JPS60225375A - Secondary battery - Google Patents

Abstract

PURPOSE:To reduce the amount of an electrolytic solution so as to make a secondary battery light and compact by using the electrolytic solution that contains a part of the electrolyte not in a dissolved state in all processes of charge and discharge. CONSTITUTION:In a secondary battery based on doping or intercalation mechanism, an electrolytic solution is formed so as to contain a part of the electrolyte not in a dissolved state in all processes of charge and discharge. For example, the electrolytic solution is formed in which propylene carbonate and such are used as the solvent and ammonium tetraethyl perchlorate or lithium perchlorate is used as the electrolyte. When the electrolyte of a battery in the charge completion state is most consumed, the electrolytic solution contains solid phases and the amount of non-dissolution (the amount of deposition) is set to within 50%, desirably within 20% of the entire electrolyte. Since the amount of solvent can be reduced in this battery, energy density can be improved.

Description

[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to a secondary battery, and in particular to a secondary battery that is suitable for reducing the amount of electrolyte and improving energy density. This invention relates to a secondary battery using an electrolytic solution containing a portion of the electrolyte in an undissolved state.

[Background of the Invention 1 Conventionally, in batteries using electrode materials that can be doped and undoped, there are systems in which the entire amount of electrolyte that constitutes the doping species is dissolved in a solvent (hereinafter referred to as a completely dissolved battery), Alternatively, a system in which a solid phase consisting of an electrolyte that is to constitute a doping species is impregnated with the minimum necessary amount or an extremely small amount of solvent at 1F that provides ion mobility for the doping species (hereinafter referred to as a solid electrolyte battery) ) is known.

Regarding battery performance, especially energy density and power density, the battery suitability of the electrode material itself, the doping species, and the battery suitability of the electrolyte are particularly important, but from a practical standpoint, other battery constituent materials, such as TEPCO It is equally important to reduce the weight of structural materials such as separators, containers, or solvents, or to reduce their size or volume as much as possible, thereby reducing the energy density and power density of the battery. can be improved.

In the fully dissolved battery described above, it is necessary to achieve the mass transfer of the stone doping species required during charging or discharging at a practically desirable rate, and to reduce the liquid resistance of the battery to a desired low level. The entire amount of electrolyte required for maintenance is present dissolved in the liquid phase. In order to increase the energy density or power density of the battery by increasing the amount of doping or dedoping per unit weight of the electrode material, the required amount of doping or dedoping is limited due to the solubility of the electrolyte. melt tsff accordingly
Although it is necessary to increase i, this increases the total weight of the battery, which is not practical.

Furthermore, in a periphery electrolyte battery, a minimum amount of solvent or an extremely small amount close to the minimum amount necessary for ensuring the ion mobility of the doping species required during charging or discharging is used. However, when considering simply securing the ion mobility of the doping species, the amount of solvent may be sufficient to impregnate a small amount of solvent into the solid phase consisting of the electrolyte, but it is necessary for electrode materials and practical batteries. In order to achieve the required amount of doping or dedoping at the required rate, it is necessary to further increase the conductivity of the electrolyte and to reduce the resistance overvoltage due to the electrolyte as much as possible. Therefore, solid electrolyte batteries containing only a very small amount of solvent compared to the solid electrolyte are subject to significant practical limitations, and are particularly disadvantageous for applications requiring high power density.

As mentioned above, both completely dissolved batteries and solid electrolyte batteries have drawbacks that are undesirable in practical use.

In recent years, various types of secondary batteries have been devised as high-energy density secondary batteries that use interlayer compounds or organic polymer compounds with conjugated double bonds in their main chains, such as polyacetylene, as electrodes.
There is.

Hereinafter, a secondary battery using polyacetylene as a positive electrode and a negative electrode will be explained as an example. Polyacetylene is prepared by converting acetylene into Degla-Natsuta catalyst [for example, Ti(OC4F+9
)4 ・AI (C2H5)3 ) Te It is an organic polymer compound obtained by polymerization. Since this compound can be doped with various anions and cations by electrochemical techniques, it has been revealed that polyacetylene can be used as an electrode material for secondary batteries (for example, JP-A-56-136469). This results in
It is possible to construct a secondary battery using polyacetylene as the positive and negative electrodes, and using an electrolyte consisting of ions with a wide electrochemical stability range dissolved in a solvent with a wide electrochemical stability range. can. As the electrolyte in this case, alkali metal or quaternary ammonium perchlorates, borofluorates, etc. are often used, and
As the solvent, tetrahydrofuran, propylene carbonate, etc. are often used.

