CA1248173A - Nonaqueous electrolyte cell - Google Patents
Nonaqueous electrolyte cellInfo
- Publication number
- CA1248173A CA1248173A CA000484770A CA484770A CA1248173A CA 1248173 A CA1248173 A CA 1248173A CA 000484770 A CA000484770 A CA 000484770A CA 484770 A CA484770 A CA 484770A CA 1248173 A CA1248173 A CA 1248173A
- Authority
- CA
- Canada
- Prior art keywords
- separator
- electrode
- aqueous electrolyte
- positive electrode
- positive
- 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.)
- Expired
Links
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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Primary Cells (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
NONAQUEOUS ELECTROLYTE CELL
ABSTRACT OF THE DISCLOSURE
A nonaqueous electrolyte cell comprising a negative electrode which contains as active material a light metal such as lithium or sodium or an alloy of these metals. The cell comprises a positive electrode of a material with the apparent volume thereof increased with a discharge reaction, a separator of a microporous resin film disposed on the surface of either electrode facing the other electrode, and an electrolyte layer formed between the above-described other electrode and the separator.
ABSTRACT OF THE DISCLOSURE
A nonaqueous electrolyte cell comprising a negative electrode which contains as active material a light metal such as lithium or sodium or an alloy of these metals. The cell comprises a positive electrode of a material with the apparent volume thereof increased with a discharge reaction, a separator of a microporous resin film disposed on the surface of either electrode facing the other electrode, and an electrolyte layer formed between the above-described other electrode and the separator.
Description
~4~3~'7;~
The present invention relates to a nonaqueous electrolyte cell having a positive electrode of a material with the apparent volume thereof increased with the discharge reaction.
There are materials with the apparent volume thereof increased with the discharge reaction, e.g., carbon fluorides, silver chromate and manganese dio~ide as disclosed in Japanese Patent Publication 54-35,653 published Nov. 5, 1979 and metal sulphides (such as F`eS, FeS2, CuS, Cu2S) or copper oxide and bismuth oxide, as disclosed in Japanese Laid-Open Patent Publication No. 57-174871, published oct. 27, 1982. Where such materials are used as positive electrode active material for a nonaqueous electrolyte cell, the following problem arises.
As the separator for this type of cell, unwoven ~abric of polypropylene is generally used as disclosed in the literatures described above. However, as the volume of the positive electrode is increased with the discharge reaction, the separator of polypropylene unwoven fabric disposed between the positive and negative electrodes is compressed to squeeze out the retained electrolyte from the separator. Consequently, a local portion of polypropylene unwoven fabric where there is substantially no electrolyte contained therein is present between the positive and negative electrodes, so that the internal .~
" i-,. ..
;:~Z4~73 resistance ls sharply increased, resulting in deterioration of cell characteristics.
The present invention provides an improved non-aqueous electrolyte cell ~hich has desirous discharge voltage character-istics, without a sharp increase of the internal resistance.
The present invention also provides an improved non-aqueous electrolyte cell which can suppress a sharp increase of the internal reistance thereo~, the cell having a positive electrode with the apparent volume thereof increase with the discharge reaction in the process of discharge.
The present invention again affords a new non-aqueous electrolyte cell ~hich provides improved cell characteristics with a stable internal resistance and a discharge voltage.
According to the present invention, there is provided a non aqueous elecrolyte cell, which comprises a negative electrode containing as active material a light metal such as lithium or sodium or an alloy of these light metals, and a positive elec-trode consisting substantially i;Z4~73 of a material wi-th the apparent volume thereof increasing by a discharge reaction. The cell has a separator formed substan-tially of a microporous resin film on the surface of either elec-trode facing the other electrode, and an electrolyte layer filled in a space between the above-described other electrode and the separator wherein said electrolyte layer is formed by filling said space with liquid electrolyte.
In the non-aqueous electrolyte cell according to the present invention, the apparent volume increase of the positive electrode caused with the discharge reaction is substantially absorbed by the electrolyte layer. In addition, since the sepa-rator provided between the positive and negative electrodes is formed of a very thin synthetic resin film or films, even if the volume of the positive electrode is increased until the positive and negative electrodes are in contact with the separator where there is locally substantially no electrolyte present, the dis-tance between the positlve and negative electrodes is very small, and the internal resistance will never be sharply increased.
