery according to Claim 1, the carbonaceous material having the atomic ratio of hydrogen/carbon not more than 0.10, the spacing of (002) planes, d002, as determined by X-ray wide-angle diffraction being 3.39 .ANG. to 3.75 .ANG. and the crystallite size in the directlon of c axis, Lc, being 8 .ANG. to 100 .ANG..

5. A secondary battery according to Claim 4, the carbonaceous material having the atomic ratio of hydrogen/carbon being not more than 0.07, the d002 being 3.41 .ANG. to 3.70 .ANG. and the Lc being 10 .ANG. to 70 .ANG..

6. A secondary battery according to Claim 1, the carbonaceous material having the atomic ratio of hydrogen/carbon being not more than 0.10, the spacing of (002) planes, d002, as determined by X-ray wide-angle diffraction being 3.39 .ANG. to 3.75 .ANG., the crystallite size in the direction of c axis, LC, being 8 .ANG. to 100.ANG., a crystallite size in the direction of a axis, La, being 10 .ANG. or more and a distance a0 twice the spacing d110 of the (110) planes measured by X-ray wide-angle diffraction being 2.38 .ANG. to 2.47 .ANG..

7. A secondary battery according to Claim 6, the carbonaceous material having the atomic ratio of hydrogen/carbon being not more than 0.07, the d002 being 3.41 .ANG. to 3.70 .ANG., the Lc being 10 .ANG. to 70 .ANG., the La being 15 .ANG. to 150 .ANG. and the a0 being 2.39 .ANG. to 2.46 .ANG..

8. A secondary battery according to Claim 1, wherein said positive electrode is constituted by a metallic chalogen compound.

9. A secondary battery according to Claim 8, wherein said metallic chalcogen compound is selected from the group consisting of Cr3O8, V2O5, V6O13, LiCoO2, MoO3, WO3, TiS2, V2S5, MoS2, MoS3, CuS, Fe0.25V0.75S2, Cr0.25V0.75S2 Cr0.5V0.5S2, Na0.1CrS2, NiPS3, FePS3, VSe2 and NbSe3.

10. A secondary battery according to Claim 1, wherein a discharging capacity of said positive electrode is set 1.1-fold or more to that of said negative electrode.

11. A secondary battery according to Claim 1, wherein said positive electrode is constituted by a carbonaceous material obtained by carbonizing at least one compound selected from the group consisting of an organic high molecular compound, a condensed polycyclic hydrocarbon compound and polycyclic heterocyclic compound having an atomic ratio of hydrogen/carbon being 0.10 or more to 0.70 or less.

12. A secondary battery according to Claim 11, wherein the carbonaceous material of said positive electrode having the atomic ratio of hydrogen/carbon being 0.10 to 0.60, a spacing of (002) planes, d002, as determined by X-ray wide-angle diffraction being 3.42 .ANG. or more and a crystallite size in the direction of c axis, Lc, being 70 .ANG. or less.

13. A secondary battery according to Claim 12, the carbonaceous material of said positive electrode having the atomic ratio of hydrogen/carbon being 0.10 to 0.05, the d002 being 3.44 .ANG. or more and the Lc being 50 .ANG. or less.

14. A secondary battery according to Claim 13, the carbonaceous material of said positive electrode having the atomic ratio of hydrogen/carbon being 0.10 to 0.50, the d002 being 3.46 .ANG. or more and the Lc being 30 .ANG. or less.

15. A secondary battery according to Claim 1, wherein said carbonaceous material is previously doped with alkali metal cation.

16. A secondary battery according to Claim 8, wherein said chalcogen compound is previously doped with an alkali metal cation.