The operation of the battery is as follows, taking as an example the case where tetra]-derammonium perchlorate is used as the electrolyte. That is, during charging, perchlorate ions are doped from the electrolyte into the polyacetylene of the positive electrode (incorporated into the polyacetylene), and tetraethylammonium ions are doped from the electrolyte into the polyacetylene of the negative electrode.

On the other hand, in the discharge process, the anions and cations doped into the polyacetylene as described above are released into the electrolytic solution again.

Therefore, in this battery, since the sufficient amount of electrolyte incorporated into the polyacetylene during charging is about 1 mol/hour, it is not necessary to use an electrolyte solution in which the electrolyte is completely dissolved in the solvent as in the past. In this case, it is necessary to increase the amount of electrolyte, which causes a problem in that the energy density of the battery decreases.

[Object of the Invention] The present invention has been made in view of the above, and its objectives are to reduce the amount of electrolyte, improve energy density, and realize lighter and more compact batteries. Our goal is to provide rechargeable batteries that can.

[Summary of the Invention 1 The feature of the present invention is doping or interreaction]
In a secondary battery based on the intercalation mechanism, the electrolyte forms a doping species during the entire process of charging and discharging.
It lies in the point of being υ.

In the battery of the present invention, -C, which is the material for the electrode 14 that performs the electrode reaction based on the doping mechanism, is a right-handed polymer compound having a conjugated double bond in its main chain. Specific examples of organic polymer compounds having a conjugated double bond in the main chain include acetylene polymer (polyacetylene), polyphenylacetylene, polyvaraphenylene, polymetaphenylene,
Poly(2゜5-chenylene), poly(3-methyl-2,
5-chenylene), polypyrrole, poly(ethynylnaphthalene), polyimide, polyacrylonitrile, poly-
The examples include, but are not limited to, thermal decomposition products of α-cyanoacrylic, polyacene, polyacetylene, quinacin polymer, and polyarylene quinone, and organic polymer compounds having a conjugated double bond in the main chain (
Hereinafter, it may be abbreviated as a conjugated polymer compound). These conjugated polymer compounds may be homopolymers or copolymers. Among the above conjugated polymer compounds, preferred are acetylene high polymer, polyparaphenylene, poly(2,5-chenylene), and polypyrrole, and more preferred is acetylene high polymer. Especially preferred are highly crystalline acetylene polymers.

The method for producing the acetylene polymer preferably used in the present invention is particularly limited to 4T, and any method can be used. 5!
i-129404, i-55-128419, i-5
No. 5-142012, No. 56-10428, No. 56-
No. 133133, Trans, raradySoc,
, 64.823 (1968), J. Polymer
Sci, ^-1,7゜3419 (1969), Ma
kromol, Chem, Rapid Conun,
, 1°621 (1980), J. Chcm, Phy.
s, 69(1), 10 & (1978).

5ynthetic Metals, 4.8H1981
)W method can be cited.

In the battery of the present invention, the electrode materials that perform the electrode reaction based on the intercalation z1 mechanism include graphite, carbon, TiS2. NbS3. NbSe3゜NbSe 4
,N! PS3, V205, Mn02.

Ve O+a , Mo O3, MO02, Fe OCI
.

Intercalation compounds such as WO2 can be mentioned, but among these, preferred intercalation compounds are graphite, carbon, and Ti3.
2, and particularly preferred intercalation compounds include graphite and Ti.
I can give you 82. In order to maximize the effects of the present invention, it is preferable that at least one of the positive electrode and the negative electrode is a conjugated polymer compound. The conjugated polymer compound that undergoes the doping or intercalation reaction used as an electrode material in the present invention may be in the form of a film, powder, short fibers, etc., and the intercalation compound may be in any form such as mica, granules, or lumps. However, if the shape of the conjugated polymer compound is other than film-like, or if the shape of the intercalation compound is other than mica-like, molded products with the necessary mechanical strength can be formed by methods known to those skilled in the art. It is desirable to keep it as In addition, other suitable η for the conjugated polymer compound
It is also possible to mix electrically conductive materials such as graphite, carbon black, acetylene black, metal powder, carbon fiber, etc., or to mix other electrically conductive materials such as carbon black, acetylene black, metal powder, carbon fiber, etc. with the intercalation compound. There is no problem at all with mixing these compounds, or with adding a metal net or the like as a current collector to these compounds.

