GB2131597A - Organic electrolyte battery - Google Patents
Organic electrolyte battery Download PDFInfo
- Publication number
- GB2131597A GB2131597A GB08329576A GB8329576A GB2131597A GB 2131597 A GB2131597 A GB 2131597A GB 08329576 A GB08329576 A GB 08329576A GB 8329576 A GB8329576 A GB 8329576A GB 2131597 A GB2131597 A GB 2131597A
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- GB
- United Kingdom
- Prior art keywords
- positive electrode
- battery
- organic electrolyte
- electrolyte battery
- woven fabric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005486 organic electrolyte Substances 0.000 title claims abstract description 13
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000011149 active material Substances 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- -1 polypropylene Polymers 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 230000000052 comparative effect Effects 0.000 description 14
- 238000007599 discharging Methods 0.000 description 14
- 239000007774 positive electrode material Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229920013683 Celanese Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- POIUWJQBRNEFGX-XAMSXPGMSA-N cathelicidin Chemical compound C([C@@H](C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CO)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H]([C@@H](C)CC)C(=O)NCC(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CO)C(O)=O)NC(=O)[C@H](CC=1C=CC=CC=1)NC(=O)[C@H](CC(O)=O)NC(=O)CNC(=O)[C@H](CC(C)C)NC(=O)[C@@H](N)CC(C)C)C1=CC=CC=C1 POIUWJQBRNEFGX-XAMSXPGMSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/172—Arrangements of electric connectors penetrating the casing
- H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
- H01M50/179—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for cells having curved cross-section, e.g. round or elliptic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/172—Arrangements of electric connectors penetrating the casing
- H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
- H01M50/181—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for button or coin cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides an organic electrolyte battery comprising a positive electrode, a negative electrode composed of a light metal as active material and a separator disposed between the positive and negative electrodes, wherein the separator is composed of double layers of a non-woven fabric made of polyolefinic fibres and an electrolyte-resisting microporous film which is permeable to electrolyte ions but is impermeable or substantially impermeable to particles of the active material for the positive electrode liberated from the positive electrode, said microporous film being disposed on the positive electrode side.
Description
SPECIFICATION
Organic electrolyte battery
The present invention is concerned with an organic electrolyte battery.
In an organic electrolyte battery, a metal oxide or sulphide or a carbon halide is used as the active material for the positive electrode, a light metal, such as lithium or sodium, is used as the active material for the negative material and a separator impregnated with an organic electrolyte is disposed between the positive and negative electrodes. Such a battery has many merits, for example, it gives a high voltage, has a high energy density and is less self-discharging.
However, in such a conventional battery, a polypropylene non-woven fabric or a polyethylene non-woven fabric is, in many cases, used alone as the separator and the use of such a separator encounters the following problem:
During discharging or storing, the particles of the active material for the positive electrode are liberated from the positive electrode, pass through the pores of the separator made of the non-woven fabric, reach the surface of the negative electrode and attach thereto to increase the internal resistance of the battery and the amount of self-discharging. Furthermore, attachment of these particles to the non-woven fabric separator brings about a change and deterioration of the quality of the separator, which increases the internal resistance of the battery.
One object of the present invention is to ameliorate the above problem.
In addition, published Japanese Utility
Model Application No. 45, 657/82 describes a battery comprising a rolled electrode body formed by rolling up a zonal positive electrode and a zonal negative electrode with a separator between both electrodes, the zonal negative electrode being composed of a plate of a light metal, such as lithium or the like, having a current-collecting netting for the negative electrode attached under pressure to one surface of the metal plate, microporous films being disposed at both surfaces of the negative electrode plate having the current-collecting netting.
However, the structure of the battery described in the above-mentioned Japanese Utility Model Application is intended to prevent the occurrence of damage to the separator by the cutting burr of the current-collecting netting for negative electrode and to improve the mould-releasing property in the step of attaching the current-collecting netting to the plate of a light metal, thereby improving the worka biiity of the operation. Thus, the object thereof is different from that of the present invention and the above-mentioned Japanese
Utility Model Application does not disclose the structure of the battery of the present invention, which is described hereinafter. Furthermore, the object of the above-mentioned prior art cannot be attained by the structure of the present invention.
Thus, according to the present invention, there is provided an organic electrolyte battery comprising a positive electrode, a negative electrode composed of a light metal as active material, and a separator disposed between the positive and negative electrodes, wherein the separator is composed of double layers of a non-woven fabric made of polyolefinic fibres and an electrolyte-resisting microporous film which is permeable to electrolyte ions but is impermeable or substantially impermeable to particles of the active material for the positive electrode liberated from the positive electrode, said microporous film being disposed on the positive electrode side.
