JPS6372063A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPS6372063A JPS6372063A JP61213991A JP21399186A JPS6372063A JP S6372063 A JPS6372063 A JP S6372063A JP 61213991 A JP61213991 A JP 61213991A JP 21399186 A JP21399186 A JP 21399186A JP S6372063 A JPS6372063 A JP S6372063A
- Authority
- JP
- Japan
- Prior art keywords
- separator
- positive electrode
- aqueous electrolyte
- negative electrode
- electrolyte battery
- 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.)
- Pending
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 29
- -1 polyethylene Polymers 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 16
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004743 Polypropylene Substances 0.000 claims abstract description 12
- 229920001155 polypropylene Polymers 0.000 claims abstract description 12
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 7
- 239000007774 positive electrode material Substances 0.000 claims abstract description 7
- 238000010030 laminating Methods 0.000 claims abstract description 6
- 239000004698 Polyethylene Substances 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 229920000573 polyethylene Polymers 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 239000007773 negative electrode material Substances 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000339 iron disulfide Inorganic materials 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052960 marcasite Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 229910052683 pyrite Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 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
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は、非水電解液電池に関し、更に詳しくは、放電
時の内部抵抗増大が抑制され、かつ内部短絡も防止でき
る非水電解液電池に関する。[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention relates to a non-aqueous electrolyte battery, and more specifically, to a non-aqueous electrolyte battery, and more specifically, to a non-aqueous electrolyte battery that can suppress an increase in internal resistance during discharging and can also prevent internal short circuits. Regarding non-aqueous electrolyte batteries.
（従来の技術）
酸化第二銅（ＣｕＯ）や二硫化鉄（ＦｅＳ２）は、正極
活物質としての中位体積占りの理論電気容量が大きく、
資源としても“３富であり、したがって比較的安価に入
手できるという利点を有している。しかもＣｕＯやＦｅ
Ｓを正極活物質とする正極と、アルカリ金属またぼアル
カリ土類金属を負極活物質とする負極とから成る非水電
解液電池、例えば、ＣｕＯ−リチウム（Ｌ ｉ）系電池
または、ＦｅＳ２−Ｌｉ系電池は、その作動電圧が１．
４〜１，５■であり、酸化銀電池や水銀電池との互換使
用が可能であるため近年、種々の電子機器の電源として
注目を集めている。(Prior art) Cupric oxide (CuO) and iron disulfide (FeS2) have a large theoretical electric capacity at a medium volume as positive electrode active materials.
As a resource, it has the advantage of being one of the three richest resources and therefore can be obtained relatively cheaply.Moreover, CuO and Fe
A non-aqueous electrolyte battery consisting of a positive electrode using S as a positive electrode active material and a negative electrode using an alkali metal or alkaline earth metal as a negative electrode active material, such as a CuO-lithium (Li)-based battery or a FeS2-Li The operating voltage of the system battery is 1.
4 to 1.5 square meters, and can be used interchangeably with silver oxide batteries and mercury batteries, so in recent years it has attracted attention as a power source for various electronic devices.
上記したような従来の非水電解液゛電池を一例として図
示した第１図において説明する。The conventional non-aqueous electrolyte battery as described above will be explained with reference to FIG. 1, which shows it as an example.
第１図で、まず、１は正極缶であり、例えばステンレス
鋼から成る。２は、正極であり正極活物質であるＣｕＯ
および／またはＦｅＳ２と導電材である例えば黒鉛と結
着剤であるポリテトラフルオロエチレンとをＵｆｉし、
この混合物をペレット状に加圧成形したものである。３
は、正極２の上面に載置されたセパレータであり、例え
ば、ポリプロピレンから成る不織布である。４は、アル
キル金属またはアルカリ土類金属から成り、上記した正
極２の上に載置されている負極で、例えば、ステンレス
鋼から成る負極缶５の内壁面に密着している。負極缶５
は、例えば、ポリプロピレンから成る絶縁バッキング６
を介して正極缶１の上方開口部に冠若され、該開口部縁
辺を内側に屈曲せしめて電池全体を封口しである。なお
、セパレータ３には、例えば、プロピレンカーボネート
と１．２−ジメトキシエタンとの等体積比混合溶媒に過
塩素酸リチウムを所定量溶解させた電解液が含浸されて
いる。In FIG. 1, numeral 1 denotes a positive electrode can, which is made of stainless steel, for example. 2 is a positive electrode and positive electrode active material CuO
and/or Ufi FeS2, a conductive material such as graphite, and a binder polytetrafluoroethylene,
This mixture is pressure molded into pellets. 3
is a separator placed on the upper surface of the positive electrode 2, and is, for example, a nonwoven fabric made of polypropylene. Reference numeral 4 denotes a negative electrode made of an alkyl metal or an alkaline earth metal and placed on the above-mentioned positive electrode 2, and is in close contact with the inner wall surface of a negative electrode can 5 made of stainless steel, for example. Negative electrode can 5
is, for example, an insulating backing 6 made of polypropylene.