As the electrode material for the battery of the present invention, not only a conjugated polymer compound or an intercalation compound but also a conjugated polymer compound or an intercalation compound with enhanced conductivity by doping or intercalation can be used.

Various conventionally known electron-accepting compounds and electron-accepting compounds can be used to dope or intercalate a conjugated polymer compound or an intercalation compound using either a chemical method or an electrochemical method. Donor compounds, namely (1) halogens such as iodine, bromine and bromine iodide; (II) arsenic pentafluoride, andimony pentafluoride, silicon tetrafluoride, phosphorus pentachloride, phosphorus guttide, aluminum chloride, bromide; Aluminum, aluminum fluoride, Nb R5, Ta R5, WFe, Fe
C! metal halides such as L3 and CdCl2, etc.
(1) Pronic acids such as sulfuric acid, perchloric acid, nitric acid, fluorosulfuric acid, trifluoromethanesulfuric acid and chlorosulfuric acid,
(IV) oxidizing agents such as sulfur trioxide, nitrogen dioxide, difluorosulfonyl peroxide; (V) A(l ClO
4, (vl) Tetracyanoethylene, Detracyanoquinodimethane, RiOranyl, 2-13-dichloro-5,6
-Dicyatsubara benzoquinone, 2,3-dibrome-5,
6-disiacbenzoquinone, (■) No" sb Fe -, NO2" Sb Fs
−.

NO+AS Fe-, No+PFe.

NO2+PF6-, NO+BF4-.

Examples include nido-O or nitroso compounds such as No' ClO4-, alkali metals such as (X)Li, Na, and Ni.

On the other hand, as ions for electrochemical doping or intercalation, (i) PFe −.

Halide anions of elements of the va group such as Sb Fe-, As Fe-, Sb C1e-, halide anions of elements of the lla group such as BF4-, 1- (1
3'->, halogen anion such as Br-, Cl-, C
Anions such as perchlorate anions such as nO4-, and (ii) alkali metal ions such as Li'', K+, Na, quaternary ammoniums such as R4N+ (R: hydrocarbon group having 1 to 20 carbon atoms). Examples include cations such as ions, but are not necessarily limited to these.

Compounds providing the above-mentioned anions and cations 0) Specific examples and LT are Li PFa, Li Sb Fe.

Li As Fe, Li ClO4, Na I.

Na P[e, Na sb Fe, Na As
Fa'.

Na C(10+, K I, KPFe, KSb R
6゜KAs toe, KCt'104((n -BU
)4 N) +・(As Fe)−, ((n−E3
u )4 N)4・(PF6)−, ((n −Bu)4
N”・Cf1.04゜LiAIG斐4.1-iBF
4 etc., but it is not necessarily limited to these.

These compounds may be used alone or in combination of two or more.

Anions other than the above or 14F2-anions, and cations other than the above include biryllium or pyridinium cations represented by the following formula (I): (wherein, X is an oxygen atom or a nitrogen atom, R' Sweet ice hydrogen atom or alkyl group having 1 to 15 carbon atoms, 6 to 15 carbon atoms
aryl group, R'' is a halogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, the sheath is an oxygen atom, and X is a nitrogen atom. This is atomic sword 1.

n is 0 or 1-5. ) or a carbonium cation represented by the following formula (II) or (III): and [wherein R1, R2, and R3 are hydrogen atoms (R1°R2,
R3 is not a hydrogen atom at the same time), carbon number 1 ~
15 alkyl group, )7 allyl group, 15 aryl group to 6 carbon atoms, or (31-O
R5 group, provided that R5 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R
4 is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and 3, which is an aryl group having 6-15 carbon atoms.