In one embodiment of the present invention said separa-tor is disposed on the surface of said positive electrode and said electrolyte layer is formed between said separator and sald ne~ative electrode. Suitably said microporous resln film is a polypropylene film. Desirably the polypropylene film has a thickness of approximately 0.025 mm.
In another embodiment of the present invention said separator comprises a first separator element of a polyethylene film and a second separator element of a polypropylene film, and wherein said first separator element is closely contacted with said positive electrode and said second separator is closely con-tacted with said electrolyte layer. Desirably the cell ~urther comprises a third separator element of a polyethylene film between said first separator element and said second separator element in a closely contacted three-layer structure. Suitably ,~,..~.
,. ;,~
iZ4~ 3 said :Eirst separator element consisks of two polyethylene films closely con-tacte~ together.
The present inven-tion also provides a non-aqueous elec-trolyte cell comprising a negative electrode containlng an active material of at least a single light metal or its alloy, an annu-lar insulating gasket along an edge of said negative electrode, a positive electrode composed of a material with an apparent volume thereof increased with a discharge reaction, a separator having a microporous polyethylene film disposed on a surface of said posl-tive electrode, and an electrolyte layer filled in a space between said separator and said negative electrode wherein said separator is held at a circumferential end thereof be-tween said positive electrode and said annular insulating gasket and wherein said electrolyte layer is formed by filling said space with liquid electrolyte such that said electrolyte layer is disposed in the direction of stacking of said separator and the positive and negative electrodes.
The present invention will be further illustrated by way of -the accompanying drawings, in which:-Figure 1 is a sectional view of a non-aqueous elec~
trolyte cell according to the present invention;
Figure 2 is a sectional view of a comparative cell which is known in the art;
~, - 4a -l.,i,.
vJ ,~ .
.1;24~3~73 Figure 3 is a graph showing cell voltage characteristics and internal resistance characteristics plotted relative to a discharge time, with respect to the inventive cell of Figure 1 and the comparative cell of Figure 2; and Figure 4 is a sectional view of a cell according to another embodiment of the invention.
Referring to Figure 1 of the drawing, a cell has a positive electrode 1, a negative electrode 2, a separator 3 and an electrolyte layer 4. The positive electrode 1 is obtained by adding 10 wt~ of graphite as electrical conductor and 5 wt~ of fluorine resin powder as binder to 85wt~ of iron disulfide (FeS2) as active material press molding the mixture with a pressure of 2 tons/cm2 to produce pellets with a diameter of approximately 11.0 mm and a thickness of approximately 1.8 rnm, and sintering the pellets at a temperature of 200 to 300C.
The negative electrode 2 is a stamped lithium sheet with a diameter of approximately 7.5 mm and a thickness of approximately 2.2 mm. The separator 3 is a stamped microporous polypropylene film with a diameter of approximately 11.0 mm and a thickness of approximately 0.025 mm.
The electrolyte layer 4 is formed by filling the space between the negati~e electrode 2 and the separator 3 4 ~ ~,q ~, with liquid electrolyte. The microporous resin film may be a polyethylene film instead of the polypropylene film as in the above embodiment.
An assembly operation of the nonaqueous electrolyte cell illustrated in Figure 1 will be explained. First, the lithium negative electrode 2 is press bonded to a negative electrode collector 7, which is secured to the inner surface of a seal cap 6 also serving as a negative electrode terminal with an annular insulating gasket 5 provided along the edge by insert molding, so that the lithium negative electrode 2 will not fall when the cell is inverted. At this time, a space is defined by the lithium negative electrode 2 and the annular insulating gasket 5.
Meanwhile, the positive electrode 1 is held in forced contact with a positive elec,rode collector 9 secured to the inner surface of a container 8 also serving as a positive electrode terminal. Then, the separator 3 is placed in position on the positive electrode 1.
In this state, the seal cap 6 is fitted in the open top of the container 8.
The battery thus assembled is then put in a sealed vessel (not shown) and the sealed vessel is vacuumized.