The upper opening of the positive electrode can 1 is capped through the opening, and the edges of the opening are bent inward to seal the entire battery. The separator 3 is impregnated with, for example, an electrolytic solution in which a predetermined amount of lithium perchlorate is dissolved in a mixed solvent of propylene carbonate and 1,2-dimethoxyethane in an equal volume ratio.
（発明が解決しようとする問題点）
ところで、上記したような非水電解液電池において、放
電すると正極が膨張する。この正極の膨張現象により以
下のような間開が生ずる。(Problems to be Solved by the Invention) By the way, in the above-mentioned non-aqueous electrolyte battery, the positive electrode expands when it is discharged. This expansion phenomenon of the positive electrode causes the following gap.
第１の問題は、正極が膨張することによりセパレータと
密着するのでセパレータに含浸せしめていた非水電解液
が正極側にも一部吸収され、その結果、セパレータに残
存する非水電解液が減少することにより電池全体の内部
抵抗が上昇するという問題である。特に、不織布のよう
に目の粗いセパレータを用いたときは、この現象が顕著
に発現する。The first problem is that as the positive electrode expands and comes into close contact with the separator, some of the non-aqueous electrolyte that was impregnated into the separator is absorbed into the positive electrode, resulting in a decrease in the amount of non-aqueous electrolyte remaining in the separator. The problem is that this increases the internal resistance of the entire battery. This phenomenon is particularly noticeable when a coarse separator such as a nonwoven fabric is used.
第２の問題は、膨張した正極とセパレータとは相互に強
く圧接することになるのでセパレータに亀裂が入ったり
、また、正極それ自身が破損して微粉が生ずるという問
題である。The second problem is that the expanded positive electrode and separator come into strong pressure contact with each other, which may cause cracks in the separator or damage to the positive electrode itself, resulting in the production of fine powder.
このような事態になると、例えば、正極の微粉がセパレ
ータ内に侵入したり、または、セパレータの亀裂を介し
て正極と負極とが直接接触したりして結局は内部短絡が
発生して電池としての機能を喪失する。If this happens, for example, fine powder from the positive electrode may enter the separator, or the positive electrode and negative electrode may come into direct contact through cracks in the separator, resulting in an internal short circuit that may cause the battery to fail. Loss of function.
特に、この第２の問題は、電池としての信頼性を著しく
損なわせるものであり、この解決は強く要請されている
。In particular, this second problem significantly impairs the reliability of the battery, and a solution to this problem is strongly desired.
本発明は、上記した問題点を解決し、保液性が優れ、か
つ強度も大きい後述するｖＬ層シートをセパレータとす
ることにより、放電時にける内部抵抗の増大が抑制され
、また、内部短絡を起すこともない新規構造の非水電解
液電池の提供を目的とする。The present invention solves the above-mentioned problems and uses a vL layer sheet, which will be described later, which has excellent liquid retention and high strength, as a separator, thereby suppressing an increase in internal resistance during discharge and preventing internal short circuits. The purpose of the present invention is to provide a non-aqueous electrolyte battery with a new structure that does not cause any damage.