The 11[2-anion used] usually has the following general formula (IV), (V) or (Vl):
(v) [However, in the above formula, 8' and R'' are hydrogen atoms or carbon atoms of 1
~15 alkyl group, aryl having 6 to 15 carbon atoms (ar
yl) group, R″′ is an alkyl group having 1 to 10 carbon atoms,
An aryl group having 6 to 15 carbon atoms, x is an oxygen atom or a nitrogen atom, and n is O or a positive integer of 5 or less. M is an alkali metal]
Hydrogen fluoride salt) is used as a supporting electrolyte and dissolved in a suitable organic solvent. The above formula (rV), (
Specific examples of compounds represented by V) and (W) include H4N.HF2. B'u4nNl-HF2. Na-H
F2゜K・(-1to2, Li-HF2 and 4 can be raised.

The pyrylium or pyridinium cation represented by <I) above is the cation represented by the formula (I) and ClO
4-, BF4-, A-C 4-2Fe C(14-, S
nC1! i −, PFe −.

PCus −, Sb Fe −, As l=6 −
.

It can be obtained by dissolving a salt with an anion such as CF3SO3- or H12-2- as a supporting electrolyte in a suitable organic solvent. Specific examples of such salts include (hereinafter referred to as the margin).

Specific examples of carbonium cations represented by the above formula (n) are (Co 1-15 )3 C'', (CH3)3 C
”, HC”.

1 CoHbC4 can be mentioned.

1 The carbonium Kab-A from here on can be obtained by dissolving them and an anion salt (carbonium salt) in a suitable organic solvent as a supporting electrolyte. Representative examples of anions used here include BF4-, AIC!
L4-, AlBr3C(1-.

Fe　CUq　-, 3u　C(A3-, PFa　-.

PCl3-. 5t) Cue-, Sb [a-.

ClO4-,', CF3SO3-, etc. can be added, and carbonium salt systems include, for example, (Ce R5)3 C-BF4, (CH3)3
C・BF4. HCO・81 (11-4, HCCIBF
i.

Examples include C8H:1Go-3n Cu5.

The amount of dope suspension or intercalation can be freely controlled by controlling the amount of electricity flowing during electrolysis. The doping or intercalation may be carried out either under a constant current, under a constant voltage, or under conditions where the current J-3 and the voltage are varied. The current value, voltage value, and time during doping or intercalation depend on the type of electrode material, height density, area, type of ion, type of electrolyte, and required electrical conductivity. Since they are different, it is not possible to make a general rule.

As the supporting electrolyte of the electrolyte used in the battery of the present invention, the same electrolyte used in the electrochemical doping or intercalation described above can be used.

Doping amount or ink, - force ration is,
It can be controlled in the same way as described above.

Examples of organic solvents for the electrolyte of the battery of the present invention include ethers, ketones, aliphatic nitriles, amines, amides, sulfur compounds, chlorinated hydrocarbons, and esters. compounds, carbonates, nido-0 compounds, phosphoric ester compounds, sulfolane compounds, etc. can be used, but among these, - thials, ketones, aliphatic and aromatic nitriles, Chlorinated hydrocarbons, carbonates 1 to 1, and sulborane compounds are preferred, and aliphatic or aromatic nitriles are particularly preferred. Typical examples of solvents listed above include tetrahydrofuran, 2-
Methyl-trahydronolane, 1,4-dioxane, anisole, mono-glyme, acetonitrile, propylene A
-1-lyl, butyronitrile, benznitrile, 4-methyl-2-pentanone, butyronitrile, 1,2-dichloroethane, T-butyrolactone, dimethoxyethane, medilphalmate, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfate Small oxide, dimethylthioformamide, sulfolane,
Examples include 3-methyl-sulfolane, trimethyl phosphate, triethyl phosphate, etc., but are not necessarily limited to these.

In the battery of the present invention, the ratio of the electrolyte that constitutes the doping species or the organic solvent to be intercalated is within a range that does not belong to either the completely dissolved type battery or the solid electrolyte type battery. (below,
It is necessary to select a solid-liquid coexistence battery.

The present invention is based on the discovery and experimental confirmation of conditions for increasing both energy density and power density as much as possible in a harmonious state. That is, in the present invention, the electrolyte solution in the state where the electrolyte is consumed the most (this corresponds to the fully charged state) contains a solid phase, and the undissolved 1? l
(Precipitation m) is within 50% of the total electrolyte, preferably 20%
within 10%, particularly preferably within 10%. In the solvent (2), the ionic mobility of the electrolysis v1 necessary to maintain the battery's liquid resistance at the required low level can be ensured at the same time as h2.

