JP3631985B2 - Ion conductive organic-inorganic composite electrolyte - Google Patents
Ion conductive organic-inorganic composite electrolyte Download PDFInfo
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- JP3631985B2 JP3631985B2 JP2001197298A JP2001197298A JP3631985B2 JP 3631985 B2 JP3631985 B2 JP 3631985B2 JP 2001197298 A JP2001197298 A JP 2001197298A JP 2001197298 A JP2001197298 A JP 2001197298A JP 3631985 B2 JP3631985 B2 JP 3631985B2
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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
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Description
【０００１】
【産業の属する技術分野】
本発明は、電池あるいはセンサー等に利用するのに十分に適したイオン伝導性有機−無機複合電解質に関するものである。
【０００２】
【従来の技術】
リチウム電池においては電解質として液体を使用している。電極間のイオンの移動速度が速いからである。しかし、電解質として液体を使用する場合、液漏れの心配がある。電解質として固体電解質を使用することで液漏れの問題を無くすことが提案されている。例えばヨウ化リチウムにゼオライトを添加した組成物よりなるリチウムイオン伝導性固体電解質（特開昭５８−１７２８０２号）、２相高分子固体電解質（特開平４−１６２３０６号）等がある。
【０００３】
これらのリチウムイオン伝導性固体電解質では、そのイオン伝導率が１０−５Ｓ／ｃｍのオーダーあるいは１０−４Ｓ／ｃｍの低いところにあり、充分なイオン移動度を得ることができないため、電池への利用には不十分である。特に、小電流型の電池では、１０−４−１０−３Ｓ／ｃｍのイオン伝導度が必要であり、さらに大電流型の電池では、１０−３Ｓ／ｃｍ以上のイオン伝導度が必要となる。
従来のリチウムイオン伝導性固体電解質においては、イオン伝導率が低く、電池として利用するのに充分な伝導度を得ることができないことから、電池あるいはセンサー等に利用するのに十分ではないという問題があった。
【０００４】
有機−無機複合材料に関する従来の研究では、有機ポリマーに無機微粒子を添加することによってポリマーのイオン伝導率を向上することが報告されている。イオン伝導率の向上は無機微粒子の添加によってポリマーの結晶性が抑制されることから説明されている。一方、イオンの拡散は界面を通して行いやすいことから、面積の大きい多孔性無機微粒子／ポリマー界面におけるイオンの高速拡散が複合電解質のイオン伝導率の向上に寄与することが期待される。
【０００５】
【発明が解決しようとする課題】
本発明は、従来技術の問題を解消するために成されたもので、固体内において伝導に寄与する溶媒和イオンが充分な移動度を有するものとして、電池あるいはセンサー等に利用するのに充分な伝導度を得ることが可能なイオン伝導性有機−無機複合電解質を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明は、無機化合物としてメソ多孔性材料、高分子化合物としてポリアルキレンオキシド、および電解質塩としてアルカリ金属塩の複合反応生成物を用いたイオン伝導性有機−無機複合電解質である。
【０００７】
メソ多孔性材料がゼオライトまたは層状粘土鉱物であり、その場合、本発明は、無機化合物としてゼオライトまたは層状粘土鉱物、高分子化合物としてポリアルキレンオキシド、および電解質塩としてアルカリ金属塩の複合反応生成物を用いたイオン伝導性有機−無機複合電解質である。
【０００８】
複合反応生成物の組成が、多孔性材料とポリアルキレンオキシドを重量比で１：０．２〜５、アルカリ金属塩２〜２０モルパーセントを含むものであり、その場合、本発明は、無機化合物としてメソ多孔性材料、より具体的にはゼオライトまたは層状粘土鉱物、高分子化合物としてポリアルキレンオキシド、および電解質塩としてアルカリ金属塩の、組成がメソ多孔性材料とポリアルキレンオキシドを重量比で１：０．２〜５、アルカリ金属塩２〜２０モルパーセントを含む複合反応生成物を用いたイオン伝導性有機−無機複合電解質である。
【０００９】
常温における伝導度が１０−３Ｓ／ｃｍ以上を示しており、その場合、本発明は、無機化合物としてメソ多孔性材料、より具体的にはゼオライトまたは層状粘土鉱物、高分子化合物としてポリアルキレンオキシド、および電解質塩としてアルカリ金属塩の複合反応生成物、より具体的には組成がメソ多孔性材料とポリアルキレンオキシドを重量比で１：０．２〜５、アルカリ金属塩２〜２０モルパーセントを含む複合反応生成物を用いた、常温における伝導度が１０−３Ｓ／ｃｍ以上を示すイオン伝導性有機−無機複合電解質である。
【００１０】
【発明の実施の形態】
原料化合物としては、いずれも公知のものが使用できる。
