JP4056123B2 - Lithium ion battery - Google Patents
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- JP4056123B2 JP4056123B2 JP08377898A JP8377898A JP4056123B2 JP 4056123 B2 JP4056123 B2 JP 4056123B2 JP 08377898 A JP08377898 A JP 08377898A JP 8377898 A JP8377898 A JP 8377898A JP 4056123 B2 JP4056123 B2 JP 4056123B2
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- 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
Description
【０００１】
【発明の属する技術分野】
本発明は、厚みが０．４ｍｍ以下の金属アルミニウム又はアルミニウム合金から成る外装体を有し、この外装体内に、リチウム含有複合酸化物を正極材料とする正極と、格子面（００２）面におけるｄ値（ｄ002 ）が３．４０Å以下の炭素材料を負極材料とする負極と、溶媒及び溶質から成る電解液とが収納されたリチウムイオン電池に関する。
【０００２】
【従来の技術】
従来、リチウムイオン電池の外装体としては、鉄、ステンレスから成るものが用いられていたが、このような外装体を用いた電池では、鉄等の比重が大きいことに起因して、電池重量が増大するという課題を有していた。そこで、外装缶に金属アルミニウム又はアルミニウム合金（これらを総称して、アルミニウム材料という）を用いることにより、電池の軽量化を達成し、これによって電池の重量エネルギー密度の増大を図るようなリチウムイオン電池が提案されている。
【０００３】
ここで、上記リチウムイオン電池の電解液の溶質（リチウム塩）としては、一般的にＬｉＰＦ6 が用いられるが、このＬｉＰＦ6 は負極材料である炭素材料と反応してガスが発生し易く、特に、電池の高容量化を図るべく負極材料として格子面（００２）面におけるｄ値（ｄ002 ）が３．４０Å以下の炭素材料（結晶性が高い、すなわち黒鉛化度が大きい炭素材料）を用いた場合にはガスが多量に発生する。この場合、外装体として鉄、ステンレスを用いた場合には、これら金属は強度が大きいので、電池の膨れという課題は余り生じないが、外装体として上記鉄等と同程度の厚み（０．４ｍｍ以下）を有するアルミニウム材料を用いた場合には、アルミニウム材料は強度が小さいということに起因して、電池の膨れという課題を生じる。この場合、アルミニウム材料の厚みを大きくすることにより外装缶の強度を大きくするようなことも考えられるが、これでは、電池の軽量化を達成することができない。
【０００４】
【発明が解決しようとする課題】
本発明は、以上の事情に鑑みなされたものであって、電池の軽量化を図りつつ、電池内部でガスが発生するのを抑制することにより、電池の膨らみを最小限に抑えることができるリチウムイオン電池の提供を目的とする。
【０００５】
【課題を解決するための手段】
上記目的を達成するために、本発明のうちで請求項１記載の発明は、厚みが０．４ｍｍ以下の金属アルミニウム又はアルミニウム合金から成る外装体を有し、この外装体内に、リチウム含有複合酸化物を正極材料とする正極と、格子面（００２）面におけるｄ値（ｄ002 ）が３．４０Å以下の炭素材料を負極材料とする負極と、溶媒及び溶質から成る電解液とが収納されたリチウムイオン電池において、上記電解液の溶質として、下記化２に示すリチウム塩とＬｉＰＦ6 との混合リチウム塩が用いられると共に、この混合リチウム塩におけるＬｉＰＦ6 の割合が２０モル％以下に規制されることを特徴とする。
【０００６】
【化２】
ＬｉＮ（ＣnＦ2n+1ＳＯ2）2 〔ｎは２、３または４〕
【０００７】
上記化２に示すリチウム塩は、格子面（００２）面におけるｄ値（ｄ002 ）が３．４０Å以下の炭素材料と反応し難いので、このようなリチウム塩を用いた電池では、電池内でのガス発生が大幅に低減する。但し、上記化２に示すリチウム塩を単独で用いると電池容量が小さくなるので、ＬｉＰＦ6 と混合して用いる必要がある。その一方、ＬｉＰＦ6 の量が余り多くなると電池内でのガス発生という問題が生じるので、混合リチウム塩におけるＬｉＰＦ6 の割合は２０モル％以下に規制する必要がある。
【０００８】
尚、上記化２に示すリチウム塩中のｎを２以上に規制するのは、ｎが１である場合には、アルミニウムの腐食という問題が生じるからである。また、外装缶にアルミニウム合金を用いる場合には、電池の軽量化という観点より、アルミニウムの含有率が９０％以上（アルミニウム合金の比重が３以下）のものを用いるのが望ましい。
【０００９】
また、請求項２記載の発明は請求項１記載の発明において、上記炭素材料が黒鉛であることを特徴とする。
このように、炭素材料として黒鉛を用いた場合には、黒鉛は結晶性が高いということに起因して、電池の高容量化を達成することができる。
【００１１】