By configuring the battery in this way, it is possible to obtain a completely dissolved battery or a solid-liquid coexistence battery having an extremely high energy density or power density compared to a solid electrolyte battery.

In the battery of the present invention, the amount of solvent can be reduced compared to a completely dissolved type battery, and therefore the energy density of the battery can be further increased.

In this case, in the state of the electrolytic solution, it is preferable that the undissolved electrolyte exists as microcrystals, but it does not necessarily have to be uniformly dispersed.

In the present invention, the conjugated polymer compound or intercalation compound is used in (i) the positive electrode, (ii) the negative electrode, or (i) of the battery.
ii) It can be used as both positive and negative active material, but preferred batteries are of the (+) or (iii) type, particularly preferred are (iii) type batteries.

As a specific example in the case of a secondary battery, for example, if acetylene polymer is (CH)x, (ON)i (positive ll
1)/Li C 04 (supporting electrolyte)/Li (negative electrode)
, (CH)x (positive electrode)/LiCuO+ (supporting electrolyte)/
(CH)x (negative electrode), (((,H)"002'(Cu
O+)-) (positive 0.024 x pole)/(n-BLI 4 N)” ・(CuO4)
−(Supporting electrolyte) / ((n −Bu 4N> +0
．． (,24+0.06 (CH)'°024]x(negative electrode),((CH)(1)F
'a)-) (Positive electrode) 1 0.06 x (Et4N)+・(PFa)-(Supporting electrolyte)/
((Li) + (CH)-0°06) (negative electrode), o
, oe x [(CH)+0°050((,104) −) (positive 0
．． 050
((CH) +0”20(CjLO4) −□,020
) x (negative electrode), ((n-13u 4 N )'.

H2(CH”2) x (positive ll) / (n-Bu
4 N) 4・(Cs04)-(supporting electrolyte)/((BU4N)"(CH)-"')x(negative 0
1 pole), ((CH)+0.010(13)-)0.01
0 x (positive electrode) / Li1 (supporting electrolyte) / ((CH 0°"0 (Li) + ) (negative electrode), o,
oi.

(CI-1) <Positive electrode)/LiC 04 (Supporting electrolyte)/Graphite (negative electrode), (CI-port).

(Positive electrode)/LiC 04 (Supporting electrolyte)/Carbon (Negative electrode), (CH)x (Positive electrode)/Li CfLO+ (Supporting electrolyte)/1-is2 (Negative electrode), and the like.

Voriparaf, [In the case of nylene, (Co H4) In the case of (C4
H3N)X is used as a secondary battery of the same type as above.

Furthermore, in the present invention, different conjugated polymer compounds or intercalation compounds can be used for the positive and negative electrodes, and a specific example thereof is (G H) / L + C104/ (Ce H4).
x, (CH) /Li ClO4/ (04H2S)
x.

(Co H4)x (Li ClO4/(C482"'
S), etc.

In the present invention, if necessary, a porous membrane of synthetic resin such as polyethylene or polypropylene or natural fiber navy blue paper may be used as the diaphragm.

In addition, some of the conjugated polymer compounds used in the present invention undergo gradual oxidation reactions with oxygen, reducing the performance of the battery. It is preferable that the state is as follows. Additionally, the cells of the present invention may be thin cells, even paper-thin cells, multiple layers may be stacked on top of each other and coupled together in series or parallel, or a single long cell may be assembled by itself. It may be rolled or spiraled.

The battery of the present invention has high energy density, high charge/discharge efficiency, long cycle life (low self-discharge rate,
Good voltage flatness during discharge. Furthermore, the battery of the present invention is lightweight, compact, and has a high energy density, so it is suitable for use in portable devices, electric vehicles, gasoline vehicles, and power storage batteries.

EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples.

[Example for valve] [Production of film-like polyacetylene 1.
．． Add 7 mQ of titanium detrabutoxide,
A catalyst solution was prepared by dissolving d in anisole and then adding triethylaluminum with a C of 2.77 with stirring.

This reaction vessel was cooled with liquid nitrogen, and the nitrogen gas in the system was exhausted using a vacuum pump. Next, this reaction vessel was
The catalyst solution was cooled to 11° C. and purified acetylene gas at a pressure of 1 atm was blown into the reactor while the catalyst solution remained static.

