JP2008310981A - Lithium ion polymer battery - Google Patents
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- 229920000642 polymer Polymers 0.000 title claims abstract description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 60
- 239000012528 membrane Substances 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 150000002500 ions Chemical class 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 22
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims abstract description 20
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 17
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 15
- 229920000620 organic polymer Polymers 0.000 claims abstract description 15
- 229920002635 polyurethane Polymers 0.000 claims abstract description 14
- 239000004814 polyurethane Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000003541 multi-stage reaction Methods 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical group [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000007784 solid electrolyte Substances 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000010408 film Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012424 LiSO 3 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
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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
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
【課題】 原料化合物としていずれも公知のものを使用したイオン伝導性に優れた、ボロン‐高分子複合電解質膜およびそれを使用したリチウムイオンポリマー電池を提供すること。
【解決手段】 有機ホウ素化合物、ポリエチレンオキシド系の酸素原子含有有機高分子化合物、アルカリ金属電解質塩、およびポリウレタンから成るイオン伝導性ボロン‐高分子複合電解質膜。複合反応生成物の組成が、有機ホウ素化合物とポリエチレンオキシド系の酸素原子含有有機高分子化合物をモル比で０．５〜３：３、アルカリ金属電解質塩を前記酸素原子含有有機高分子化合物が含有する酸素原子とアルカリ金属原子のモル比で５〜２０：１になるように含む。電解質に対してポリウレタン５〜４０ｗｔ％を添加する。前記酸素原子含有有機高分子化合物が、ポリアルキレンオキシドに、ポリアルキレンオキシドの両末端をメトキシドで置換したポリアルキレンオキシドジメチルエーテルを添加したものである。常温におけるイオン伝導度が１０−３Ｓ/ｃｍ以上である。上記イオン伝導性ボロン‐高分子複合電解質膜を用いたリチウムイオンポリマー電池。
【選択図】 なしPROBLEM TO BE SOLVED: To provide a boron-polymer composite electrolyte membrane excellent in ion conductivity using a known compound as a raw material compound and a lithium ion polymer battery using the same.
An ion conductive boron-polymer composite electrolyte membrane comprising an organic boron compound, a polyethylene oxide-based oxygen atom-containing organic polymer compound, an alkali metal electrolyte salt, and polyurethane. The composition of the composite reaction product is an organic boron compound and a polyethylene oxide-based oxygen atom-containing organic polymer compound in a molar ratio of 0.5 to 3: 3, and the alkali metal electrolyte salt contains the oxygen atom-containing organic polymer compound. The molar ratio of oxygen atoms to alkali metal atoms is 5 to 20: 1. Add 5-40 wt% of polyurethane to the electrolyte. The oxygen atom-containing organic polymer compound is obtained by adding polyalkylene oxide dimethyl ether in which both ends of polyalkylene oxide are substituted with methoxide to polyalkylene oxide. The ionic conductivity at room temperature is 10 −3 S / cm or more. A lithium ion polymer battery using the ion conductive boron-polymer composite electrolyte membrane.
[Selection figure] None
Description
本発明は、常温において高いイオン伝導性と機械的強度が優れているボロン‐高分子複合電解質膜に関するものである。 The present invention relates to a boron-polymer composite electrolyte membrane having high ionic conductivity and excellent mechanical strength at room temperature.
固体電解質膜を用いる電気化学素子は、薄膜小型で製造できるので、携帯用電気製品、自動車などに利用される。特に、固体重合体電解質薄膜は、高い充放電効率を有する種々な型の電池形態が可能な化学電池を提供することができ、かつ軽量であることなどから、研究・開発の注目を集めている。 An electrochemical device using a solid electrolyte membrane can be manufactured in a small thin film, and is therefore used in portable electric products, automobiles, and the like. In particular, solid polymer electrolyte thin films are attracting the attention of research and development because they can provide chemical batteries capable of various types of battery configurations having high charge / discharge efficiency and are lightweight. .