また、請求項３記載の発明は、請求項１又は２記載の発明において、上記外装缶の厚みが０．２〜０．３ｍｍであることを特徴とする。このように、外装缶の厚みを極めて小さくすると、電池の軽量化という目的が十分達成される一方、上記の如くガス発生という課題は十分に解決されるので、外装缶の厚みを極めて小さくしても電池の膨れという問題は生じない。
【００１２】
【発明の実施の形態】
本発明の実施の形態を、以下に説明する。
【００１３】
本発明の角型電池は、ＬｉＣｏＯ2 から成る正極と、黒鉛〔格子面（００２）面におけるｄ値（ｄ002 ）が３．３５Å〕から成る負極と、これら両電極を離間するセパレータとから成る発電要素を有しており、この発電要素は、有底筒状の外装缶（Ａｌ３００３から成り、厚さは０．２ｍｍ）内に配置されている。この外装缶内には、エチレンカーボネート（ＥＣ）とメチルエチルカーボネート（ＭＥＣ）とが体積比で３０：７０の割合で混合された混合溶媒に、ＬｉＰＦ6 が０．１Ｍ（モル／リットル）の割合で、ＬｉＮ（Ｃ2 Ｆ5 ＳＯ2 ）2 が０．９Ｍ（モル／リットル）の割合で各々溶解された電解液が注入されている。
【００１４】
また、上記正極は正極集電タブを介して正極端子に、また上記負極は負極集電タブを介して負極端子にそれぞれ接続され、電池内部で生じた化学エネルギーを電気エネルギーとして外部へ取り出し得るようになっている。
尚、この角型電池の大きさは、幅が３０．０ｍｍ、厚みが６．０ｍｍ、高さが４８．０ｍｍ、となるように構成されている。
【００１５】
ここで、上記構造の電池を、以下のようにして作製した。
先ず、正極活物質としてのＬｉＣｏＯ2 を９０重量％と、導電剤としてのカーボンブラックを５重量％と、結着剤としてのポリフッ化ビニリデンを５重量％と、溶剤としてのＮ−メチル−２−ピロリドン（ＮＭＰ）溶液とを混合して正極用スラリーを調製した後、この正極用スラリーを正極集電体としてのアルミニウム箔（厚さ：２０μｍ）の両面に塗布した。その後、溶剤を乾燥し、ローラーで所定の厚みにまで圧縮した後、所定の幅及び長さになるように切断して、正極を作成した。
【００１６】
これと並行して、負極活物質としての黒鉛粉末を９５重量％と、結着剤としてのポリフッ化ビニリデンを５重量％と、溶剤としてのＮＭＰ溶液とを混合して負極用スラリーを調製した後、この負極用スラリーを負極集電体としての銅箔（厚さ：１６μｍ）の両面に塗布した。その後、溶剤を乾燥し、ローラーで所定の厚みにまで圧縮した後、所定の幅及び長さになるように切断して、負極を作成した。
次に、正負極をセパレータを介して配置して発電要素を作製した後、これを外装缶内に挿入し、更にこの外装缶内に、ＥＣとＭＥＣとが体積比で３０：７０の割合で混合された混合溶媒に、ＬｉＰＦ6 が０．１Ｍ（モル／リットル）の割合で、ＬｉＮ（Ｃ2 Ｆ5 ＳＯ2 ）2 が０．９Ｍ（モル／リットル）の割合で各々溶解された電解液を注入することにより、電池を作製した。
【００１７】
尚、正極材料としては上記ＬｉＣｏＯ2 の他、例えば、ＬｉＮｉＯ2 、ＬｉＭｎＯ4 或いはこれらの複合体等が好適に用いられ、また負極材料としては天然黒鉛、人造黒鉛等が好適に用いられる。
【００１８】
【実施例】
〔実施例１〕
実施例１としては上記発明の実施の形態に示す電池を用いた。
このようにして作製した電池を、以下、本発明電池Ａ１と称する。
【００１９】
〔実施例２〕
電解液の溶質として、０．２ＭのＬｉＰＦ6 と０．８ＭのＬｉＮ（Ｃ2 Ｆ5 ＳＯ2 ）2 とを用いる他は、上記実施例１と同様にして電池を作製した。
このようにして作製した電池を、以下、本発明電池Ａ２と称する。
【００２０】
〔実施例３〕
電解液の溶質として、０．０５ＭのＬｉＰＦ6 と０．９５ＭのＬｉＮ（Ｃ2 Ｆ5 ＳＯ2 ）2 とを用いる他は、上記実施例１と同様にして電池を作製した。
このようにして作製した電池を、以下、本発明電池Ａ３と称する。
【００２１】
〔実施例４〕
電解液の溶質として、０．１ＭのＬｉＰＦ6 と０．９ＭのＬｉＮ（Ｃ3 Ｆ7 ＳＯ2 ）2 とを用いる他は、上記実施例１と同様にして電池を作製した。
このようにして作製した電池を、以下、本発明電池Ａ４と称する。
【００２２】
〔実施例５〕
電解液の溶質として、０．１ＭのＬｉＰＦ6 と０．９ＭのＬｉＮ（Ｃ4 Ｆ9 ＳＯ2 ）2 とを用いる他は、上記実施例１と同様にして電池を作製した。
このようにして作製した電池を、以下、本発明電池Ａ５と称する。
【００２３】
〔比較例１〕
電解液の溶質として、１ＭのＬｉＰＦ6 を用いる他は、上記実施例１と同様にして電池を作製した。
このようにして作製した電池を、以下、比較電池Ｘ１と称する。
【００２４】
〔比較例２〕
電解液の溶質として、０．５ＭのＬｉＰＦ6 と０．５ＭのＬｉＮ（Ｃ2 Ｆ5 ＳＯ2 ）2 とを用いる他は、上記実施例１と同様にして電池を作製した。
このようにして作製した電池を、以下、比較電池Ｘ２と称する。
【００２５】
〔予備実験１〕
外装缶の材料及び厚みを変化させて電池を作製し、電解液の注液後の厚みに対する電池充電後の電池厚みの増加量を調べたので、その結果を表１に示す。
尚、充電条件は、電流１Ｃで電池電圧４．１Ｖまで充電するという条件である。
【００２６】
【表１】