Since the battery according to the present invention uses double layers of the non-woven fabric and microporous film as the separator and the microporous film is disposed on the positive electrode side, the liberation of particles of the active material for the positive electrode from the positive electrode can be inhibited more than in the comparative battery wherein the microporous film is disposed on the negative electrode side. Furthermore, in the comparative battery, the particles can diffuse into the non-woven fabric and be finely disposed therein and pass through the film to reach the surface of the negative electrode. In the battery of the present invention, this cannot take place.
Accordingly, in the battery of the present invention, the increase of the internal resistance and the reduction of the discharging capacity can be depressed more greatly than in the comparative battery. Additionally, since, in the battery of the present invention, the particles scarcely become attached to the nonwoven fabric, a change and deterioration of the non-woven fabric hardly occurs so that the increase of the internal resistance of the battery is less than that of the comparative battery. Thus, the characteristics of this kind of battery are greatly improved by the present invention.
The present invention will now be described in more detail, with reference to the accompanying drawings, in which:~
Figure 1 is a cross-sectional view of a flat type embodiment of the battery of the present invention;
Figure 2 is a cross-sectional view of a cylindrical type embodiment of the battery of the present invention;
Figure 3 is a graph showing the relationship between the internal resistance and the storing period (in months) in the case of storing a
battery of the present invention (curve A) and comparative batteries (curves B and CO at a temperature of 60 C. and a humidity of 90%;; and
Figure 4 is a graph showing discharging characteristics in the case of discharging a battery of the present invention (curve A) and comparative batteries (curves B and C) at a load of 12 K53 and at 20 C. after storing the batteries for 40 days at a temperature of 60 C. and in the case of discharging a battery (a) of the present invention directly after production thereof at a load of 1 2KSa and at 20 C. (curve a).
The non-woven fabric used as the separator for the battery of the present invention can be any non-woven fabric hitherto used as a separator for conventional batteries, for example, a non-woven fabric composed of polyolefinic synthetic fibres and, in particular, of polypropylene and/or polyethylene fibres. Such a non-woven fabric is generally prepared by melt spinning a polyolefine resin to form fibres and arranging the fibres in a sheet form, followed by pressing under heat, or melt extruding a polyolefine resin followed by fabricating in sheet form. The mean pore size of the non-woven fabric is preferably 1 to 20 microns, the weight of the non-woven fabric per unit surface area is 40 to 60 g/m2 and the thickness thereof is 0.10 to 0.30 mm., these values being appropriately selected according to the kind, dimensions and the like of the battery.Specific examples of nonwoven fabrics which can be used according to the present invention are "TAPYLS" (trade name; made by Tonen Sekiyukagaku K. K.,
Japan) and the like.
The microporous film can be a film produced from polypropylene, polyethylene or the like which has a resisitivity to the electrolyte used for the battery of the present invention, as described hereinafter. The film used according to the present invention has pores of sizes which do not permit or do not substantially permit the passage of particles of the positive electrode active material liberated from the positive electrode during use or storage of the battery but do permit the passage of the electrolyte ions. The pore size, the porosity, the thickness and the like of the film are appropriately selected according to the kind of particles of the positive electrode active materials generated from the positive electrode, a film having a pore size of 0.05 to 0.5 m. or less, a porosity of 30 to 90% and a thickness of 10 to 50ym. usually being used.
Specific examples of such a microporous fìlffi include Celgard, made of polypropylene film (made by Celanese Plastics Company) and the like.
The positive electrode, negative electrode and electrolyte used for the battery of the present invention can be made of materials normally used for conventional batteries.
Thus, for example, the positive electrode active materials used in the present invention can be metal oxides, such as manganese dioxide (MnO2) or molybdenum oxide (MoO3), silver chromate (Ag2CrO4), metal halides, such as nickel fluoride (NiF2), copper fluoride (Cu F2) and silver chloride (AgOl); metal sulphides, such as copper sulphide (CuS), and fluorinated carbon (CF), and the like. The positive electrode of the present invention can be produced by using a mixture of the active material with a conducting agent, such as graphite, and a binder, such as fluoric resin.
The negative electrode as used according to the present invention is made of a light metal, such as lithium, sodium, magnesium, calcium or the like.
The electrolyte used in the present invention can be an aprotic solvent, such as dimethoxyethane (DME), dimethyl sulphoxide (DMSO), propylene carbonate (PC), acetonitrile (AN), butyrolactone (BL), dimethyl-formamide (DMF) or the like having a solute dissolved therein, such as potassium hexafluorophosphate (KPF,), lithium perchlorate (Li Coo,), potassium thiocyanate (KCNS) or the like.