［発明の構成コ
（問題点を解決するだめの手段）
本発明の非水電解液電池は、アルカリ金属またはアルカ
リ土類金属を負極活物質とする負極と、ＣｕＯおよび／
またはＦｅＳ２を正極活物質とする正極と、負極と正極
との間に介在されるセパレータと、該セパレータに含浸
されている非水電解液とから成る非水電解液電池におい
て、該セパレータが、ポリエチレンまたはポリプロピレ
ンから成る平均粒径０．０１〜１μｍの多孔質フィルム
を２枚重上積層した積層シートであることを特徴とする
。[Configuration of the Invention (Means for Solving the Problems)] The non-aqueous electrolyte battery of the present invention comprises a negative electrode containing an alkali metal or an alkaline earth metal as a negative electrode active material, CuO and/or
Alternatively, in a non-aqueous electrolyte battery comprising a positive electrode using FeS2 as a positive electrode active material, a separator interposed between the negative electrode and the positive electrode, and a non-aqueous electrolyte impregnated in the separator, the separator is made of polyethylene Alternatively, it is characterized in that it is a laminated sheet in which two porous films made of polypropylene and having an average particle diameter of 0.01 to 1 μm are laminated.
本発明の非水電解液電池は、セパレータに後述するよう
なりｉ層シートを用いたことに特徴を有するものであっ
て他の要素は第１図に例示した従来構造の電池と変わる
ことはない。The non-aqueous electrolyte battery of the present invention is characterized by the use of an i-layer sheet for the separator, as will be described later, and other elements are the same as the battery of the conventional structure illustrated in FIG. .
本発明にかかるセパレータは、ポリエチレンフィルムま
たはポリプロピレンフィルムから成る平均孔径が０．０
１〜１胛の多孔質フィルムを２枚重上積層した積層シー
トである。セパレータを構成する多孔質フィルムの平均
孔径が１μ贋を超えると、正極から溶は出した銅イオン
や鉄イオンが孔を透過して負極表面上に銅や鉄として析
出し、これらが酸化されて負極表面上で酸化被膜となる
ため内部抵抗が増す。更に、膨張し、かつセパレータに
圧接させる正極側に該孔内に保持されている非水電解液
が吸収され易くなるため上記した理由で内部抵抗の増大
が促進される。また、平均孔径がＯ，ＱＩＩｊＪ１未満
の場合には、孔径が小さすぎるのでイオン伝導性が悪く
なり、電池の作動電圧が低くなる。好ましくは、０．０
５〜０．６牌である。また、セパレータに用いる多孔質
フィルムは、適正量の非水電解液をフィルムに分散する
孔内に保持されるために、気孔率が３０〜６５％である
ものを用いることが好ましい。The separator according to the present invention is made of polyethylene film or polypropylene film and has an average pore diameter of 0.0.
It is a laminated sheet made by laminating two porous films of 1 to 1 layer. If the average pore diameter of the porous film constituting the separator exceeds 1μ, copper and iron ions dissolved from the positive electrode will pass through the pores and precipitate on the negative electrode surface as copper and iron, which will be oxidized. An oxide film forms on the surface of the negative electrode, increasing internal resistance. Furthermore, the non-aqueous electrolyte held in the pores is more likely to be absorbed by the positive electrode that expands and is brought into pressure contact with the separator, which promotes an increase in internal resistance for the reasons described above. Furthermore, when the average pore diameter is less than O,QIIjJ1, the pore diameter is too small, resulting in poor ionic conductivity and a low battery operating voltage. Preferably 0.0
5 to 0.6 tiles. Further, the porous film used for the separator preferably has a porosity of 30 to 65% so that an appropriate amount of non-aqueous electrolyte is retained in the pores that are dispersed in the film.
上記した多孔質フィルム１枚では、その機械的強度が充
分でなく、膨張したときセパレータに亀裂が入る虞れが
あるので本発明においては上記多孔質フィルムを２枚以
上績層した積層シートをセパレータとする。A single porous film described above does not have sufficient mechanical strength and may cause cracks in the separator when it expands. Therefore, in the present invention, a laminated sheet made of two or more of the above porous films is used as a separator. shall be.
更に、これらの多孔質フィルムを２枚以上績層する時に
、その延伸方向がそれぞれ異なるように積層することが
好ましくこれにより、得られた積層シートは充分な強度
を有するようになるので放電途中で正極が膨張しても亀
裂が入ることをほぼ完全に防止できる。Furthermore, when two or more of these porous films are laminated, it is preferable to laminate them so that their stretching directions are different, so that the resulting laminated sheet has sufficient strength. Even if the positive electrode expands, cracking can be almost completely prevented.
本発明にかかるセパレータは、例えば、次のようにして
製造することができる。The separator according to the present invention can be manufactured, for example, as follows.