上記表１から明らかなように、外装缶が鉄であれば厚みが０．２ｍｍであっても電池厚みの増加は殆どなく、また外装缶がアルミニウム材料であっても厚みが０．５ｍｍであれば電池厚みの増加は殆どない。これに対して、外装缶がアルミニウム材料でしかも厚みが０．４ｍｍ又は０．２ｍｍであれば電池厚みが増加し、特に厚みが０．２ｍｍであれば大幅に増加していることが認められる。
但し、外装缶が鉄から構成されていたり、外装缶がアルミニウム材料であっても厚みが大きければ、電池の軽量化を図ることができない。したがって、外装缶としては厚みの小さなアルミニウム材料を用いるのが望ましい。
【００２８】
〔予備実験２〕
負極材料を変化させて電池を作製した後、上記予備実験１と同様の条件で充電し、電解液の注液後の厚みに対する電池充電後の電池厚みの増加量を調べたので、その結果を表２に示す。
【００２９】
【表２】
上記表２から明らかなように、負極材料がコークス〔ｄ値（ｄ002 ）が３．４５Å〕であれば電池厚みの増加は殆どないのに対して、負極材料が黒鉛（ｄ値（ｄ002 ）が３．３５Å〕であれば電池厚みが増加していることが認められる。
但し、負極材料としてコークスを用いた場合には、電池容量が低下するので、負極材料としては黒鉛を用いるのが望ましい。
そこで、上記予備実験１及び２の結果を踏まえて、下記の本実験を行った。
【００３１】
〔本実験〕
上記本発明電池Ａ１〜Ａ５及び比較電池Ｘ１、Ｘ２において、上記予備実験１と同様の条件で充電し、電解液の注液後の厚みに対する電池充電後の電池厚みの増加量を調べたので、その結果を表３に示す。
【００３２】
【表３】
上記表３から明らかなように、比較電池Ｘ１、Ｘ２では電池厚みの増加量が０．２５ｍｍ以上であるのに対して、本発明電池Ａ１〜Ａ５では電池厚みの増加量が０．０５ｍｍ以下と小さくなっていることが認められる。
したがって、厚みが０．４ｍｍ以下（本発明電池Ａ１〜Ａ５では０．２ｍｍ）のアルミニウム材料から成る外装体を有していても、電解液の溶質として、ＬｉＮ（Ｃ2 Ｆ5 ＳＯ2 ）2 等のリチウム塩とＬｉＰＦ6 との混合リチウム塩が用いられ、且つこの混合リチウム塩におけるＬｉＰＦ6 の割合が２０モル％以下に規制されていれば、充電後の電池厚みの増加量が少なくなることがわかる。加えて、この場合、負極に黒鉛（ｄ002 が３．３５Å）を用いているので、電池容量の低下を招くこともない。
【００３４】
【発明の効果】
以上説明したように、本発明によれば、電池の軽量化を図りつつ、電池内部でガスが発生するのを抑制することにより、電池の膨らみを最小限に抑えることができるといった優れた効果を奏する。[0001]
BACKGROUND OF THE INVENTION
The present invention has an outer package made of metallic aluminum or aluminum alloy having a thickness of 0.4 mm or less, and a positive electrode using a lithium-containing composite oxide as a positive electrode material in the outer package, and d on the lattice plane (002) plane. The present invention relates to a lithium ion battery in which a negative electrode using a carbon material having a value (d 002 ) of 3.40% or less as a negative electrode material, and an electrolytic solution composed of a solvent and a solute.
[0002]
[Prior art]
Conventionally, as an exterior body of a lithium ion battery, one made of iron or stainless steel has been used. However, in a battery using such an exterior body, the weight of the battery is high due to the large specific gravity of iron or the like. It had the problem of increasing. Therefore, a lithium ion battery that achieves weight reduction of the battery by using metal aluminum or aluminum alloy (generically referred to as an aluminum material) for the outer can, thereby increasing the weight energy density of the battery. Has been proposed.
[0003]