The following Example is given for the purpose of illustrating the present invention:
Example
Fig. 1 of the accompanying drawings is a cross-sectional view of a flat type battery embodiment of the present invention. A positive electrode 1 is produced by moulding, under pressure, a positive electrode mixture of a manganese dioxide active material heattreated at a temperature of 350 to 430 C.
with acetylene black and graphite as a conducting agent and a fluorine resin powder as a binder in a 85:10:5 by weight ratio, followed by heat-treating the mixture at 250 to 300 C. The positive electrode 1 is stuck, under pressure, to a positive electrode current collecting netting 2' fixed to the inner surface of the bottom of a positive electrode can 2. A negative electrode 3, composed of a rolled lithium plate, is stuck, under pressure, to a negative electrode current collecting netting 4' fixed to the inner surface of a negative electrode can 4.
A separator 5 is composed of double layers of a first layer 6 made by a non-woven fabric of poly-propylene fibres (TAPYLS, a nonwoven fabric having a means pore size of 3 to 4,us., a weight per unit surface area of 56 g/m2 and a thickness of 0.11 mm., made by
Tonen Sekiykagaku K. K.) and a second layer 7 of a microporous film (Celgarå, having a pore size of 0.04 X 0.4,us. or iess, a porosotiy of 45% and a thickness of 25cm., made by Celanese Plastic Co.), which is disposed on the positive electrode side. The positive can 2 is insulated from the negative can 4 by an insulating packing 8. In addition, a solution prepared by dissolving lithium perchlorate (1 M concentration) in a mixture of equal volumes of PC and DME is used as electrolyte in the battery.
Fig. 2 of the accompanying drawings is a cross-sectional view showing a cylindrical battery embodiment of the present invention. A cylindrical positive electrode 11 is disposed inside a battery container 12, which also acts as a positive electrode terminal. The positive electrode 11 is composed of the same positive electrode mixture as that used in the foregoing flat type battery. A negative electrode 13 composed of lithium is disposed in the hollow space of the cylindrical positive electrode 11 via a separator 15 composed of double layers of a first layer 16 of non-woven fabric and a second layer 17 of microporous film such as those used in the foregoing flat type battery.
The negative electrode 13 is electrically connected to a negative electrode terminal member 20, which is fixed to a central hole of a container cap 18 through an insulator 19, by a negative electrode current collecting rod 14.
In addition, the electrolyte used in this embodiment can have the same composition as the electrolyte used in the foregoing flat type battery.
For comparative purposes, a battery (A) according to the present invention was compared with a battery (B) which was the same as battery (A) except that only the foregoingpolypropylene fabric was used as the separator for the battery, and with a battery (C) which was the same as battery (A) except that the microporous film was disposed on the negative electrode side. The battery characteristics were measured as follows:
First batteries (A), (B) and (C) were stored in an atmosphere of 60 C. and 90% relative humidity and the internal resistance of each battery was measured, the relationship between the storing period of time and the internal resistance being shown in Fig. 3 of the accompanying drawings.From the results shown in Fig. 3, it will be appreciated that battery (A) of the present invention and comparative battery (C) showed a lesser increase of the internal resistance as compared with comparative battery (B), which does not use a microporous film and hence batteries (A) and (C) have an excellent storing property and, furthermore, battery (A) is superior to comparative battery (C) with regard to the storing property.
The following are considered to be the reasons for the above results:
When comparative battery (B) is stored for a long period of time, the particles of the positive electrode active material liberated from the positive electrode pass through the pores of the non-woven separator, reach the surface of the negative electrode and become attached thereto, reducing the effective surface area of the negative electrode and increasing the internal resistance of the battery. On the other hand, in batteries (A) and (C), the particles liberated from the positive electrode are prevented from reaching and becoming attached to the surface of the negative electrode by the microporous film so that the increase of the internal resistance of these batteries is less than that in battery (B).Furthermore, in comparative battery (C), the particles liberated from the positive electrode easily diffuse into the non-woven fabric so that the particles are more finely divided and pass through the microporous film to reach and become attached to the surface of the negative electrode. Since, in battery (A) of the present invention, the microporous film is disposed on the positive electrode side, particles of the positive electrode active material can only be liberated with difficulty from the positive electrode and a fine dividing of the particles by diffusion thereof into the non-woven fabricdoes not occur so that the increase of the internal resistance is less than that of comparative battery (C).