Then it is immersed in an electrolyte which i9 obtained by dissolving 1 mole/Q of lithium tetrafluoroborate in a mixed solution of propylene carbonate and 1,2-dimethoxyethane to fill the space described above with the electrolytej thus 1'73 forming the electrolyte layer 4. Thereafter, the open edge of the container 8 is sealed on the insulating gasket 5 to complete the cell.
Figure 2 is a sectional view showing a comparative cell which has a generally known structure. The cell illustrated in Figure 2 has no electrolyte layer and the separator 13 thereof is different from the separator 3 of the cell of the invention shown in Figure 1. The separator 13 in the comparative cell consists of an unwoven fabric of polypropylene with a thickness of approximately 0.5 mm.
Figure 3 shows the voltage and internal resistance of the cell of Figure 1, indicated at '`A" and the comparative cell of Figure 2, indicated at "B" plotted relative to the time of discharge under a constant load of 5.6 K~ at a temperature of 20C.
As is apparent from Figure 3, the cell "A" according to the present invention provided a constant internal resistance and no sharp increase in the internal resistance was examined. Thus, desirable discharge voltage characteristics were obtained. By contrast, the comparative "B" showed that the internal resistance was abruptly and sharply increased in a certain stage of ~he discharge and, therefore, the cell "B'' has a "two-stage" discharge voltage characteristic as shown.
The "two~stage" characteristic of the comparative cell "B" is considered to stem from the following ground.
i2~ 73 With the process of the discharge, the electrolyte that has been held by the polypropylene unwoven fabric as separator is squeezed out and, consequently, the separator has a portion or portions which include substantially no electrolyte between the positive and negative electrodes.
This portion f the polypropylene unwoven fabric, which has a considerable thickness, will function as a sort of insulator to sharply increase the internal resistance.
As the discharge proceeds further, however, the thickness of the polypropylene unwoven fabric is reduced, so that the internal resistance increase curve becomes much gentler and the dlscharge proceeds with a low cell voltage.
With the cell "A" according to the invention, which uses the thin microporous film as separator, even when the volume of the positive electrode is increased, the distance between the positive and negative electrodes is small, so that the internal resistance is not increased rapidly. Further , although the microporous polypropylene film has less liquid holdlny capacity compared to the polypropylene unwoven fabric, this gives rise to no --problem with the cell "A" since the electrolyte layer consisting of the electrolyte only is formed between the separator and the negative electrode.
Figure 4 shows a modified structure of the nonaqueous electrolyte cell according to the present invention.
In the embodiment of Figure 4, the separator 3 has three separator elements and the positive electrode 1 has ~l24~173 a conductive ring 10 therearound. A first or lower separa-tor element 3A, which is placed on the positive electrode 1 with the ring 10 is made of a microporous polyethylene film having a thickness of 0.05 mm. A desired microporous poyethylene film for the separator element 3A is "HIPORE 3050" produced by Asahi Kasei Co., Ltd., Tokyo, Japan, which has desired characte~istics for holding the electrolyte, that is, 500~ and more, and provides e~cellent extensibility toward the negative electrode 2 when the volume of the positive electrode 1 is increased. Although the first separator element 3A has two "HIPORE 3050" ( a trademark) films simply superposed in the illustrated embodiment, these films can be laminated together.
Above the first separator element 3A is disposed a sec-ond or upper separator element 3B contacted with a lower surface of the electrolyte layer 4 with a spac0 therebetween. The second separator element 3B is a microporous polypropylene film having a thickness of 0.03 mm, and for this purpose "DURAGAR~ 2400" (a trademark) produced by Celanese Corp. is found to be desirable.
The second separator element 3B of "DURAGARD 2400", which pro-vides lower property for holding the electrolyte but has smaller pore opening than the first separator element 3A of "HIPORE
3050", can prevent the positive electrode powder from adhering to the lithium surEace of the negative electrode 2, and consequently C~ll characteristics are improved.