複合反応に用いられるメソ多孔性材料は、ゼオライトや層状粘土鉱物などがあげられる。ゼオライトとしては、ＬＴＡ型、ＦＡＵ型、ＣＨＡ型、ＭＯＲ型の少なくともいずれかの構造を有するアルミノシリケート系ゼオライトであって、ゼオライト骨格におけるＡｌ／Ｓｉ比が１０以下であるものが好適に用いられる。このうち、ＬＴＡ型のものとしては、３Ａ（Ｋ−Ａ）型や４Ａ（Ｎａ−Ａ）型、あるいは５（Ｃａ−Ａ）型のものが好適に用いられ、ＦＡＵ型のものとしては、Ｘ（Ｎａ−Ｘ）型もしくはＹ（Ｎａ−Ｙ）型のものが好適に用いられる。使用するゼオライトは用いる高分子の形態や分子量によって選択できるが、複合反応に用いたポリエチレンオキシド（ＰＥＯ）を界面活性剤として合成したゼオライトが好ましい。すなわち、ゼオライト骨格におけるＡｌ／Ｓｉ比が１０以下であれば、一般的に親水性であり、低水分圧下での吸着特性に優れるため好ましい。
【００１１】
高分子化合物としては、ポリアルキレンオキシド、好ましくはポリエチレンオキシド（ＰＥＯ）、ポリプロピレンオキシド（ＰＰＯ）などである。
複合反応を進行する際には、多孔性材料とポリアルキレンオキシドを重量比で１：０．２〜１０、好ましくは０．５〜２となるように混合すればよい。
アルカリ金属塩の添加量は、ＰＥＯに対して０〜２０モルパーセント、好ましくは２〜２０モル％の量で含まれる。
【００１２】
電解質塩としてはアルカリ金属塩、好ましくはリチウム塩、その具体例として過塩素酸リチウム（ＬｉＣｌＯ４）、テトラフルオロホウ酸リチウム（ＬｉＢＦ４）、ヘキサフルオロリン酸リチウム（ＬｉＰＦ６）、トリフルオロメタンスルホン酸リチウム（ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＣＦ３ＳＯ２）２）などがある。リチウム塩の含量は、高分子固体電解質において使用する通常的な水準である。
【００１３】
【作用】
有機−無機複合材料に関する従来の研究では、有機ポリマーに無機微粒子を添加することによってポリマーのイオン伝導率を向上することが報告されている。本発明では、多孔性の無機微粒子にポリマーを吸着させることによってポリマーの結晶性が抑制され、イオン伝導率が向上させることができる。用いる多孔性の無機化合物にＰＥＯの分子鎖の一部あるいはその全体を吸着させれば、ＰＥＯ分子鎖が無機微粒子中に固定され、ポリマーの結晶性が確実に抑制できる。更に、低分子で液状のＰＥＯの場合には、ポリマーの無機微粒子の細孔への吸着によって複合電解質固化体を作製することが可能になる。
【００１４】
一方、イオンの拡散は界面を通して行いやすいことから、面積の大きい多孔性無機微粒子／ポリマー界面におけるイオンの高速拡散が複合電解質のイオン伝導率の向上に寄与することが期待される。すなわち、通常の溶液中におけるイオン導電を無機微粒子のような大きな空孔を有する固体中で行なうことにより、固体内において導電に寄与する溶媒和イオンが充分な移動度を有し、電池あるいはセンサー等に利用するのに充分な伝導度を得ることができる。
即ち、この複合電解質のイオン伝導率を向上させる効果としてはポリマーの結晶性の抑制と界面におけるイオンの高速移動の両方にある。
従って、本発明のリチウムイオンを含むアルミノ珪酸塩よりなるリチウムイオン伝導性固体電解質においては、アルミノ珪酸塩中のすなわち固体内で溶媒和したリチウムイオンが導電に寄与し、かつ十分な移動度を持たせることができるという性質を有するため、極めて良好な固体電解質となる。
【００１５】
【実施例】
本願発明の詳細を実施例で説明する。本願発明はこれら実施例によって何ら限定されるものではない。
【００１６】
実施例１
ゼオライトは市販のＦ−９（組成式：ＮＡ２Ｏ・Ａｌ２Ｏ３・２．５ＳｉＯ２）を１６０℃で真空乾燥したものを使用した。
一方、分子量２００のＰＥＯ １５ｇを注入した二つのビーカーにＬｉＳＯ３ＣＦ３ １．５ｇを溶解したＰＥＯ−ＬｉＳＯ３ＣＦ３溶液を調整した。
ＰＥＯ−ＬｉＳＯ３ＣＦ３溶液とＦ−９を重量比で２：１混合した。その後、真空で一日保持した。
得られた複合電解質をローラプレスで成膜した後イオン伝導率を測定した。インピーダンスアナライザで測定した結果を図１に示す。Ｌｉイオン伝導率は３．５×１０−３Ｓ／ｃｍである。
【００１７】
実施例２
ゼオライトＦ−９ １０ｇを２Ｍ ＬｉＮＯ３中に２日間撹拌し、Ｎａ＋／Ｌｉ＋イオン交換反応を進行することによってＬｉ型Ｆ−９を作製した。
実施例１と同様な方法で作製したＰＥＯ−ＬｉＳＯ３ＣＦ３溶液１．２ｇにＬｉ型Ｆ−９ １ｇを添加し、乳鉢で混合した後、室温で真空一日処理した。
得られた複合電解質をローラプレスで製膜し、そのイオン伝導率をインピーダンスアナライザで測定した。得られた測定結果を図２に示す。Ｌｉイオン伝導率は１．４×１０−３Ｓ／ｃｍである。
【００１８】
【発明の効果】
電池あるいはセンサー等に利用するのに充分な伝導度を得ることが可能なイオン伝導性有機−無機複合電解質を提供することができる。
【図面の簡単な説明】
【図１】実施例１のゼオライト−ＰＥＯ−ＬｉＳＯ３ＣＦ３複合電解質のインピーダンスアナライザ分析結果を示す図面である。
【図２】実施例２のＬｉ型ゼオライト−ＰＥＯ−ＬｉＳＯ３ＣＦ３複合電解質のインピーダンスアナライザ分析結果を示す図面である。[0001]
[Technical field to which industry belongs]
The present invention relates to an ion conductive organic-inorganic composite electrolyte that is sufficiently suitable for use in a battery, a sensor, or the like.
[0002]
[Prior art]