Here, as the solute (lithium salt) of the electrolyte solution of the lithium ion battery, LiPF 6 is generally used. However, this LiPF 6 easily reacts with the carbon material that is the negative electrode material, and gas is easily generated. In order to increase the capacity of the battery, a carbon material having a d value (d 002 ) on the lattice plane ( 002 ) of 3.40 mm or less (a carbon material having high crystallinity, that is, a high degree of graphitization) is used as the negative electrode material. If so, a large amount of gas is generated. In this case, when iron or stainless steel is used as the exterior body, these metals have high strength, so the problem of battery swelling does not occur so much, but the exterior body has the same thickness (0.4 mm) as the above-described iron or the like. In the case of using an aluminum material having the following), the aluminum material has a problem of swelling of the battery due to its low strength. In this case, it is conceivable to increase the strength of the outer can by increasing the thickness of the aluminum material, but this makes it impossible to reduce the weight of the battery.
[0004]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and is capable of minimizing battery swelling by suppressing the generation of gas inside the battery while reducing the weight of the battery. The purpose is to provide an ion battery.
[0005]
[Means for Solving the Problems]
In order to achieve the above object, the invention according to claim 1 of the present invention has an exterior body made of metal aluminum or an aluminum alloy having a thickness of 0.4 mm or less, and the lithium-containing composite oxidation is included in the exterior body. A positive electrode using a material as a positive electrode material, a negative electrode using a carbon material having a d value (d 002 ) of 3.40% or less on the lattice plane (002) as a negative electrode material, and an electrolyte composed of a solvent and a solute were stored. In the lithium ion battery, a mixed lithium salt of lithium salt and LiPF 6 shown in the following chemical formula 2 is used as a solute of the electrolytic solution, and the ratio of LiPF 6 in the mixed lithium salt is regulated to 20 mol% or less. It is characterized by that.