小型、薄型で高出力の二次電池を実現するイオン伝導性高分子電解質には(１)金属塩がイオン解離することによって生成する金属イオンが動きやすいこと、すなわち高いイオン導電率を有することと、(２)自立性薄膜が形成でき、その薄膜が圧縮や引っ張りの力に対して充分な耐性があること、すなわち力学的強度が高いこと、の条件が重要である。これらのことから、高イオン伝導度、高強度を兼ね備えた、性能の優れた固体電解質の開発が望まれ、精力的な検討が進められて来た。その主流はポリエチレンオキシド系の酸素原子含有有機高分子化合物であるが、その室温でのイオン伝導度は液体電解質と比較すると低く、１０−４〜１０−５Ｓ/ｃｍ程度が限界である。また、高分子化合物に液体成分（溶媒）を含有させたゲルタイプの電解質の開発も同時に進められており、そのイオン伝導度は含有する溶媒にも依存するが、多量に含有可能な高分子の場合、１０−３Ｓ/ｃｍ以上の実用化可能なレベルの報告もある。しかしこれらのゲル電解質の場合、溶媒の含浸による強度低下、加圧力が作用すると溶媒の浸出等の問題がある。 The ion-conductive polymer electrolyte that realizes a small, thin, and high-power secondary battery has the following features: (1) metal ions generated by ion dissociation of metal salts are easy to move, that is, have high ionic conductivity. (2) The condition that a self-supporting thin film can be formed and that the thin film is sufficiently resistant to compression and tension, that is, has high mechanical strength, is important. For these reasons, development of a solid electrolyte having high ion conductivity and high strength and excellent performance has been desired, and energetic studies have been advanced. Its main stream is an oxygen atom-containing organic polymer compound polyethylene oxide-based, the ionic conductivity at room temperature is lower when compared to liquid electrolytes, approximately 10 -4 ~10 -5 S / cm is the limit. In addition, the development of gel-type electrolytes in which a liquid component (solvent) is contained in a polymer compound is also underway, and the ionic conductivity depends on the solvent contained, but a polymer that can be contained in large quantities. In some cases, there is a report of a practical level of 10 −3 S / cm or more. However, in the case of these gel electrolytes, there are problems such as a decrease in strength due to the impregnation of the solvent and leaching of the solvent when a pressure is applied.
このゲル電解質の強度的な欠点を改良する方法として、高分子化合物の微多孔膜、不織布、織物等の強度を有する基布に固体電解質を塗布、含浸する方法が種々提案されている。これらの案の場合、用いる基布は主としてポリオレフィン系であるため耐熱、強度的にも限界があり、また高分子化合物の含浸、塗布にも技術的困難性がある。前記の欠点を改良した方法として、基布に全芳香属ポリアミドであるアラミド繊維を用いる方法が特許文献１に提案されている。しかし当方法では得られる電解質膜の厚みは４０〜５０μｍが限界と思われる。 As a method for improving the strength defect of the gel electrolyte, various methods for applying and impregnating a solid electrolyte to a base fabric having a strength such as a microporous film of a polymer compound, a nonwoven fabric or a woven fabric have been proposed. In these cases, since the base fabric used is mainly polyolefin, there are limits in heat resistance and strength, and there are technical difficulties in impregnation and coating of the polymer compound. As a method for improving the above drawbacks, Patent Document 1 proposes a method of using an aramid fiber, which is a wholly aromatic polyamide, as a base fabric. However, the thickness of the electrolyte membrane obtained by this method seems to be limited to 40 to 50 μm.
また、ウレタン結合を有するオキシアルキレン基を含有する（メタ）アクリレートモノマー混合物を用いた重合体及び電解質からなる複合体を用いたイオン伝導性の高分子固体電解質が特許文献２で提案されている。この高分子固体電解質のイオン伝導度は、溶媒未添加で１０-4Ｓ/ｃｍ（室温）であり高いレベルであるが、さらに溶媒を添加すると、室温またはそれより低温であっても１０-3Ｓ/ｃｍ以上となり、また膜質も厚膜であれば自立膜として得られる程度に改善された。また、このモノマーは重合性が良好で、電池や電気二重層コンデンサに応用する場合、モノマー状態で電池や電気二重層コンデンサに組込んだ後に重合し、固体化できるという加工上のメリットもあった。しかしながら、数十μｍ程度の薄膜にした場合における膜強度の点、及び電気二重層コンデンサや電池に応用した際の短絡のしやすさの点で改善の余地が残されていた。 Further, Patent Document 2 proposes an ion conductive polymer solid electrolyte using a polymer and a composite comprising an (meth) acrylate monomer mixture containing an oxyalkylene group having a urethane bond and an electrolyte. The ionic conductivity of this polymer solid electrolyte is 10 −4 S / cm (room temperature) with no solvent added, which is a high level, but when a solvent is further added, it is 10 −3 at room temperature or lower. If the film quality is S / cm or more and the film quality is thick, it is improved to the extent that it can be obtained as a free-standing film. In addition, this monomer has good polymerizability, and when applied to a battery or an electric double layer capacitor, it has a processing advantage that it can be polymerized and solidified after being incorporated in the battery or electric double layer capacitor in a monomer state. . However, there remains room for improvement in terms of film strength when thin films of about several tens of μm and ease of short circuits when applied to electric double layer capacitors and batteries.