Lithium batteries use liquid as the electrolyte. This is because the moving speed of ions between the electrodes is fast. However, when a liquid is used as the electrolyte, there is a risk of liquid leakage. It has been proposed to eliminate the problem of liquid leakage by using a solid electrolyte as the electrolyte. For example, there are a lithium ion conductive solid electrolyte (Japanese Patent Laid-Open No. 58-172802) and a two-phase polymer solid electrolyte (Japanese Patent Laid-Open No. Hei 4-162306) made of a composition obtained by adding zeolite to lithium iodide.
[0003]
In these lithium ion conductive solid electrolytes, the ion conductivity is in the order of 10-5 S / cm or as low as 10-4 S / cm, and sufficient ion mobility cannot be obtained. It is insufficient for use. In particular, a small current type battery requires an ion conductivity of 10 −4 -10 −3 S / cm, and a large current type battery requires an ion conductivity of 10 −3 S / cm or more. Become.
The conventional lithium ion conductive solid electrolyte has a low ionic conductivity and cannot obtain sufficient conductivity for use as a battery, so that it is not sufficient for use in a battery or a sensor. there were.
[0004]
Previous studies on organic-inorganic composite materials have reported improving the ionic conductivity of polymers by adding inorganic particulates to organic polymers. The improvement in ionic conductivity is explained by the fact that the crystallinity of the polymer is suppressed by the addition of inorganic fine particles. On the other hand, since ion diffusion is easy to be performed through the interface, high-speed ion diffusion at the porous inorganic fine particle / polymer interface having a large area is expected to contribute to improvement of the ionic conductivity of the composite electrolyte.
[0005]
[Problems to be solved by the invention]
The present invention has been made to solve the problems of the prior art, and solvated ions contributing to conduction in a solid have sufficient mobility, and are sufficient for use in batteries or sensors. It is an object to provide an ion conductive organic-inorganic composite electrolyte capable of obtaining conductivity.
[0006]
[Means for Solving the Problems]
The present invention is an ion conductive organic-inorganic composite electrolyte using a mesoporous material as an inorganic compound, a polyalkylene oxide as a polymer compound, and a composite reaction product of an alkali metal salt as an electrolyte salt.