[0006]
[Chemical 2]
LiN (C n F 2n + 1 SO 2) 2 [n is 2, 3 or 4]
[0007]
The lithium salt shown in Chemical Formula 2 is difficult to react with a carbon material having a d-value (d 002 ) of 3.40% or less on the lattice plane (002) plane. Therefore, in a battery using such a lithium salt, Gas generation is greatly reduced. However, when the lithium salt shown in Chemical Formula 2 is used alone, the battery capacity becomes small, so it is necessary to mix it with LiPF 6 . On the other hand, if the amount of LiPF 6 is excessively large, there is a problem of gas generation in the battery. Therefore, the ratio of LiPF 6 in the mixed lithium salt must be regulated to 20 mol% or less.
[0008]
Incidentally, to regulate the n in the lithium salt shown by the chemical formula 2 to 2 or more, when n is 1, because the problem of aluminum corrosion occurs. When an aluminum alloy is used for the outer can, it is desirable to use an aluminum alloy having an aluminum content of 90% or more (a specific gravity of the aluminum alloy is 3 or less) from the viewpoint of reducing the weight of the battery.
[0009]
The invention according to claim 2 is the invention according to claim 1, wherein the carbon material is graphite.
Thus, when graphite is used as the carbon material, the capacity of the battery can be increased due to the high crystallinity of graphite.
[0011]
The invention of claim 3, wherein, in the invention of claim 1 or 2, wherein the thickness of said outer can is 0.2 to 0.3 mm. As described above, when the thickness of the outer can is extremely small, the purpose of reducing the weight of the battery is sufficiently achieved, while the problem of gas generation is sufficiently solved as described above. However, the problem of battery swelling does not occur.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
[0013]
The prismatic battery of the present invention comprises a positive electrode made of LiCoO 2 , a negative electrode made of graphite (d value (d 002 ) on the lattice plane (002) plane is 3.35 Å), and a separator that separates the two electrodes. It has a power generation element, and this power generation element is arranged in a bottomed cylindrical outer can (made of Al3003, thickness is 0.2 mm). In this outer can, a ratio of 0.1 M (mol / liter) of LiPF 6 to a mixed solvent in which ethylene carbonate (EC) and methyl ethyl carbonate (MEC) are mixed at a volume ratio of 30:70. Then, electrolytic solutions in which LiN (C 2 F 5 SO 2 ) 2 is dissolved at a rate of 0.9 M (mol / liter) are injected.
[0014]
Further, the positive electrode is connected to the positive electrode terminal via the positive electrode current collecting tab, and the negative electrode is connected to the negative electrode terminal via the negative electrode current collecting tab so that chemical energy generated inside the battery can be taken out as electric energy to the outside. It has become.
In addition, the size of this square battery is configured such that the width is 30.0 mm, the thickness is 6.0 mm, and the height is 48.0 mm.
[0015]
Here, the battery having the above structure was produced as follows.
First, 90% by weight of LiCoO 2 as a positive electrode active material, 5% by weight of carbon black as a conductive agent, 5% by weight of polyvinylidene fluoride as a binder, and N-methyl-2- 2 as a solvent. After mixing with a pyrrolidone (NMP) solution to prepare a positive electrode slurry, this positive electrode slurry was applied to both surfaces of an aluminum foil (thickness: 20 μm) as a positive electrode current collector. Thereafter, the solvent was dried, compressed to a predetermined thickness with a roller, and then cut to have a predetermined width and length to prepare a positive electrode.
[0016]
In parallel with this, after preparing a negative electrode slurry by mixing 95% by weight of graphite powder as a negative electrode active material, 5% by weight of polyvinylidene fluoride as a binder, and an NMP solution as a solvent. The negative electrode slurry was applied to both sides of a copper foil (thickness: 16 μm) as a negative electrode current collector. Thereafter, the solvent was dried, compressed to a predetermined thickness with a roller, and then cut to have a predetermined width and length to prepare a negative electrode.
Next, the positive and negative electrodes are arranged via a separator to produce a power generation element, which is then inserted into an outer can, and further, EC and MEC are in a volume ratio of 30:70 in the outer can. An electrolytic solution in which LiPF 6 is dissolved in the mixed solvent at a ratio of 0.1 M (mol / liter) and LiN (C 2 F 5 SO 2 ) 2 is dissolved at a ratio of 0.9 M (mol / liter). Was injected to prepare a battery.