このように固体化学電池の製造において、最近では電解質として重合体を用いる方法が開発されているが、これまでの重合体電解質膜は、重合体薄膜の製造時、完全非結晶性の薄膜を製造し難く、製造された重合体薄膜の機械的強度の弱さ、イオン伝導度が温度によって大きく変わり、常温におけるイオン伝導度が経時により差が出たり、また、重合体主鎖に置換されている側鎖の運動によりイオンが移動していくため、イオン伝導が遅くなったり、電池や固体電気化学素子に応用するのに問題があった。
イオン伝導性と機械的物性の両者を共に向上させるための新たな電解質の開発が強く望まれている。
特許文献３と非特許文献１では、シリカやボロン−高分子複合電解質を作製したが、複合反応を進行する際に水分が生成し、特にリチウム電池の電解質として相応しくない。
In this way, in the production of solid state chemical batteries, recently, a method using a polymer as an electrolyte has been developed, but the conventional polymer electrolyte membrane produces a completely non-crystalline thin film when producing a polymer thin film. Difficult to do so, weakness of mechanical strength of polymer thin film produced, ionic conductivity varies greatly with temperature, ionic conductivity at room temperature varies with time, and polymer main chain is substituted Since ions move due to the movement of the side chain, ion conduction is slow, and there are problems in application to batteries and solid electrochemical devices.
Development of a new electrolyte for improving both ion conductivity and mechanical properties is strongly desired.
In Patent Document 3 and Non-Patent Document 1, silica or boron-polymer composite electrolyte was produced. However, when the composite reaction proceeds, moisture is generated, which is not particularly suitable as an electrolyte for a lithium battery.
電池及びコンデンサにおける高分子固体電解質層は、イオン移動だけを担っており、薄くすればするほど電池及びコンデンサ全体の体積を薄くでき、電池、コンデンサのエネルギー密度を高くすることができる。また、高分子固体電解質層を薄くすれば、電池及びコンデンサの電気抵抗を低下でき、取り出し電流、充電電流を増加でき、電池のパワー密度を向上させることができる。従って、できるだけ膜強度が良好で、薄膜化できる高イオン伝導度の高分子固体電解質が望まれていた。 The polymer solid electrolyte layer in the battery and the capacitor is responsible only for ion migration, and the thinner the volume, the thinner the volume of the battery and the capacitor, and the higher the energy density of the battery and the capacitor. If the polymer solid electrolyte layer is thinned, the electric resistance of the battery and the capacitor can be reduced, the extraction current and the charging current can be increased, and the power density of the battery can be improved. Accordingly, there has been a demand for a polymer solid electrolyte having as high a membrane strength as possible and having a high ion conductivity that can be made thin.
本発明は、原料化合物としていずれも公知のものを使用した高性能な複合電解質、特にイオン伝導性に優れた、ボロン‐高分子複合電解質膜およびそれを使用したリチウムイオンポリマー電池を提供することを目的としている。 The present invention provides a high-performance composite electrolyte using known materials as raw material compounds, particularly a boron-polymer composite electrolyte membrane excellent in ion conductivity and a lithium ion polymer battery using the same. It is aimed.
ポリエチレンオキシド、ポリプロピレンオキシド、ポリウレタンなどの高分子マトリックスについて研究した結果、それらから製造されるイオン伝導性を有するボロン‐高分子複合膜が、重合体由来の優れた機械的特性を示すとともに高いイオン伝導性を示すことを見出し、本発明を完成するに至った。 As a result of research on polymer matrices such as polyethylene oxide, polypropylene oxide, and polyurethane, boron-polymer composite membranes with ion conductivity produced from them exhibit excellent mechanical properties and high ionic conductivity derived from polymers. As a result, the present invention has been completed.