[0007]
The mesoporous material is a zeolite or a lamellar clay mineral, in which case the present invention provides a complex reaction product of a zeolite or lamellar clay mineral as an inorganic compound, a polyalkylene oxide as a polymer compound, and an alkali metal salt as an electrolyte salt. It is the ion conductive organic-inorganic composite electrolyte used.
[0008]
The composition of the composite reaction product includes a porous material and a polyalkylene oxide in a weight ratio of 1: 0.2 to 5, and 2 to 20 mole percent of an alkali metal salt. As a mesoporous material, more specifically, a zeolite or a layered clay mineral, a polyalkylene oxide as a polymer compound, and an alkali metal salt as an electrolyte salt, the composition of the mesoporous material and the polyalkylene oxide is 1: An ion conductive organic-inorganic composite electrolyte using a composite reaction product containing 0.2 to 5 and 2 to 20 mole percent of an alkali metal salt.
[0009]
The conductivity at normal temperature is 10 −3 S / cm or more. In that case, the present invention is a mesoporous material as an inorganic compound, more specifically, a zeolite or layered clay mineral, and a polyalkylene oxide as a polymer compound. , and complex reaction product of the alkali metal salt as an electrolyte salt, the more mesoporous material composition specifically and polyalkylene oxide in a weight ratio of 1: 0.2-5, 2 20 mol percent alkali metal salt It is an ion conductive organic-inorganic composite electrolyte having a conductivity at room temperature of 10 −3 S / cm or more, using a composite reaction product.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Any known compound can be used as the raw material compound.
Examples of the mesoporous material used for the composite reaction include zeolite and layered clay mineral. As the zeolite, an aluminosilicate zeolite having at least one of the LTA type, FAU type, CHA type, and MOR type structure having an Al / Si ratio of 10 or less in the zeolite skeleton is preferably used. Of these, 3A (KA), 4A (Na-A), or 5 (Ca-A) types are preferably used as LTA types, and X (Na-X) type or Y (Na-Y) type is preferably used. The zeolite to be used can be selected depending on the form and molecular weight of the polymer to be used, but zeolite synthesized using polyethylene oxide (PEO) used for the complex reaction as a surfactant is preferable. That is, if the Al / Si ratio in the zeolite skeleton is 10 or less, it is generally preferable because it is hydrophilic and has excellent adsorption characteristics under a low water pressure.
[0011]
Examples of the polymer compound include polyalkylene oxide, preferably polyethylene oxide (PEO) and polypropylene oxide (PPO).
When the composite reaction proceeds, the porous material and the polyalkylene oxide may be mixed so that the weight ratio is 1: 0.2 to 10, preferably 0.5 to 2.
The addition amount of the alkali metal salt is from 0 to 20 mole percent relative to PEO, preferably contained in an amount of 2 to 20 mol%.
[0012]
The electrolyte salt is an alkali metal salt, preferably a lithium salt, and specific examples thereof are lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), trifluoromethanesulfonic acid. Examples include lithium (LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 ). The lithium salt content is a normal level used in polymer solid electrolytes.
[0013]
[Action]
Previous studies on organic-inorganic composite materials have reported improving the ionic conductivity of polymers by adding inorganic particulates to organic polymers. In the present invention, by adsorbing the polymer to the porous inorganic fine particles, the crystallinity of the polymer can be suppressed and the ionic conductivity can be improved. If a part or the whole of the PEO molecular chain is adsorbed to the porous inorganic compound to be used, the PEO molecular chain is fixed in the inorganic fine particles, and the crystallinity of the polymer can be reliably suppressed. Furthermore, in the case of low molecular and liquid PEO, a composite electrolyte solidified body can be produced by adsorption of polymer fine particles into the pores.
[0014]
On the other hand, since ion diffusion is easy to be performed through the interface, high-speed ion diffusion at the porous inorganic fine particle / polymer interface having a large area is expected to contribute to improvement of the ionic conductivity of the composite electrolyte. That is, by conducting ionic conduction in a normal solution in a solid having large vacancies such as inorganic fine particles, the solvated ions contributing to the conduction in the solid have sufficient mobility, and the battery or sensor, etc. It is possible to obtain a sufficient conductivity for use in the above.
In other words, the effect of improving the ionic conductivity of the composite electrolyte is both the suppression of the crystallinity of the polymer and the rapid movement of ions at the interface.
Therefore, in the lithium ion conductive solid electrolyte made of an aluminosilicate containing lithium ions of the present invention, lithium ions solvated in the aluminosilicate, that is, in the solid contribute to conduction and have sufficient mobility. Therefore, it becomes a very good solid electrolyte.
[0015]
【Example】
The details of the present invention will be described in Examples. The present invention is not limited to these examples.