The discharging characteristics of batteries (A), (B) and (C) discharged at a load of 12 k# and 20 C. after storage for 40 days at 60"C.
and the initial discharging characteristic of battery (A) were measured and their utilisations of positive electrode active material were calculated [(the substantial discharging capacity of the positive electrode/the theoretical capacity of the positive electrode) X 100%], the relationship between the utilisation and the battery voltage being shown in the graph of Fig. 4 of the accompanying drawings. In this graph, solid lines A, B and C represent the discharging characteristics of batteries (A), (B) and (C) after storing as described above and the dotted line a represents the initial discharging characteristic of battery (A) directly after production thereof. As is clear from the results shown in Fig. 4, the discharging capacity of battery (A) of the present invention is greater and the self discharging amount thereof is smaller than those of comparative batteries (B) and (C) after storing as compared with the initial characteristics of battery (A). This is because, as described above, both the liberation of the particles of the positive electrode active material from the positive electrode and the attachment of the particles to the negative electrode in the battery (A) are less than those in batteries (B) and (C).
Claims (6)
1. An organic electrolyte battery comprising a positive electrode, a negative electrode composed of a light metal as active material and a separator disposed between the positive and negative electrodes, wherein the separator is composed of double layers of a non-woven fabric made of polyolefinic fibres and an electrolyte-resisting microporous film which is permeable to electrolyte ions but is impermeable or substantially impermeable to particles of the active material for the positive electrode liberated from the positive electrode, said microporous film being disposed on the positive electrode side.
2. An organic electrolyte battery according to claim 1, wherein the non-woven fabric is made of polypropylene fibres and/or polyethylene fibres.
3. An organic electrolyte battery according to claim 1 or 2, wherein the micrnpornus film is a microporous polypropylene or polyethylene film.
4. An organic electrolyte battery according to any of the preceding claims, wherein the non-woven fabric has a mean pore size of 1 to 20 microns, a weight per unit surface area of 40 to 60 g/m2 and a thickness of 0. 10 to 0.30 mm.
5. An organic electrolyte battery according to any of the preceding claims, wherein the microporous film has a pore size of 0.05 to 0.51.Lm. or less, a porosity of 30 to 90% and a thickness of 10 to 50cm.
6. An organic electrolyte battery according to claim 1, substantially as hereinbefore described and exemplified and with reference to
Figs. 1 and 2 of the accompanying drawings.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57198006A JPS5987753A (en) | 1982-11-10 | 1982-11-10 | Organic electrolytic battery |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8329576D0 GB8329576D0 (en) | 1983-12-07 |
| GB2131597A true GB2131597A (en) | 1984-06-20 |
| GB2131597B GB2131597B (en) | 1986-06-04 |
Family
ID=16383939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08329576A Expired GB2131597B (en) | 1982-11-10 | 1983-11-04 | Organic electrolyte battery |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS5987753A (en) |
| CH (1) | CH662212A5 (en) |
| DE (1) | DE3340329A1 (en) |
| GB (1) | GB2131597B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS618852A (en) * | 1984-06-22 | 1986-01-16 | Sanyo Electric Co Ltd | Nonaqueous electrolyte cell |
| US4794057A (en) * | 1987-07-17 | 1988-12-27 | Duracell Inc. | Separator for electrochemical cells |
| KR0153002B1 (en) * | 1989-06-16 | 1998-11-16 | 와따나베 히로시 | Inorganic nonaqueous electrolytic solution type cell |
| JPWO2015030230A1 (en) * | 2013-09-02 | 2017-03-02 | 日本ゴア株式会社 | Protective film, separator and secondary battery using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1319983A (en) * | 1969-10-03 | 1973-06-13 | Bosch Gmbh Robert | Separators for accumulators |
| GB1415958A (en) * | 1972-07-12 | 1975-12-03 | Yuasa Battery Co Ltd | Storage batteries |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4220693A (en) * | 1978-08-23 | 1980-09-02 | P. R. Mallory & Co. Inc. | Composite separator/absorbent |
-
1982
- 1982-11-10 JP JP57198006A patent/JPS5987753A/en active Pending
-
1983
- 1983-11-04 GB GB08329576A patent/GB2131597B/en not_active Expired
- 1983-11-08 DE DE19833340329 patent/DE3340329A1/en not_active Ceased
- 1983-11-09 CH CH6042/83A patent/CH662212A5/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1319983A (en) * | 1969-10-03 | 1973-06-13 | Bosch Gmbh Robert | Separators for accumulators |
| GB1415958A (en) * | 1972-07-12 | 1975-12-03 | Yuasa Battery Co Ltd | Storage batteries |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8329576D0 (en) | 1983-12-07 |
| DE3340329A1 (en) | 1984-05-10 |
| JPS5987753A (en) | 1984-05-21 |
| GB2131597B (en) | 1986-06-04 |
| CH662212A5 (en) | 1987-09-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PE20 | Patent expired after termination of 20 years |
Effective date: 20031103 |