Immediately, polymerization occurred on the surface of the catalyst solution, producing a film-like acetylene high polymer. 49 minutes after the introduction of acetylene, the acetylene gas in the reaction vessel system was exhausted to stop the polymerization.

After removing the catalyst solution with a syringe under nitrogen atmosphere, -78
Purified toluene while kept at ℃ 00yd! , and washed 5 times. The film-like acetylene polymer swollen with toluene was a uniform film-like swollen product containing closely entangled fibrils. This swollen product was then vacuum-dried to obtain a reddish-purple film-like acetylene high polymer with a cis content of 98% and a metallic luster. In addition, the height density of this film-like polyacetylene is 0.451/CC, and its electrical conductivity (DC four-terminal method) is 3.2X 10'Ω-1·c, -1 at 20°C.
The present invention will be explained in detail with reference to FIGS. 1 and 2.

FIG. 1 is a structural explanatory diagram showing an embodiment of the secondary battery of the present invention. In FIG. 1, a cathode current collector 2 made of a metal net is spot welded onto a stainless steel cathode battery frame 1, and a bulk density l obtained by the above method is placed on top of the TEPCO body 2.
A positive electrode 3 made of a polyacetylene film of 0.45 g/cc was provided, a leverator 4 made of a polypropylene nonwoven fabric was placed on the positive electrode 3, and the separator 4 contained pulverized l-1.
An electrolytic solution consisting of c10+ and zo[]pyrene carbonate was avoided. .

Further, on top of the separator 4, a negative electrode 5 made of the same boric acid film as the positive electrode 3 and a negative Ti current collector 6 made of metal mesh are sequentially stacked, and then a stainless steel negative electrode battery frame 7 is placed on top of the positive electrode. The battery frame 1 is crimped tightly, j, tl L,. 8 has a backing.

The electrolytic solution was prepared using micronized L-icljo4 and propylene carbonate in the proportions shown in the table. As shown in the table, 'C' (A) is a homogeneous dissolution system from the beginning of charging, that is, a completely dissolving system during the entire charging and discharging process, and (B) is a homogeneous dissolving system during the entire charging and discharging process. Homogeneous system (
This is an example of a solid-liquid coexistence battery. The electrolyte in (B) was a slurry made by mixing micronized 1-iclo4 and propylene carbonate.Also, in each battery, the thickness and area of the electrodes were constant, and the electrolyte was used as a separator. 1=The thickness of the polypropylene nonwoven fabric was set to the minimum thickness necessary to hold the amount of electrolyte.

In addition, in the table, the doping rate of the electrolyte is 6E%.
An amount equivalent to 1.2 times was used.

The results are shown in the table.

(Note) *per +CH+ unit in polyacetylene molecule Also, in Fig. 1, a positive electrode current collector 2 made of a metal mesh is spot welded onto the stainless steel positive electrode battery frame 1, and the positive electrode current collector 2 is placed on the current collector 2. Diameter 15mm, thickness 0.5111111.
The height density obtained by the above method is 0.45 fj
A positive electrode 3 made of an Icc polyacetylene film is provided, and on top of the positive electrode 3 a film made of a polypropylene nonwoven fabric with a thickness of about 0.3
A separator 4 of M is placed, and the separator 4 has the above (B
) was retained.

Further, on top of the separator 4, a polyacetylene film J similar to that of the positive electrode 3, a negative electrode 5, a negative electrode current collector 6 made of a metal mesh, etc. are sequentially stacked, and then a stainless steel negative electrode battery frame 7 is placed on top of the positive electrode battery. Seal by caulking frame 1. 8 is the backing.

This battery was used at a current density of 1 m^/cd and a voltage of 4. FIG. 2 shows the relationship between time and voltage when the battery was charged until it reached OV and then discharged at the same current density until it reached 1.5 square meters, as shown by eight curves in FIG. In addition, curve 5 in FIG. 2 is the same as the above when the above-mentioned curve (A) is used as the N dissolution to be held in the hibarator 4 in the secondary battery having the configuration shown in FIG. 1, at a current density of 111^/oJ. In this case, with the amount of electrolyte impregnated in polyacetylene and separator 4, the electrolyte will be completely consumed in about 3 hours as shown in the figure, so the voltage will be 4.0V at this point. ing. On the other hand, in the embodiment of the present invention, the undissolved electrolyte in the electrolyte dissolves as the electrolyte is consumed and is used for the charging reaction, so it takes about 4.3 As time passes, the electrical capacity increases accordingly. Further, in the case of the example of the present invention, even after repeated charging and discharging three times, the same charging and discharging characteristics as the 8 curves in FIG. 2 were obtained, and it was confirmed that the battery was stable.