[0016]
Example 1
The zeolite used was a commercially available F-9 (composition formula: NA 2 O · Al 2 O 3 · 2.5SiO 2 ) vacuum-dried at 160 ° C.
Meanwhile, a PEO-LiSO 3 CF 3 solution prepared by dissolving 1.5 g of LiSO 3 CF 3 in two beakers into which 15 g of PEO having a molecular weight of 200 was injected was prepared.
The PEO-LiSO 3 CF 3 solution and F-9 were mixed at a weight ratio of 2: 1. Thereafter, it was kept in a vacuum for a day.
The resulting composite electrolyte was formed into a film with a roller press, and the ionic conductivity was measured. The results measured with the impedance analyzer are shown in FIG. Li ion conductivity is 3.5 × 10 −3 S / cm.
[0017]
Example 2
Li-type F-9 was produced by stirring 10 g of zeolite F-9 in 2M LiNO 3 for 2 days and proceeding with Na + / Li + ion exchange reaction.
1 g of Li-type F-9 was added to 1.2 g of the PEO-LiSO 3 CF 3 solution prepared in the same manner as in Example 1, mixed in a mortar, and then treated at room temperature for one day in a vacuum.
The obtained composite electrolyte was formed into a film with a roller press, and its ionic conductivity was measured with an impedance analyzer. The obtained measurement results are shown in FIG. Li ion conductivity is 1.4 × 10 −3 S / cm.
[0018]
【The invention's effect】
It is possible to provide an ion conductive organic-inorganic composite electrolyte capable of obtaining a sufficient conductivity for use in a battery or a sensor.
[Brief description of the drawings]
1 is a drawing showing the results of an impedance analyzer analysis of a zeolite-PEO-LiSO 3 CF 3 composite electrolyte of Example 1. FIG.
2 is a drawing showing impedance analyzer analysis results of Li-type zeolite-PEO-LiSO 3 CF 3 composite electrolyte of Example 2. FIG.
Claims (4)
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| JP2001197298A JP3631985B2 (en) | 2001-06-28 | 2001-06-28 | Ion conductive organic-inorganic composite electrolyte |
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| JP2001197298A JP3631985B2 (en) | 2001-06-28 | 2001-06-28 | Ion conductive organic-inorganic composite electrolyte |
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| JP2003016834A JP2003016834A (en) | 2003-01-17 |
| JP3631985B2 true JP3631985B2 (en) | 2005-03-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2850301B1 (en) * | 2003-01-23 | 2007-10-19 | Commissariat Energie Atomique | ORGANIC-INORGANIC HYBRID MATERIAL COMPRISING A MESOPOROUS MINERAL PHASE AND AN ORGANIC PHASE, MEMBRANE AND FUEL CELL |
| FR2850300B1 (en) * | 2003-01-23 | 2006-06-02 | Commissariat Energie Atomique | CONDUCTIVE ORGANIC-INORGANIC HYBRID MATERIAL COMPRISING A MESOPOROUS PHASE, MEMBRANE, ELECTRODE, AND FUEL CELL |
| JP4324697B2 (en) * | 2003-05-27 | 2009-09-02 | 国立大学法人東京工業大学 | Ion conductive polymer composition |
| JP2006040853A (en) * | 2004-06-25 | 2006-02-09 | Tokyo Institute Of Technology | Ion conductive filler and ion conductive polymer composition |
| TWI368347B (en) | 2006-02-16 | 2012-07-11 | Lg Chemical Ltd | Electrode including organic/inorganic composite coating layer and electrochemical device prepared thereby |
| CN109768324A (en) * | 2019-01-22 | 2019-05-17 | 广东天劲新能源科技股份有限公司 | A method of enhancing composite solid electrolyte stability |
| RU2731364C1 (en) * | 2019-06-27 | 2020-09-02 | Федеральное государственное бюджетное образовательное учреждение высшего образования Иркутский государственный университет путей сообщения (ФГБОУ ВО ИрГУПС) | Method of producing solid electrolyte |
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| JPH08884B2 (en) * | 1990-05-30 | 1996-01-10 | 松下電器産業株式会社 | Solid electrolyte composition |
| JPH0794014A (en) * | 1993-09-28 | 1995-04-07 | Toppan Printing Co Ltd | Lithium ion conductive solid electrolyte |
| JP3717092B2 (en) * | 1997-03-27 | 2005-11-16 | Ｔｄｋ株式会社 | Solid electrolyte, lithium secondary battery and electric double layer capacitor |
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