_ g ' ' . ~ , ~Z~ 3 A third or middle separator element 3C is disposed in the space confined between the first or lower separator element 3A and the second or upper separator element 3B in a closely contacted relation to form a three-layered separator 3. The third separator element 3C
is a micropor~us polyethylene film having a thickness of 0.1 rnm, and for this purpose "HIPORE 2100" produced by Asahi Kasei Co., Ltd. is desirable. The third separator element 3C of "HIPORE 2100" has an excellent property of holding the electrolyte, but may be omitted if necessary.
Other elements and structure may be considered to be substantially similar to those of the embodiment of figure 1, and a detailed description is omitted.
The cell according to the present invention has a separator of a microporous resin film or films and an electrolyte layer consisting of an electrolyte only between the separator and either electrode, while the positive electrode consists of a material with the apparent volume thereof increased by the discharge reaction.
Thus, it is possible to suppress a sharp increase of the internal resistance with the progress of the discharge and provide a flat or constant discharge voltage characteristic, which is remarkablybeneficial in industries.
The aforementioned Japanese Laid-Open Patent Publication No. 57-174871 discloses formation of an electrolyte layer between a separator and a negative electrode.
In this case, however, the separator consists of an ., , ~24~fl~3 unwoven fabric of polypropylene. Therefore, the internal resistance will increase sharply like the co~parative cell which has been described above with reference to Figure 2.
The present invention relates to a nonaqueous electrolyte cell having a positive electrode of a material with the apparent volume thereof increased with the discharge reaction.
There are materials with the apparent volume thereof increased with the discharge reaction, e.g., carbon fluorides, silver chromate and manganese dio~ide as disclosed in Japanese Patent Publication 54-35,653 published Nov. 5, 1979 and metal sulphides (such as F`eS, FeS2, CuS, Cu2S) or copper oxide and bismuth oxide, as disclosed in Japanese Laid-Open Patent Publication No. 57-174871, published oct. 27, 1982. Where such materials are used as positive electrode active material for a nonaqueous electrolyte cell, the following problem arises.
As the separator for this type of cell, unwoven ~abric of polypropylene is generally used as disclosed in the literatures described above. However, as the volume of the positive electrode is increased with the discharge reaction, the separator of polypropylene unwoven fabric disposed between the positive and negative electrodes is compressed to squeeze out the retained electrolyte from the separator. Consequently, a local portion of polypropylene unwoven fabric where there is substantially no electrolyte contained therein is present between the positive and negative electrodes, so that the internal .~
" i-,. ..
;:~Z4~73 resistance ls sharply increased, resulting in deterioration of cell characteristics.
The present invention provides an improved non-aqueous electrolyte cell ~hich has desirous discharge voltage character-istics, without a sharp increase of the internal resistance.
The present invention also provides an improved non-aqueous electrolyte cell which can suppress a sharp increase of the internal reistance thereo~, the cell having a positive electrode with the apparent volume thereof increase with the discharge reaction in the process of discharge.
The present invention again affords a new non-aqueous electrolyte cell ~hich provides improved cell characteristics with a stable internal resistance and a discharge voltage.
According to the present invention, there is provided a non aqueous elecrolyte cell, which comprises a negative electrode containing as active material a light metal such as lithium or sodium or an alloy of these light metals, and a positive elec-trode consisting substantially i;Z4~73 of a material wi-th the apparent volume thereof increasing by a discharge reaction. The cell has a separator formed substan-tially of a microporous resin film on the surface of either elec-trode facing the other electrode, and an electrolyte layer filled in a space between the above-described other electrode and the separator wherein said electrolyte layer is formed by filling said space with liquid electrolyte.
In the non-aqueous electrolyte cell according to the present invention, the apparent volume increase of the positive electrode caused with the discharge reaction is substantially absorbed by the electrolyte layer. In addition, since the sepa-rator provided between the positive and negative electrodes is formed of a very thin synthetic resin film or films, even if the volume of the positive electrode is increased until the positive and negative electrodes are in contact with the separator where there is locally substantially no electrolyte present, the dis-tance between the positlve and negative electrodes is very small, and the internal resistance will never be sharply increased.