[0017]
In addition to LiCoO 2 described above, for example, LiNiO 2 , LiMnO 4, or a composite thereof is preferably used as the positive electrode material, and natural graphite, artificial graphite, or the like is preferably used as the negative electrode material.
[0018]
【Example】
[Example 1]
As Example 1, the battery described in the embodiment of the invention was used.
The battery thus produced is hereinafter referred to as the present invention battery A1.
[0019]
[Example 2]
A battery was fabricated in the same manner as in Example 1 except that 0.2 M LiPF 6 and 0.8 M LiN (C 2 F 5 SO 2 ) 2 were used as the solute of the electrolytic solution.
The battery thus produced is hereinafter referred to as the present invention battery A2.
[0020]
Example 3
A battery was fabricated in the same manner as in Example 1 except that 0.05 M LiPF 6 and 0.95 M LiN (C 2 F 5 SO 2 ) 2 were used as the solute of the electrolytic solution.
The battery thus produced is hereinafter referred to as the present invention battery A3.
[0021]
Example 4
A battery was fabricated in the same manner as in Example 1 except that 0.1 M LiPF 6 and 0.9 M LiN (C 3 F 7 SO 2 ) 2 were used as the solute of the electrolytic solution.
The battery thus produced is hereinafter referred to as the present invention battery A4.
[0022]
Example 5
A battery was fabricated in the same manner as in Example 1 except that 0.1 M LiPF 6 and 0.9 M LiN (C 4 F 9 SO 2 ) 2 were used as the solute of the electrolytic solution.
The battery thus produced is hereinafter referred to as the present invention battery A5.
[0023]
[Comparative Example 1]
A battery was fabricated in the same manner as in Example 1 except that 1M LiPF 6 was used as the solute of the electrolytic solution.
The battery thus produced is hereinafter referred to as comparative battery X1.
[0024]
[Comparative Example 2]
A battery was fabricated in the same manner as in Example 1 except that 0.5 M LiPF 6 and 0.5 M LiN (C 2 F 5 SO 2 ) 2 were used as the solute of the electrolytic solution.
The battery thus produced is hereinafter referred to as comparative battery X2.
[0025]
[Preliminary experiment 1]
A battery was produced by changing the material and thickness of the outer can, and the amount of increase in battery thickness after battery charging relative to the thickness after injection of the electrolyte was examined. The results are shown in Table 1.
The charging condition is that the battery voltage is charged to 4.1 V with a current of 1 C.
[0026]
[Table 1]
As is clear from Table 1 above, if the outer can is made of iron, the battery thickness hardly increases even if the thickness is 0.2 mm, and even if the outer can is an aluminum material, the thickness is 0.5 mm. There is almost no increase in battery thickness. On the other hand, when the outer can is made of an aluminum material and the thickness is 0.4 mm or 0.2 mm, the battery thickness is increased. In particular, when the thickness is 0.2 mm, it is recognized that the thickness is greatly increased.
However, if the outer can is made of iron, or the outer can is made of an aluminum material, the battery cannot be reduced in weight if the thickness is large. Therefore, it is desirable to use a thin aluminum material as the outer can.
[0028]
[Preliminary experiment 2]
After making the battery by changing the negative electrode material, the battery was charged under the same conditions as in Preliminary Experiment 1 above, and the amount of increase in battery thickness after battery charging relative to the thickness after electrolyte injection was investigated. It shows in Table 2.
[0029]
[Table 2]
As apparent from Table 2 above, when the negative electrode material is coke [d value (d 002 ) is 3.45 mm], the battery thickness hardly increases, whereas the negative electrode material is graphite (d value (d 002). ) Is 3.35 mm], it is recognized that the battery thickness has increased.
However, when coke is used as the negative electrode material, the battery capacity decreases, so it is desirable to use graphite as the negative electrode material.
Therefore, based on the results of the preliminary experiments 1 and 2, the following main experiment was performed.
[0031]
[This experiment]
In the present invention batteries A1 to A5 and comparative batteries X1 and X2, charging was performed under the same conditions as in the preliminary experiment 1, and the amount of increase in battery thickness after battery charging with respect to the thickness after injection of the electrolyte was investigated. The results are shown in Table 3.