すなわち、本発明は、以下の（１）〜（５）に記載のイオン伝導性ボロン‐高分子複合電解質膜を要旨とする。
（１）有機ホウ素化合物、ポリエチレンオキシド系の酸素原子含有有機高分子化合物、アルカリ金属電解質塩、およびポリウレタンから成るイオン伝導性ボロン‐高分子複合電解質膜。
（２）複合反応生成物の組成が、有機ホウ素化合物とポリエチレンオキシド系の酸素原子含有有機高分子化合物をモル比で０．５〜３：３、アルカリ金属電解質塩をポリエチレンオキシド系の酸素原子含有有機高分子化合物が含有する酸素原子とアルカリ金属原子のモル比で５〜２０：１になるように含む（１）に記載のイオン伝導性ボロン‐高分子複合電解質膜。
（３）電解質に対してポリウレタン５〜４０ｗｔ％を添加する（１）または（２）に記載のイオン伝導性ボロン‐高分子複合電解質膜。
（４）ポリエチレンオキシド系の酸素原子含有有機高分子化合物が、ポリアルキレンオキシドに、ポリアルキレンオキシドの両末端をメトキシドで置換したポリアルキレンオキシドジメチルエーテルを添加したものである（１）、（２）または（３）に記載のイオン伝導性ボロン‐高分子複合電解質膜。
（５）常温におけるイオン伝導度が１０−３Ｓ/ｃｍ以上である（1）ないし （4）のいずれかに記載のイオン伝導性ボロン‐高分子複合電解質膜。
That is, the gist of the present invention is the ion conductive boron-polymer composite electrolyte membrane described in the following (1) to (5).
(1) An ion conductive boron-polymer composite electrolyte membrane comprising an organic boron compound, a polyethylene oxide-based organic polymer compound containing oxygen atoms, an alkali metal electrolyte salt, and polyurethane.
(2) The composition of the composite reaction product is 0.5 to 3: 3 in molar ratio of the organic boron compound and the polyethylene oxide-based organic polymer compound containing polyethylene oxide, and the alkali metal electrolyte salt contains a polyethylene oxide-based oxygen atom. The ion conductive boron-polymer composite electrolyte membrane according to (1), which is included so that the molar ratio of oxygen atoms to alkali metal atoms contained in the organic polymer compound is 5 to 20: 1.
(3) The ion conductive boron-polymer composite electrolyte membrane according to (1) or (2), wherein 5 to 40 wt% of polyurethane is added to the electrolyte.
(4) The polyethylene oxide-based oxygen atom-containing organic polymer compound is obtained by adding polyalkylene oxide dimethyl ether in which both ends of polyalkylene oxide are substituted with methoxide to polyalkylene oxide (1), (2) or The ion conductive boron-polymer composite electrolyte membrane according to (3).
(5) The ion conductive boron-polymer composite electrolyte membrane according to any one of (1) to (4), wherein the ion conductivity at room temperature is 10 −3 S / cm or more.
また、本発明は、以下の（６）に記載のリチウムイオンポリマー電池を要旨とする。
（６）（1）ないし（５）のいずれかに記載のイオン伝導性ボロン‐高分子複合電解質膜を用いたリチウムイオンポリマー電池。
Moreover, this invention makes a summary the lithium ion polymer battery as described in the following (6).
(6) A lithium ion polymer battery using the ion conductive boron-polymer composite electrolyte membrane according to any one of (1) to (5).
本発明によれば、高いイオン伝導度を示し、電気化学的に安定し、機械的強度も良好なイオン伝導性ボロン‐高分子複合電解質膜を提供することができる。該イオン伝導性ボロン‐高分子複合電解質膜のイオン伝導度は常温で１０−３Ｓ/ｃｍであるために、特にリチウムイオン電池および固体電気化学素子等に応用することができる。 According to the present invention, it is possible to provide an ion conductive boron-polymer composite electrolyte membrane that exhibits high ionic conductivity, is electrochemically stable, and has good mechanical strength. Since the ion conductivity of the ion conductive boron-polymer composite electrolyte membrane is 10 −3 S / cm at room temperature, it can be applied particularly to lithium ion batteries and solid electrochemical devices.