In one embodiment of the present invention said separa-tor is disposed on the surface of said positive electrode and said electrolyte layer is formed between said separator and sald ne~ative electrode. Suitably said microporous resln film is a polypropylene film. Desirably the polypropylene film has a thickness of approximately 0.025 mm.
In another embodiment of the present invention said separator comprises a first separator element of a polyethylene film and a second separator element of a polypropylene film, and wherein said first separator element is closely contacted with said positive electrode and said second separator is closely con-tacted with said electrolyte layer. Desirably the cell ~urther comprises a third separator element of a polyethylene film between said first separator element and said second separator element in a closely contacted three-layer structure. Suitably ,~,..~.
,. ;,~
iZ4~ 3 said :Eirst separator element consisks of two polyethylene films closely con-tacte~ together.
The present inven-tion also provides a non-aqueous elec-trolyte cell comprising a negative electrode containlng an active material of at least a single light metal or its alloy, an annu-lar insulating gasket along an edge of said negative electrode, a positive electrode composed of a material with an apparent volume thereof increased with a discharge reaction, a separator having a microporous polyethylene film disposed on a surface of said posl-tive electrode, and an electrolyte layer filled in a space between said separator and said negative electrode wherein said separator is held at a circumferential end thereof be-tween said positive electrode and said annular insulating gasket and wherein said electrolyte layer is formed by filling said space with liquid electrolyte such that said electrolyte layer is disposed in the direction of stacking of said separator and the positive and negative electrodes.
The present invention will be further illustrated by way of -the accompanying drawings, in which:-Figure 1 is a sectional view of a non-aqueous elec~
trolyte cell according to the present invention;
Figure 2 is a sectional view of a comparative cell which is known in the art;
~, - 4a -l.,i,.
vJ ,~ .
.1;24~3~73 Figure 3 is a graph showing cell voltage characteristics and internal resistance characteristics plotted relative to a discharge time, with respect to the inventive cell of Figure 1 and the comparative cell of Figure 2; and Figure 4 is a sectional view of a cell according to another embodiment of the invention.
Referring to Figure 1 of the drawing, a cell has a positive electrode 1, a negative electrode 2, a separator 3 and an electrolyte layer 4. The positive electrode 1 is obtained by adding 10 wt~ of graphite as electrical conductor and 5 wt~ of fluorine resin powder as binder to 85wt~ of iron disulfide (FeS2) as active material press molding the mixture with a pressure of 2 tons/cm2 to produce pellets with a diameter of approximately 11.0 mm and a thickness of approximately 1.8 rnm, and sintering the pellets at a temperature of 200 to 300C.
The negative electrode 2 is a stamped lithium sheet with a diameter of approximately 7.5 mm and a thickness of approximately 2.2 mm. The separator 3 is a stamped microporous polypropylene film with a diameter of approximately 11.0 mm and a thickness of approximately 0.025 mm.
The electrolyte layer 4 is formed by filling the space between the negati~e electrode 2 and the separator 3 4 ~ ~,q ~, with liquid electrolyte. The microporous resin film may be a polyethylene film instead of the polypropylene film as in the above embodiment.
An assembly operation of the nonaqueous electrolyte cell illustrated in Figure 1 will be explained. First, the lithium negative electrode 2 is press bonded to a negative electrode collector 7, which is secured to the inner surface of a seal cap 6 also serving as a negative electrode terminal with an annular insulating gasket 5 provided along the edge by insert molding, so that the lithium negative electrode 2 will not fall when the cell is inverted. At this time, a space is defined by the lithium negative electrode 2 and the annular insulating gasket 5.
Meanwhile, the positive electrode 1 is held in forced contact with a positive elec,rode collector 9 secured to the inner surface of a container 8 also serving as a positive electrode terminal. Then, the separator 3 is placed in position on the positive electrode 1.
In this state, the seal cap 6 is fitted in the open top of the container 8.
The battery thus assembled is then put in a sealed vessel (not shown) and the sealed vessel is vacuumized.
Then it is immersed in an electrolyte which i9 obtained by dissolving 1 mole/Q of lithium tetrafluoroborate in a mixed solution of propylene carbonate and 1,2-dimethoxyethane to fill the space described above with the electrolytej thus 1'73 forming the electrolyte layer 4. Thereafter, the open edge of the container 8 is sealed on the insulating gasket 5 to complete the cell.