すなわち、上記したような多孔質の延伸フィルムを用意
し、延伸方向がそれぞれ異なるように積層して積層シー
トとし、これに所定の大きさに打抜き加工を施せば本発
明にかかるセパレータを製造することができる。That is, the separator according to the present invention can be produced by preparing porous stretched films as described above, laminating them in different stretching directions to form a laminated sheet, and punching this into a predetermined size. Can be done.
得られたセパレータを従来と同じように組込むことによ
り本発明の非水電解液電池を製造することができる。The non-aqueous electrolyte battery of the present invention can be manufactured by incorporating the obtained separator in a conventional manner.
（実施例）
実施例１〜２、比較例１〜３
（イ）非水電解液電池の製造
平均孔径０．０５ｕ、気孔率５０％、厚さ３０μ肩のポ
リプロピレンから成る２枚の多孔質フィルムをそれぞれ
の延伸方向が直交するように積層して積層シートとした
。これを実施例１の積層シート（試料Ａ）とした。(Example) Examples 1 to 2, Comparative Examples 1 to 3 (a) Production of nonaqueous electrolyte battery Two porous films made of polypropylene with an average pore diameter of 0.05 μ, a porosity of 50%, and a thickness of 30 μ. were laminated so that their stretching directions were perpendicular to each other to form a laminated sheet. This was used as the laminated sheet (sample A) of Example 1.
平均孔径０．０５ｇ、気孔率６０％、厚さ５０−のポリ
エチレンから成る２枚の多孔質フィルムを用いたことを
除いては、資ネ１Ａと同様にして積層シートを製造した
。これを実施例２の積層シート（試料Ｂ）とした。A laminate sheet was produced in the same manner as in Material 1A, except that two porous films made of polyethylene having an average pore diameter of 0.05 g, a porosity of 60%, and a thickness of 50 mm were used. This was used as the laminated sheet of Example 2 (Sample B).
平均孔径０．００８．、気孔率１０％、厚さ２０−のポ
リプロピレンから成る２枚の多孔質フィルムを用いたこ
とを除いては試料Ａと同様にして積層シートを製造した
。これを比較例１の積層シート （試料Ｃ）とした。Average pore diameter 0.008. A laminated sheet was produced in the same manner as Sample A except that two porous films made of polypropylene having a porosity of 10% and a thickness of 20 mm were used. This was used as the laminated sheet of Comparative Example 1 (Sample C).
平均孔径３戸、気孔率６５％、厚さ４５μｍのポリプロ
ピレンから成る２枚の多孔質フィルムを用いたことを除
いては試料Ａと同様にして積層シートを製造した。これ
を比較例２の積層シート （試料Ｄ）とした。A laminated sheet was produced in the same manner as Sample A except that two porous films made of polypropylene having an average pore diameter of 3, a porosity of 65%, and a thickness of 45 μm were used. This was used as the laminated sheet of Comparative Example 2 (Sample D).
ポリプロピレンから成る不織布（試料Ｅ）を比較例３と
して用いた。A nonwoven fabric made of polypropylene (Sample E) was used as Comparative Example 3.
次に、ステンレス鋼からなる正極缶の底面内壁に、Ｃａ
Ｏ８５重量部と導電材である黒鉛１０重量部と結着剤で
あるポリテトラフルオロエチレン５重量部とを混練後、
ペレット状に加圧成形した正極を装填し、その上に上記
の方法で得られた各積層シートまたは不織布に打抜き加
工を施してセパレータとしたものをそれぞれ載置した。Next, Ca
After kneading 85 parts by weight of O, 10 parts by weight of graphite as a conductive material, and 5 parts by weight of polytetrafluoroethylene as a binder,
A positive electrode press-molded into a pellet was loaded, and a separator obtained by punching each laminated sheet or nonwoven fabric obtained by the above method was placed on top of the positive electrode.
なお、セパレータには、プロピレンカーボネートと１．
２−ジメトシキエタンとの等体積比混合溶媒に過塩素酸
リチウムを１モル／交溶解せしめた電解液を含浸した。Note that the separator contains propylene carbonate and 1.
It was impregnated with an electrolytic solution in which 1 mol/mol of lithium perchlorate was dissolved in a mixed solvent with 2-dimethoxyethane in an equal volume ratio.