本発明は有機ホウ素化合物、ポリエチレンオキシド系の酸素原子含有有機高分子化合物、アルカリ金属電解質塩、およびポリウレタンの複合反応生成物を用いたイオン伝導性有機‐無機複合電解質膜である。 The present invention is an ion-conducting organic-inorganic composite electrolyte membrane using a composite reaction product of an organic boron compound, a polyethylene oxide-based oxygen-containing organic polymer compound, an alkali metal electrolyte salt, and polyurethane.
原料化合物としてはいずれも公知のものが使用できる。
［有機ホウ素化合物］
複合反応に用いられる有機ホウ素化合物としては、アルコキシボロン、好ましくはトリエトキシボロン〔B(OCH2CH3)3〕などが挙げられる。トリエトキシボロンは水素化カルシウム(CaH2)を用い、公知の乾燥方法に従って無水化した。
Any known compound can be used as the raw material compound.
[Organic boron compounds]
Examples of the organoboron compound used in the complex reaction include alkoxyboron, preferably triethoxyboron [B (OCH 2 CH 3 ) 3 ]. Triethoxyboron was dehydrated using calcium hydride (CaH 2 ) according to a known drying method.
［ポリエチレンオキシド系の酸素原子含有有機高分子化合物］
該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。またこのときイオン伝導度を向上させるため、ポリアルキレンオキシドの両末端をメトキシ置換したポリエチレンオキシドジメチルエーテル(PEODME)、ポリプロピレンオキシドジメチルエーテル(PPODME)などをポリアルキレンオキシドと等重量以上加えることが望ましい。
複合反応を進行する際には、アルコキシボロンとポリアルキレンオキシドをモル比で０．５~３：３になるように混合すればよい。アルカリ金属の最適添加量は金属塩の種類によって異なるが、アルカリ金属の添加量は通常PEOとPEODMEに含有する酸素原子とアルカリ金属原子のモル比が５〜２０：１の割合で含まれるように混合すればよい。
[Polyethylene oxide-based organic polymer compound containing oxygen atoms]
Examples of the polymer compound include polyalkylene oxide, preferably polyethylene oxide (PEO), polypropylene oxide (PPO), and the like. Further, at this time, in order to improve the ionic conductivity, it is desirable to add polyethylene oxide dimethyl ether (PEODME), polypropylene oxide dimethyl ether (PPODME) or the like having methoxy-substituted both ends of polyalkylene oxide in an amount equal to or more than that of polyalkylene oxide.
When the composite reaction proceeds, alkoxyboron and polyalkylene oxide may be mixed so that the molar ratio is 0.5 to 3: 3. The optimum addition amount of alkali metal varies depending on the type of metal salt, but the addition amount of alkali metal is usually included so that the molar ratio of oxygen atom to alkali metal atom contained in PEO and PEODME is 5 to 20: 1. What is necessary is just to mix.
［アルカリ金属電解質塩］
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である。その具体例として、LiClO4、LiBF4、LiPF6、LiSO3CF3、LiN(SO2CF3)2などである。
[Alkali metal electrolyte salt]
The electrolyte salt is an alkali metal salt, preferably a lithium salt. Specific examples thereof include LiClO 4 , LiBF 4 , LiPF 6 , LiSO 3 CF 3 , and LiN (SO 2 CF 3 ) 2 .
［ポリウレタン］
支持体としてはポリウレタン、好ましくはポリエステル系ポリウレタンエラストマー、ポリエーテル系ポリウレタンエラストマーである。電解質に対して機械的強度を増加するため５−４０ｗｔ％のポリウレタンを添加する。
[Polyurethane]
The support is polyurethane, preferably a polyester polyurethane elastomer or a polyether polyurethane elastomer. Add 5-40 wt% polyurethane to increase mechanical strength relative to electrolyte.