Figure 2 is a sectional view showing a comparative cell which has a generally known structure. The cell illustrated in Figure 2 has no electrolyte layer and the separator 13 thereof is different from the separator 3 of the cell of the invention shown in Figure 1. The separator 13 in the comparative cell consists of an unwoven fabric of polypropylene with a thickness of approximately 0.5 mm.
Figure 3 shows the voltage and internal resistance of the cell of Figure 1, indicated at '`A" and the comparative cell of Figure 2, indicated at "B" plotted relative to the time of discharge under a constant load of 5.6 K~ at a temperature of 20C.
As is apparent from Figure 3, the cell "A" according to the present invention provided a constant internal resistance and no sharp increase in the internal resistance was examined. Thus, desirable discharge voltage characteristics were obtained. By contrast, the comparative "B" showed that the internal resistance was abruptly and sharply increased in a certain stage of ~he discharge and, therefore, the cell "B'' has a "two-stage" discharge voltage characteristic as shown.
The "two~stage" characteristic of the comparative cell "B" is considered to stem from the following ground.
i2~ 73 With the process of the discharge, the electrolyte that has been held by the polypropylene unwoven fabric as separator is squeezed out and, consequently, the separator has a portion or portions which include substantially no electrolyte between the positive and negative electrodes.
This portion f the polypropylene unwoven fabric, which has a considerable thickness, will function as a sort of insulator to sharply increase the internal resistance.
As the discharge proceeds further, however, the thickness of the polypropylene unwoven fabric is reduced, so that the internal resistance increase curve becomes much gentler and the dlscharge proceeds with a low cell voltage.
With the cell "A" according to the invention, which uses the thin microporous film as separator, even when the volume of the positive electrode is increased, the distance between the positive and negative electrodes is small, so that the internal resistance is not increased rapidly. Further , although the microporous polypropylene film has less liquid holdlny capacity compared to the polypropylene unwoven fabric, this gives rise to no --problem with the cell "A" since the electrolyte layer consisting of the electrolyte only is formed between the separator and the negative electrode.
Figure 4 shows a modified structure of the nonaqueous electrolyte cell according to the present invention.
In the embodiment of Figure 4, the separator 3 has three separator elements and the positive electrode 1 has ~l24~173 a conductive ring 10 therearound. A first or lower separa-tor element 3A, which is placed on the positive electrode 1 with the ring 10 is made of a microporous polyethylene film having a thickness of 0.05 mm. A desired microporous poyethylene film for the separator element 3A is "HIPORE 3050" produced by Asahi Kasei Co., Ltd., Tokyo, Japan, which has desired characte~istics for holding the electrolyte, that is, 500~ and more, and provides e~cellent extensibility toward the negative electrode 2 when the volume of the positive electrode 1 is increased. Although the first separator element 3A has two "HIPORE 3050" ( a trademark) films simply superposed in the illustrated embodiment, these films can be laminated together.
Above the first separator element 3A is disposed a sec-ond or upper separator element 3B contacted with a lower surface of the electrolyte layer 4 with a spac0 therebetween. The second separator element 3B is a microporous polypropylene film having a thickness of 0.03 mm, and for this purpose "DURAGAR~ 2400" (a trademark) produced by Celanese Corp. is found to be desirable.
The second separator element 3B of "DURAGARD 2400", which pro-vides lower property for holding the electrolyte but has smaller pore opening than the first separator element 3A of "HIPORE
3050", can prevent the positive electrode powder from adhering to the lithium surEace of the negative electrode 2, and consequently C~ll characteristics are improved.
_ g ' ' . ~ , ~Z~ 3 A third or middle separator element 3C is disposed in the space confined between the first or lower separator element 3A and the second or upper separator element 3B in a closely contacted relation to form a three-layered separator 3. The third separator element 3C
is a micropor~us polyethylene film having a thickness of 0.1 rnm, and for this purpose "HIPORE 2100" produced by Asahi Kasei Co., Ltd. is desirable. The third separator element 3C of "HIPORE 2100" has an excellent property of holding the electrolyte, but may be omitted if necessary.
