JP4945992B2 - Ion conductive electrolyte and secondary battery using the ion conductive electrolyte - Google Patents
Ion conductive electrolyte and secondary battery using the ion conductive electrolyte Download PDFInfo
- Publication number
- JP4945992B2 JP4945992B2 JP2005288472A JP2005288472A JP4945992B2 JP 4945992 B2 JP4945992 B2 JP 4945992B2 JP 2005288472 A JP2005288472 A JP 2005288472A JP 2005288472 A JP2005288472 A JP 2005288472A JP 4945992 B2 JP4945992 B2 JP 4945992B2
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- cation
- conductive electrolyte
- ion conductive
- room temperature
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- 238000012690 ionic polymerization Methods 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- 239000011855 lithium-based material Substances 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 229910052748 manganese Chemical group 0.000 description 1
- 239000011572 manganese Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000006626 methoxycarbonylamino group Chemical group 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004676 n-butylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- BGDTWOQNFJNCKH-UHFFFAOYSA-N n-ethyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(CC)CC=C BGDTWOQNFJNCKH-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006252 n-propylcarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(*)=O 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- FDVWKHPUNHWEJY-UHFFFAOYSA-N oct-1-ene-1-sulfonic acid Chemical compound CCCCCCC=CS(O)(=O)=O FDVWKHPUNHWEJY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000004962 sulfoxyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Secondary Cells (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Conductive Materials (AREA)
Description
本発明は、イオン伝導性電解質及び該イオン伝導性電解質を使用した二次電池に関するものである。 The present invention relates to an ion conductive electrolyte and a secondary battery using the ion conductive electrolyte.
電子機器の小型軽量化やポータブル化に伴い、高電圧および高エネルギー密度などの特性を有するリチウム二次電池の研究開発が活発に行われている。特に最近のポータブル電子機器では、急速な性能向上に伴い、消費電力も急速に増大しつつある。こうした背景の中で、更なる高電圧、高エネルギー密度を実現できるようなリチウム二次電池が要求されている。
このような二次電池に対応するためには、高いイオン伝導性を発現し、広い電位範囲で電気化学的に安定であり耐電圧の高いイオン伝導性電解質が必要とされてきている。
Research and development of lithium secondary batteries having characteristics such as high voltage and high energy density have been actively conducted along with the downsizing and weight reduction of electronic devices. Particularly in recent portable electronic devices, power consumption is also rapidly increasing with rapid performance improvement. In such a background, a lithium secondary battery capable of realizing higher voltage and higher energy density is required.
In order to cope with such a secondary battery, an ion conductive electrolyte that exhibits high ion conductivity, is electrochemically stable in a wide potential range, and has a high withstand voltage has been required.
優れたイオン伝導度を実現させるために、アルキレンオキシド骨格、酸の脱プロトン残基、含窒素化合物のカチオンを有する高分子を利用する方法によって、良好なイオン伝導度を得る電解質が提案されている（例えば、特許文献１参照。）。しかしながら、ここで開示されている方法では、電解質中に占めるイオン結合部位の割合が十分ではなく、イオン伝導度向上に効果があるものの十分なイオン伝導度を実現できているとはいえなかった。
また、高いイオン伝導性を示すという理由から、二次電池、電気二重層キャパシタ等の電気化学デバイスに常温溶融塩を利用するという試みがなされている。（例えば、特許文献２参照。）。しかしながら、ここで提案されている常温溶融塩では、常温溶融塩の耐電圧が十分ではなく、高容量の二次電池などに利用するのは困難である。さらに、常温溶融塩そのものは、室温付近の温度で液状であり、二次電池に利用する際、電池の形状の自由度が狭くなり、特に、大型のリチウム二次電池への適用は困難であるという問題もあった。
そのような背景から、さらに良好なイオン伝導度を実現でき、かつ、広い電位範囲で電気化学的に安定であり耐電圧の高いイオン伝導性電解質が求められていた。
In addition, because of high ion conductivity, attempts have been made to use room temperature molten salts in electrochemical devices such as secondary batteries and electric double layer capacitors. (For example, refer to Patent Document 2). However, the room temperature molten salt proposed here does not have a sufficient withstand voltage of the room temperature molten salt and is difficult to use for a high capacity secondary battery or the like. Furthermore, the room temperature molten salt itself is in a liquid state at a temperature near room temperature, and when used in a secondary battery, the degree of freedom of the shape of the battery is narrowed, and in particular, it is difficult to apply to a large lithium secondary battery. There was also a problem.
Against this background, there has been a demand for an ion-conducting electrolyte that can realize better ion conductivity, is electrochemically stable in a wide potential range, and has a high withstand voltage.