本発明の好ましい態様において、複合反応生成物の組成がアルコキシボロンとポリアルキレンオキシドをモル比で０．５〜３：３、ポリアルキレンオキシドとポリアルキレンオキシドジメチルエーテルを重量比１：１〜５、アルカリ金属塩がポリアルキレンオキシドに含まれる酸素原子とアルカリ金属原子のモル比が５〜２０：１の割合で含む電解質をポリウレタンとの重量比１〜９：１の混合物であり、その場合、本発明は有機ホウ素化合物、高分子化合物としてポリアルキレンオキシドとポリアルキレンオキシドジメチルエーテル、電解質塩としてアルカリ金属塩、および当該電解質の機械的強度を増加するためにポリウレタンの混合物から成る複合反応生成物を用いたイオン伝導性ボロン‐高分子複合電解質膜、好ましくは常温における伝導度が１０−３Ｓ/ｃｍ以上を示すイオン伝導性ボロン‐高分子複合電解質膜である。 In a preferred embodiment of the present invention, the composition of the composite reaction product is alkoxyboron and polyalkylene oxide in a molar ratio of 0.5 to 3: 3, polyalkylene oxide and polyalkylene oxide dimethyl ether in a weight ratio of 1: 1 to 5, alkali The metal salt is a mixture having a weight ratio of 1 to 9: 1 with polyurethane in which the molar ratio of oxygen atom to alkali metal atom contained in the polyalkylene oxide is 5 to 20: 1. In this case, the present invention Is an ion using an organic boron compound, a polyalkylene oxide and polyalkylene oxide dimethyl ether as a polymer compound, an alkali metal salt as an electrolyte salt, and a composite reaction product comprising a mixture of polyurethanes to increase the mechanical strength of the electrolyte. Conductive boron-polymer composite electrolyte membrane, preferably at room temperature A polymer composite electrolyte membrane - conductivity ion conductive boron showing the least 10 -3 S / cm.
［複合電解質膜の製造］
複合電解質膜は例えば以下の方法で製造する。複合電解質膜は、アルコキシボロンとポリアルキレンオキシドとの縮合反応生成物にアルカリ金属塩を添加した電解質溶液を、ポリウレタンを溶かしたテトラヒドロフラン(THF)溶液に加え溶媒を蒸発させることにより得られる。得られた複合電解質膜は、大気中の水分の吸着を避けるために、窒素、アルゴンなどの不活性ガス中での乾燥が好ましい。このようにして得た複合電解質膜は極めて高いイオン伝導度を有する。
[Manufacture of composite electrolyte membrane]
The composite electrolyte membrane is manufactured, for example, by the following method. The composite electrolyte membrane can be obtained by adding an electrolyte solution obtained by adding an alkali metal salt to a condensation reaction product of alkoxyboron and polyalkylene oxide to a tetrahydrofuran (THF) solution in which polyurethane is dissolved, and evaporating the solvent. The obtained composite electrolyte membrane is preferably dried in an inert gas such as nitrogen or argon in order to avoid adsorption of moisture in the atmosphere. The composite electrolyte membrane thus obtained has an extremely high ionic conductivity.
［作用］
本発明によるイオン伝導性ボロン‐高分子複合電解質膜は、溶液キャスティング等の一般的溶液コーティングの方法によるフィルム形成工程を用いて製造することができるので、薄膜を製造する工程が単純かつ経済的である利点も有している。さらに、薄膜状態での機械的強度が優れると共に、常温において高いイオン伝導特性を有するイオン伝導性ボロン‐高分子複合電解質膜製造することができ、電池、センサー、電気変色装置などの全ての電気化学素子に応用される可能性が高い。
[Action]
The ion conductive boron-polymer composite electrolyte membrane according to the present invention can be manufactured using a film forming process by a general solution coating method such as solution casting, so that the process of manufacturing a thin film is simple and economical. It also has certain advantages. Furthermore, it is possible to produce ion conductive boron-polymer composite electrolyte membranes with excellent mechanical strength in the thin film state and high ionic conductivity at room temperature, and all electrochemical such as batteries, sensors, electrochromic devices, etc. It is likely to be applied to devices.
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。 The details of the present invention will be described in Examples. The present invention is not limited to these examples.