Other elements and structure may be considered to be substantially similar to those of the embodiment of figure 1, and a detailed description is omitted.
The cell according to the present invention has a separator of a microporous resin film or films and an electrolyte layer consisting of an electrolyte only between the separator and either electrode, while the positive electrode consists of a material with the apparent volume thereof increased by the discharge reaction.
Thus, it is possible to suppress a sharp increase of the internal resistance with the progress of the discharge and provide a flat or constant discharge voltage characteristic, which is remarkablybeneficial in industries.
The aforementioned Japanese Laid-Open Patent Publication No. 57-174871 discloses formation of an electrolyte layer between a separator and a negative electrode.
In this case, however, the separator consists of an ., , ~24~fl~3 unwoven fabric of polypropylene. Therefore, the internal resistance will increase sharply like the co~parative cell which has been described above with reference to Figure 2.
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A non-aqueous electrolyte cell comprising a nega-tive electrode containing an active material of at least a single light metal or its alloy, a positive electrode composed of a material with an apparent volume thereof increased with a dis-charge reaction, a separator having a microporous resin film dis-posed on a surface of one of the positive and negative elec-trodes, and an electrolyte layer filled in a space between said separator and another one of the positive and negative electrodes wherein said electrode layer is formed by filling said space with liquid electrolyte.
2. A non-aqueous electrolyte cell according to claim 1, wherein said separator is disposed on the surface of said pos-itive electrode and said electrolyte layer is formed between said separator and said negative electrode.
3. A non-aqueous electrolyte cell according to claim 1, wherein said microporous resin film is a polypropylene film.
4. A non-aqueous electrolyte cell according to claim 1, wherein said separator comprises a first separator element of a polyethylene film and a second separator element of a polypropylene film, and wherein said first separator element is closely contacted with said positive electrode and said second separator is closely contacted with said electrolyte layer.
5. A non-aqueous electrolyte cell according to claim 4, further comprising a third separator element of a polyethylene film between said first separator element and said second separa-tor element in a closely contacted three-layer structure.
6. A non-aqueous electrolyte cell according to claim 4, wherein said first separator element consists of two polyethy-lene films closely contacted together.
7 . A non-aqueous electrolyte according to claim 3, in which the polypropylene film has a thickness of approximately 0.025 mm.
8. A non-aqueous electrolyte cell comprising a nega-tive electrode containing an active material of at least a single light metal or its alloy, an annular insulating gasket along an edge of said negative electrode, a positive electrode composed of a material with an apparent volume thereof increased with a dis-charge reaction, a separator having a microporous polyethylene film disposed on a surface of said positive electrode, and an electrolyte layer filled in a space between said separator and said negative electrode wherein said separator is held at a cir-cumferential end thereof between said positive electrode and said annular insulating gasket and wherein said electrolyte layer is formed by filling said space with liquid electrolyte such that said electrolyte layer is disposed in the direction of stacking of said separator and the positive and negative electrodes.