次に、金属Ｌ＋から成る負極を内填したステンレス鋼の
負極毎に正極缶をバッキングを介して嵌合し、正極缶の
開口周縁部を内方に屈曲せしめて電池全体を封口して、
セパレータがそれぞれ異なる５種類の電池を得た。Next, a positive electrode can is fitted to each stainless steel negative electrode containing a negative electrode made of metal L+ via a backing, and the opening periphery of the positive electrode can is bent inward to seal the entire battery.
Five types of batteries with different separators were obtained.
（ロ）評価試験
上記方法で得られた電池を用いて、ｚｏ’ｃにおいて外
部抵抗３０にΩの定抵抗放電を行なったときの電池の内
部抵抗の変化を周波数１ ｋＨｚにて交流インピーダン
ス法にて測定した。結果を第２図に示した。(b) Evaluation test Using the battery obtained by the above method, the change in internal resistance of the battery was measured using the AC impedance method at a frequency of 1 kHz when a constant resistance discharge of Ω was performed to an external resistor 30 in zo'c. It was measured using The results are shown in Figure 2.
実施例３〜４、比較例４〜６
平均粒径０．０５．、気孔率５０％、厚さ３０μｍのポ
リプロピレンから成る多孔質フィルムを用意して、これ
を表に示したように組合わせて積層シートとしたものと
ポリプロピレンから成る不織布に打抜き加工を施して各
種類のセパレータを用意した。Examples 3-4, Comparative Examples 4-6 Average particle size 0.05. A porous film made of polypropylene with a porosity of 50% and a thickness of 30 μm was prepared, and this was combined into a laminated sheet as shown in the table, and a nonwoven fabric made of polypropylene was punched out to form various types. A separator was prepared.
これら５種類のセパレータを用いて実施例１と同様にし
て非水電解液電池をそれぞれ５０個製造し、それらの評
価試験を行なった。放電途中で作動電圧が急激に落ち込
んだ個数とその時の負極であるリチウムの利用率を表に
示した。Using these five types of separators, 50 non-aqueous electrolyte batteries were manufactured in the same manner as in Example 1, and evaluation tests were conducted on them. The table shows the number of batteries whose operating voltage suddenly dropped during discharge and the utilization rate of lithium, which is the negative electrode, at that time.
［発明の効果］
以上の説明で明らかなように、本発明の非水電解液電池
は、放電時の内部抵抗の増大が抑制され、かつ内部短絡
が防止でき、信頼性は極めて高いものであり、したがっ
て、その工業的価値は大である。[Effects of the Invention] As is clear from the above explanation, the nonaqueous electrolyte battery of the present invention suppresses an increase in internal resistance during discharge, prevents internal short circuits, and has extremely high reliability. , therefore, its industrial value is great.
第１図は、従来の非水電解液電池の一例であるボタン型
非水電解液゛屯池の断面図である。第２図は、本発明の
非水電解液電池の放電時の内部抵抗の変化を比較例と共
に示したものである。
１・・・・・・正極缶 ２・・・・・・正極３・
・・・・・セパレータ ４・・印・負極５・・・・・
・負極毎 ６・・・・・・バッキング第１図
方文屯椅閾 （ｈｒ）
第２ド１FIG. 1 is a sectional view of a button-type non-aqueous electrolyte reservoir, which is an example of a conventional non-aqueous electrolyte battery. FIG. 2 shows the change in internal resistance during discharge of the non-aqueous electrolyte battery of the present invention together with a comparative example. 1...Positive electrode can 2...Positive electrode 3.
...Separator 4...mark/negative electrode 5...