１０ｇPEO（ポリエチレンオキシド、Ｍｎ＝４００）と２．４３ｇB(OCH2CH3)3 (トリエトキシドボロン)を混合し、一晩室温にて撹拌した。撹拌後、１０ｇPEODME（ポリエチレンオキシドジメチルエーテル、Ｍｎ＝４００）と３ｇLiN(SO2CF3)2を添加し、LiN(SO2CF3)2が完全に溶解するまで室温で撹拌した。この反応溶液３ｇを、０．５ｇポリエーテル系ポリウレタンエラストマーを溶かした２５ｇTHF（テトラヒドロフラン）溶液に加え、室温で1時間ほど撹拌した。撹拌後、シャーレに注ぎ室温アルゴン気流下で4時間、さらに８０℃減圧下で２４時間乾燥して複合電解質膜を得た。 10 g PEO (polyethylene oxide, Mn = 400) and 2.43 gB (OCH 2 CH 3 ) 3 (triethodoboron) were mixed and stirred overnight at room temperature. After stirring, 10gPEODME (polyethylene oxide dimethyl ether, Mn = 400) and 3gLiN (SO 2 CF 3) 2 was added, LiN (SO 2 CF 3) 2 was stirred at room temperature until completely dissolved. 3 g of this reaction solution was added to a 25 g THF (tetrahydrofuran) solution in which 0.5 g polyether polyurethane elastomer was dissolved, and the mixture was stirred at room temperature for about 1 hour. After stirring, it was poured into a petri dish and dried at room temperature under an argon stream for 4 hours, and further dried at 80 ° C. under reduced pressure for 24 hours to obtain a composite electrolyte membrane.
得られた電解質膜のイオン伝導度をインピーダンスアナライザで測定し、１．７×１０−３Ｓ/ｃｍという結果が得られた。この電解質膜のイオン伝導度は２００日以上経過しても１０−３Ｓ/ｃｍオーダーを維持し続けた。また、サイクリックボルタンメトリーも行い、その結果を図1に示した。電極にはリチウム金属を用いた３極セルで測定した。図１からリチウムの酸化還元反応がスムーズに進行していることが分かる。 The ionic conductivity of the obtained electrolyte membrane was measured with an impedance analyzer, and a result of 1.7 × 10 −3 S / cm was obtained. The ionic conductivity of the electrolyte membrane continued to maintain the order of 10 −3 S / cm even after 200 days. Cyclic voltammetry was also performed and the results are shown in FIG. The measurement was performed with a triode cell using lithium metal as an electrode. It can be seen from FIG. 1 that the oxidation-reduction reaction of lithium proceeds smoothly.
得られた電解質膜を用い、リチウムイオンポリマー電池を組み充放電測定を行った。正極はLiMn2O4、負極は金属リチウムを用いた。充放電は常温で、０．２ｍA/ｃｍ２の電流密度下で行った。その結果を図２に示した。比較的に高い容量と良好なサイクル特性を示した。 Using the obtained electrolyte membrane, a lithium ion polymer battery was assembled and charge / discharge measurement was performed. LiMn 2 O 4 was used for the positive electrode, and metallic lithium was used for the negative electrode. Charge and discharge at room temperature were carried out under a current density of 0.2 mA / cm 2. The results are shown in FIG. Relatively high capacity and good cycle characteristics were exhibited.
本発明のイオン伝導性ボロン‐高分子複合電解質膜は、高いイオン伝導度を示し、電気化学的に安定し、機械的強度も良好なため、リチウムイオン電池および固体電気化学素子等に応用することができる。 The ion-conducting boron-polymer composite electrolyte membrane of the present invention exhibits high ionic conductivity, is electrochemically stable, and has good mechanical strength. Therefore, it should be applied to lithium ion batteries and solid electrochemical devices. Can do.
Claims (6)
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| JP2011192618A (en) * | 2010-03-17 | 2011-09-29 | Hitachi Ltd | Lithium ion secondary battery |
| JP2013008558A (en) * | 2011-06-24 | 2013-01-10 | Sekisui Chem Co Ltd | Electrolyte and electrolyte membrane |
| US10256497B2 (en) | 2010-09-24 | 2019-04-09 | Sekisui Chemical Co., Ltd. | Electrolyte, electrolyte solution, gel electrolyte, electrolyte membrane, method for manufacturing gel electrolyte battery, and lithium ion secondary battery |
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| JP2011142017A (en) * | 2010-01-07 | 2011-07-21 | Nissan Motor Co Ltd | Lithium ion secondary battery |
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