9. A non-aqueous electrolyte cell according to claim 8, in which the polyethylene film has a thickness of 0.05 mm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59129659A JPS618852A (en) | 1984-06-22 | 1984-06-22 | Nonaqueous electrolyte cell |
| JP59-129,659 | 1984-06-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1248173A true CA1248173A (en) | 1989-01-03 |
Family
ID=15014970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000484770A Expired CA1248173A (en) | 1984-06-22 | 1985-06-21 | Nonaqueous electrolyte cell |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS618852A (en) |
| CA (1) | CA1248173A (en) |
| DE (1) | DE3522261A1 (en) |
| FR (1) | FR2566587B1 (en) |
| GB (1) | GB2160705B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5945234A (en) * | 1995-05-05 | 1999-08-31 | Rayovac Corporation | Metal-air cathode can having reduced corner radius and electrochemical cells made therewith |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4794057A (en) * | 1987-07-17 | 1988-12-27 | Duracell Inc. | Separator for electrochemical cells |
| JPH01258358A (en) * | 1988-04-06 | 1989-10-16 | Japan Vilene Co Ltd | Lithium battery separator |
| US6382857B1 (en) | 1998-08-27 | 2002-05-07 | Canon Kabushiki Kaisha | Bearing mechanism and conveying apparatus and recording apparatus |
| US6849360B2 (en) * | 2002-06-05 | 2005-02-01 | Eveready Battery Company, Inc. | Nonaqueous electrochemical cell with improved energy density |
| US7595133B2 (en) | 2006-07-01 | 2009-09-29 | The Gillette Company | Lithium cell |
| WO2011058745A1 (en) | 2009-11-16 | 2011-05-19 | パナソニック株式会社 | Primary lithium cell |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU64077A1 (en) * | 1970-10-29 | 1972-06-28 | ||
| CH630492A5 (en) * | 1977-04-28 | 1982-06-15 | Leclanche Sa | ALKALINE PRIMARY CELL. |
| US4129686A (en) * | 1977-11-16 | 1978-12-12 | Union Carbide Corporation | Pronged anode collector for internally shorting galvanic cells |
| US4310608A (en) * | 1980-11-06 | 1982-01-12 | Energy Research Corporation | Separator incorporating liquid layer |
| JPS57174871A (en) * | 1981-04-20 | 1982-10-27 | Hitachi Maxell Ltd | Organic electrolyte cell |
| JPS57189163A (en) * | 1981-05-16 | 1982-11-20 | Ricoh Co Ltd | Developing device |
| JPS5912569A (en) * | 1982-07-09 | 1984-01-23 | Hitachi Maxell Ltd | Manufacture of organic electrolyte battery |
| JPS5987753A (en) * | 1982-11-10 | 1984-05-21 | Sanyo Electric Co Ltd | Organic electrolytic battery |
| DE3242139C2 (en) * | 1982-11-13 | 1984-09-06 | Accumulatorenwerke Hoppecke Carl Zoellner & Sohn GmbH & Co KG, 5790 Brilon | Process for the production of positive electrodes for electrochemical elements, in particular Li / Mn0 2 cells and electrodes produced by this process |
| JPH0752656B2 (en) * | 1982-11-19 | 1995-06-05 | デュラセル インターナショナル インコーポレーテッド | Sealed nickel-zinc battery |
| JPS59169057A (en) * | 1983-03-16 | 1984-09-22 | Hitachi Maxell Ltd | Flat lithium cell with lead terminals |
| EP0138056B1 (en) * | 1983-09-19 | 1987-12-23 | Eveready Battery Company, Inc. | Nonaqueous cell with a novel organic electrolyte |
| FR2553568B1 (en) * | 1983-10-14 | 1986-04-11 | Gipelec | ELECTROCHEMICAL GENERATOR WITH NONAQUEOUS ELECTROLYTE, WHOSE POSITIVE ELECTRODE IS BASED ON MANGANESE BIOXIDE |
-
1984
- 1984-06-22 JP JP59129659A patent/JPS618852A/en active Granted
-
1985
- 1985-06-19 GB GB08515550A patent/GB2160705B/en not_active Expired
- 1985-06-21 FR FR858509472A patent/FR2566587B1/en not_active Expired - Fee Related
- 1985-06-21 CA CA000484770A patent/CA1248173A/en not_active Expired
- 1985-06-21 DE DE19853522261 patent/DE3522261A1/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5945234A (en) * | 1995-05-05 | 1999-08-31 | Rayovac Corporation | Metal-air cathode can having reduced corner radius and electrochemical cells made therewith |
| US6280876B1 (en) | 1995-05-05 | 2001-08-28 | Rayovac Corporation | Metal-air cathode can having reduced corner and electrochemical cells made therewith |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8515550D0 (en) | 1985-07-24 |
| GB2160705B (en) | 1987-09-23 |
| FR2566587B1 (en) | 1992-07-17 |
| DE3522261A1 (en) | 1986-01-02 |
| JPH0560233B2 (en) | 1993-09-01 |
| JPS618852A (en) | 1986-01-16 |
| DE3522261C2 (en) | 1989-10-26 |
| FR2566587A1 (en) | 1985-12-27 |
| GB2160705A (en) | 1985-12-24 |
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