本発明は、優れたイオン伝導度を実現でき、かつ、広い電位範囲で電気化学的に安定であり耐電圧の高いイオン伝導性電解質及びそれを用いた二次電池を提供することを目的としている。 An object of the present invention is to provide an ion conductive electrolyte that can realize excellent ionic conductivity, is electrochemically stable in a wide potential range, and has a high withstand voltage, and a secondary battery using the same. .
本発明者らは、上記の目的を達成するために鋭意検討を重ねた結果、ポリマー、リチウム塩、常温溶融塩を含むイオン伝導性電解質において、重合性官能基を有するオニウムカチオンと重合性官能基を有する有機アニオンとから構成される塩モノマー、及び、５．０V以上の耐電圧を有する常温溶融塩を用いることによって、良好なイオン伝導度を実現できつつ、広い電位範囲で電気化学的に安定であり耐電圧の高いイオン伝導性電解質が得られることを見出し、さらに検討を進めて本発明を完成させるに至った。 As a result of intensive studies in order to achieve the above object, the present inventors have determined that an onium cation having a polymerizable functional group and a polymerizable functional group in an ion conductive electrolyte containing a polymer, a lithium salt, and a room temperature molten salt. By using a salt monomer composed of an organic anion having a normal temperature and a normal temperature molten salt having a withstand voltage of 5.0 V or more, it is possible to achieve good ionic conductivity and to be electrochemically stable in a wide potential range. The present inventors have found that an ion conductive electrolyte with a high withstand voltage can be obtained, and have further studied and completed the present invention.
すなわち、
（１） ポリマー、リチウム塩および、４級アンモニウムカチオンとアニオンから構成される常温溶融塩を含むイオン伝導性電解質において、前記ポリマーが、重合性官能基を有するオニウムカチオンと重合性官能基を有する有機アニオンとから構成される塩モノマーを含んで合成されたものであり、常温溶融塩が５．０V以上の耐電圧を有し、前記常温溶融塩を構成する４級アンモニウムカチオン成分が、下記式（１）で表される４級アンモニウムカチオンであり、前記常温溶融塩を構成するアニオン成分が、下記式（２）で表されるアニオンの群から選ばれるものであることを特徴とするイオン伝導性電解質、
Ｎ + Ｒ 1 Ｒ 2 Ｒ 3 Ｒ 4 （１）
（式中、Ｒ 1 、Ｒ 2 、Ｒ 3 およびＲ 4 は、それぞれ、アルキル基、アルコキシアルキル基、アラルキル基、アリール基、アルケニル基、アラルケニル基を示し、同一であっても異なっていても良い。これらのいずれか一対又はそれ以上が環構造を形成していても良く、ヘテロ原子を含んでも良い。）
Ｎ（Ｒ 1 ＳＯ 2 ）（Ｒ 2 ＳＯ 2 ） - ， Ｎ（Ｒ 3 ＳＯ 3 ） - ， Ｃ（Ｒ 4 ＳＯ 2 ）（Ｒ 5 ＳＯ 2 ）（Ｒ 6 ＳＯ 2 ） - （２）
（式中、Ｒ 1 〜Ｒ 6 は、それぞれ、置換もしくは無置換の、アルキル基、アルコキシアルキル基、アラルキル基、アリール基、アルケニル基、アラルケニル基から選ばれる基であり、同一であっても異なっていても良く、これらは環構造を有していてもよい。また、これらはヘテロ原子を含んでもよい。）
（２） 第（１）項に記載のイオン伝導性電解質を構成要素とすることを特徴とする二次電池、
である。
That is,
(1) In an ion conductive electrolyte comprising a polymer, a lithium salt, and a room temperature molten salt composed of a quaternary ammonium cation and an anion , the polymer has an onium cation having a polymerizable functional group and an organic having a polymerizable functional group has been synthesized include composed salt monomer and an anionic, room temperature molten salt have a minimum withstand voltage 5.0V, 4 quaternary ammonium cation component constituting the ambient temperature molten salt is a compound represented by the following formula ( Ion conductivity characterized in that it is a quaternary ammonium cation represented by 1) and the anion component constituting the room temperature molten salt is selected from the group of anions represented by the following formula (2) Electrolytes,
N + R 1 R 2 R 3 R 4 (1)
(Wherein R 1 , R 2 , R 3 and R 4 each represents an alkyl group, an alkoxyalkyl group, an aralkyl group, an aryl group, an alkenyl group or an aralkenyl group, which may be the same or different. Any one or more of these may form a ring structure and may contain a hetero atom.)
N (R 1 SO 2 ) (R 2 SO 2 ) − , N (R 3 SO 3 ) − , C (R 4 SO 2 ) (R 5 SO 2 ) (R 6 SO 2 ) − (2)
Wherein R 1 to R 6 are each a substituted or unsubstituted group selected from an alkyl group, an alkoxyalkyl group, an aralkyl group, an aryl group, an alkenyl group, and an aralkenyl group. And they may have a ring structure, and they may contain heteroatoms.)