[0032]
[Table 3]
As is clear from Table 3 above, the battery thickness increases in the comparative batteries X1 and X2 are 0.25 mm or more, whereas the battery thickness increases in the present invention batteries A1 to A5 are 0.05 mm or less. It is recognized that it is getting smaller.
Accordingly, LiN (C 2 F 5 SO 2 ) 2 is used as the solute of the electrolytic solution even if it has an exterior body made of an aluminum material having a thickness of 0.4 mm or less (0.2 mm in the present invention batteries A1 to A5). If a mixed lithium salt of LiPF 6 such as LiPF 6 is used and the ratio of LiPF 6 in the mixed lithium salt is regulated to 20 mol% or less, the increase in battery thickness after charging is reduced. I understand. In addition, in this case, since graphite (d 002 is 3.35%) is used for the negative electrode, the battery capacity is not reduced.
[0034]
【The invention's effect】
As described above, according to the present invention, it is possible to minimize the swelling of the battery by suppressing the generation of gas inside the battery while reducing the weight of the battery. Play.
Claims (3)
上記電解液の溶質として、下記化１に示すリチウム塩とＬｉＰＦ6 との混合リチウム塩が用いられると共に、この混合リチウム塩におけるＬｉＰＦ6 の割合が２０モル％以下に規制されることを特徴とするリチウムイオン電池。
As the solute of the electrolytic solution, a mixed lithium salt of lithium salt and LiPF 6 shown in the following chemical formula 1 is used, and the ratio of LiPF 6 in the mixed lithium salt is regulated to 20 mol% or less. Lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP08377898A JP4056123B2 (en) | 1998-03-30 | 1998-03-30 | Lithium ion battery |
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| Application Number | Priority Date | Filing Date | Title |
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| JP08377898A JP4056123B2 (en) | 1998-03-30 | 1998-03-30 | Lithium ion battery |
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| JP4056123B2 true JP4056123B2 (en) | 2008-03-05 |
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| JP4106644B2 (en) * | 2000-04-04 | 2008-06-25 | ソニー株式会社 | Battery and manufacturing method thereof |
| JP4910239B2 (en) * | 2000-12-25 | 2012-04-04 | 三菱化学株式会社 | Non-aqueous electrolyte secondary battery |
| JP4599051B2 (en) * | 2003-11-11 | 2010-12-15 | 株式会社東芝 | Square non-aqueous electrolyte secondary battery |
| JP4319025B2 (en) * | 2003-12-25 | 2009-08-26 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
| JP5254825B2 (en) * | 2009-01-29 | 2013-08-07 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
| JP5215978B2 (en) | 2009-10-28 | 2013-06-19 | 信越化学工業株式会社 | Anode material for non-aqueous electrolyte secondary battery, method for producing the same, and lithium ion secondary battery |
| JP6865596B2 (en) * | 2016-03-31 | 2021-04-28 | マクセルホールディングス株式会社 | Lithium secondary battery |
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| JP3177299B2 (en) * | 1992-05-15 | 2001-06-18 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
| JPH07235327A (en) * | 1993-12-27 | 1995-09-05 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte secondary battery |
| JP3249305B2 (en) * | 1994-08-25 | 2002-01-21 | 三洋電機株式会社 | Non-aqueous electrolyte battery |
| JPH08335465A (en) * | 1995-04-01 | 1996-12-17 | Sony Corp | Nonaqueous electrolytic battery |
| JPH0950823A (en) * | 1995-06-01 | 1997-02-18 | Ricoh Co Ltd | Secondary battery |
| JPH09147814A (en) * | 1995-11-22 | 1997-06-06 | Shin Kobe Electric Mach Co Ltd | Organic electrolyte battery |
| JP3684561B2 (en) * | 1996-08-20 | 2005-08-17 | 日本電池株式会社 | battery |
| JP3349399B2 (en) * | 1996-11-01 | 2002-11-25 | 三洋電機株式会社 | Lithium secondary battery |
| JP4166295B2 (en) * | 1997-03-27 | 2008-10-15 | ソニー株式会社 | Non-aqueous electrolyte battery |
| JP3030263B2 (en) * | 1997-05-09 | 2000-04-10 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
| JP4056117B2 (en) * | 1997-12-17 | 2008-03-05 | 三洋電機株式会社 | Lithium secondary battery |
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