・For each negative electrode 6...Backing 1st figure Wentun chair threshold (hr) 2nd do 1
Claims (1)
とする負極と、酸化第二銅および／または二硫化鉄を正
極活物質とする正極と、負極と正極との間に介在される
セパレータと、該セパレータに含浸されている非水電解
液とから成る非水電解液電池において、該セパレータが
、ポリエチレンまたはポリプロピレンから成る平均孔径
０．０１〜１μｍの多孔質フィルムを２枚以上積層した
積層シートであることを特徴とする非水電解液電池。 ２、該セパレータが２枚以上の該多孔質フィルムをそれ
ぞれの延伸方向が異なるように積層した積層シートであ
る特許請求の範囲第１項記載の非水電解液電池。[Claims] 1. A negative electrode containing an alkali metal or an alkaline earth metal as a negative electrode active material, a positive electrode containing cupric oxide and/or iron disulfide as a positive electrode active material, and between the negative electrode and the positive electrode. In a non-aqueous electrolyte battery consisting of an interposed separator and a non-aqueous electrolyte impregnated in the separator, the separator is made of two porous films made of polyethylene or polypropylene and having an average pore diameter of 0.01 to 1 μm. A non-aqueous electrolyte battery characterized by being a laminated sheet formed by laminating the above layers. 2. The non-aqueous electrolyte battery according to claim 1, wherein the separator is a laminated sheet in which two or more of the porous films are laminated in different stretching directions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61213991A JPS6372063A (en) | 1986-09-12 | 1986-09-12 | Nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61213991A JPS6372063A (en) | 1986-09-12 | 1986-09-12 | Nonaqueous electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6372063A true JPS6372063A (en) | 1988-04-01 |
Family
ID=16648446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61213991A Pending JPS6372063A (en) | 1986-09-12 | 1986-09-12 | Nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6372063A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0723304A3 (en) * | 1994-12-22 | 1996-08-28 | Hoechst Celanese Corp | |
| JP2003346766A (en) * | 2002-05-23 | 2003-12-05 | Matsushita Electric Ind Co Ltd | Lithium ion secondary battery |
| KR100696452B1 (en) * | 1999-11-25 | 2007-03-16 | 삼성에스디아이 주식회사 | Separator for Li-ion secondary battery and Li-ion secondary battery utilizing the same |
| JP2010027617A (en) * | 2009-10-01 | 2010-02-04 | Panasonic Corp | Lithium-ion secondary battery |
| CN102263220A (en) * | 2011-06-22 | 2011-11-30 | 广东博特动力能源有限公司 | Preparation method for battery diaphragm |
| JP2016072233A (en) * | 2014-09-29 | 2016-05-09 | 株式会社Ｇｓユアサ | Power storage device and method for manufacturing power storage device |
| US11283136B2 (en) | 2014-09-29 | 2022-03-22 | Gs Yuasa International Ltd. | Energy storage device and method of producing energy storage device |
-
1986
- 1986-09-12 JP JP61213991A patent/JPS6372063A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5667911A (en) * | 1994-11-17 | 1997-09-16 | Hoechst Celanese Corporation | Methods of making cross-ply microporous membrane battery separator, and the battery separators made thereby |
| EP0723304A3 (en) * | 1994-12-22 | 1996-08-28 | Hoechst Celanese Corp | |
| JPH08236098A (en) * | 1994-12-22 | 1996-09-13 | Hoechst Celanese Corp | Production of crossing layer porosity film battery separatorand battery separator that is manufactured by it |
| CN1075248C (en) * | 1994-12-22 | 2001-11-21 | 思凯德公司 | Methods of making cross-ply microporous membrane battery separator, and battery separators made thereby |
| JP2002184381A (en) * | 1994-12-22 | 2002-06-28 | Celgard Inc | Manufacturing method of battery cell, and battery separator |
| KR100696452B1 (en) * | 1999-11-25 | 2007-03-16 | 삼성에스디아이 주식회사 | Separator for Li-ion secondary battery and Li-ion secondary battery utilizing the same |
| JP2003346766A (en) * | 2002-05-23 | 2003-12-05 | Matsushita Electric Ind Co Ltd | Lithium ion secondary battery |
| JP2010027617A (en) * | 2009-10-01 | 2010-02-04 | Panasonic Corp | Lithium-ion secondary battery |
| CN102263220A (en) * | 2011-06-22 | 2011-11-30 | 广东博特动力能源有限公司 | Preparation method for battery diaphragm |
| WO2012174998A1 (en) * | 2011-06-22 | 2012-12-27 | Guangdong Powerlink Energy Co., Ltd | Method for preparing separator of battery |
| US9705118B2 (en) | 2011-06-22 | 2017-07-11 | Guangdong Powerlink Energy Co., Ltd. | Method for preparing separator of battery |
| JP2016072233A (en) * | 2014-09-29 | 2016-05-09 | 株式会社Ｇｓユアサ | Power storage device and method for manufacturing power storage device |
| US11283136B2 (en) | 2014-09-29 | 2022-03-22 | Gs Yuasa International Ltd. | Energy storage device and method of producing energy storage device |
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