As described above, according to the embodiments of the present invention, it is possible to reduce the amount of electrolyte, and it is possible to improve energy density, and achieve weight and size reduction.

In addition, in FIG. 1, the positive electrode 3 has a diameter of 15111#.
I, thickness 0.5. The polyacetylene film of l-1cJjo
4 was soaked in a propylene carbonate saturated solution and left for 1 hour, and titanium disulfide powder 5 was used as the negative electrode 5.
Add 10ay of graphite powder and 0.1m of 10% polytetrafluoroethylene solution to 0IIFI! In addition, the mixture was kneaded in a mortar, press-molded into a disc shape with a diameter of 15 mm, and the disc-shaped titanium disulfide was fired in air at 350°C for 2 hours, and the propylene of LiCIC)+ was kneaded in the same manner as above. The electrolyte used was 20 g of micronized 1-i CuO+ dried at 150° C. and 20 ad! and mix to remove undissolved electrolyte (LiC10
Using a slurry-like electrolytic solution containing 4) and using the same method as in the above embodiment, the polyacetylene film was assembled into the battery frame 1.7 so that the positive electrode 3 and the titanium disulfide plate were the negative electrode 5 and 77, respectively.
It may also constitute a secondary battery. In this case, the current density is 0.
When charging and discharging are repeated at a rate of 1 m^/d, the charging/discharging N voltage becomes approximately 1 V, which is lower than that of the embodiment described above, but a secondary battery having the same electric capacity can be obtained.

[Effect of the invention 1 As explained above, according to the present invention, the amount of electrolyte can be reduced, the energy per density increases by -1, and the battery can be made lighter and smaller. .

[Brief explanation of the drawing]

FIG. 1 is a configuration explanatory diagram showing one embodiment of a secondary battery of the present invention, and FIG. 2 is a diagram showing a charge/discharge curve of the secondary battery for explaining the present invention in detail. 2...Positive electrode current collector 3...Positive electrode 4...Separator 5...Negative electrode 6...Negative electrode current collector Patent applicant Showa Denko Co., Ltd. Hitachi Ltd. Representative Patent attorney Sei Kikuchi - Continued from page 1 [Phase] Inventor Noboru Ebato @ Inventor Toyama Atomic @ Inventor Shigeoki Nishimura @ Inventor Matsu 1) Seiko Hitachi, Ltd., 3-1-1 Saiwai-cho, Hitachi City. 3-1-1 Saiwai-cho, Hitachi, Hitachi, Ltd. Hitachi Research Laboratory 3-1-1 Saiwai-cho, Hitachi, Hitachi, Ltd. Hitachi Research Laboratory 3-1-1 Saiwai-cho, Hitachi, Hitachi, Ltd. Works inside Hitachi Research Institute

Claims (1)

[Claims] 1. A secondary battery comprising positive and negative electrodes and an electrolytic solution containing an electrolyte interposed between these electrodes, and which is repeatedly charged and discharged by a doping or intercalation mechanism,
1. A secondary battery characterized in that the electrolytic solution contains a part of the electrolyte in an undissolved state during the entire process of charging and discharging. 2. The secondary battery according to claim 1, wherein at least one of the electrodes is composed of an organic polymer compound having two small bonds in the main chain. 3. The secondary battery according to claim 2, wherein the organic polymer compound is polyacetylene. 4. The secondary battery according to claim 1, wherein at least one of the electrodes is made of a substance that forms an intercostal compound. 5. The secondary battery according to claim 4, wherein the substance forming the intercalation compound is titanium disulfide. 6. The secondary battery according to claim 1, 2, 3, 4, or 5, wherein the electrolyte comprises an organic solvent and an electrolyte. 7. The secondary battery according to claim 6, wherein the electrolytic solution uses propylene carbonate as a solvent and tetraethylammonium perchlorate or lithium perchlorate as an electrolyte.