( 2 ) A secondary battery comprising the ion conductive electrolyte according to item (1) as a constituent element,
It is.
本発明によれば、優れたイオン伝導度と、広い電位範囲で電気化学的に安定であり高い耐電圧を発現するイオン伝導性電解質を提供でき、これを用いた二次電池は、良好な充放電特性を発現する。 ADVANTAGE OF THE INVENTION According to this invention, the ion conductive electrolyte which is excellent in ion conductivity and is electrochemically stable in a wide electric potential range and expresses a high withstand voltage can be provided. Expresses discharge characteristics.
本発明は、ポリマー、リチウム塩および常温溶融塩を含むイオン伝導性電解質において、前記ポリマーが、重合性官能基を有するオニウムカチオンと重合性を有する有機アニオンとから構成される塩モノマーを含んで合成されたものと、耐電圧が５．０Ｖ以上の常温溶融塩を用いることを特徴とするイオン伝導性電解質であり、これにより、優れたイオン伝導性と広い電位範囲で安定なイオン伝導性電解質が得られる。
これは、塩モノマーによりポリマー骨格中にイオン結合部位を導入しながら、また、常温溶融塩を併用することで、イオン結合濃度をさらに高めることができ、そのため、リチウム塩の解離を促進し、優れたイオン伝導度を発現するものと考えられる。また、耐電圧性に優れた常温溶融塩を用いることで広い電位範囲でイオン伝導性電解質を使用することが可能となる。塩モノマーを含んで得られるポリマーは、イオン伝導性電解質を固形化でき、電池作製の際、電池の形状の自由度を上げることが可能となる。さらに、塩モノマーを含んで得られるポリマーは、イオン性の化合物である常温溶融塩との親和性が高く、均質な固形物が得られる。
The present invention relates to an ion conductive electrolyte containing a polymer, a lithium salt, and a room temperature molten salt, wherein the polymer includes a salt monomer composed of an onium cation having a polymerizable functional group and a polymerizable organic anion. And an ion conductive electrolyte characterized by using a room temperature molten salt with a withstand voltage of 5.0 V or more, thereby providing an ion conductive electrolyte that has excellent ion conductivity and is stable in a wide potential range. can get.
This is because the ionic bond concentration can be further increased by introducing an ionic bond site into the polymer skeleton with a salt monomer and also using a room temperature molten salt. It is considered that the ionic conductivity is expressed. Moreover, it becomes possible to use an ion conductive electrolyte in a wide potential range by using a room temperature molten salt having excellent voltage resistance. The polymer obtained by including the salt monomer can solidify the ion conductive electrolyte, and can increase the degree of freedom of the shape of the battery during battery production. Furthermore, the polymer obtained by including the salt monomer has a high affinity with the room temperature molten salt that is an ionic compound, and a homogeneous solid is obtained.
本発明に用いる前記塩モノマーを構成する重合性官能基を有するオニウムカチオンとしては、フルオニウム（Ｆ+）、オキソニウム（Ｏ+）、スルホニウム（Ｓ+）、アンモニウム（Ｎ+）、ホスホニウム（Ｐ+）などがカチオン種として挙げられる。汎用性、作業性の点から、ホスホニウムカチオン、スルホニウムカチオン、アンモニウムカチオンがより好ましく、中でも、アンモニウムカチオンが最も好ましい。 Examples of the onium cation having a polymerizable functional group constituting the salt monomer used in the present invention include fluoronium (F + ), oxonium (O + ), sulfonium (S + ), ammonium (N + ), and phosphonium (P + ). Etc. are mentioned as cationic species. From the viewpoint of versatility and workability, a phosphonium cation, a sulfonium cation, and an ammonium cation are more preferable, and among them, an ammonium cation is most preferable.
前記スルホニウムカチオンとしては、具体的には、硫黄原子が３つの置換基Ｒで置換されたカチオンが挙げられる。３つの置換基Ｒの内、少なくとも一つは重合性官能基を含む基である。置換基Ｒは、置換または無置換の、アルキル基：ＣnＨ2n+1、アリール基：（Ｒ’）n−Ｃ6Ｈ5-n−、アラルキル基：（Ｒ’）m−Ｃ6Ｈ5-m−ＣnＨ2n−、アルケニル基：Ｒ’−ＣＨ＝ＣＨ−Ｒ’−、アラルケニル基：（Ｒ’）n−Ｃ6Ｈ5-n−ＣＨ＝ＣＨ−Ｒ’−、アルコキシアルキル基：Ｒ’−Ｏ−ＣnＨ2n−、アシルオキシアルキル基：Ｒ’−ＣＯＯ−ＣnＨ2n−などを例示することができる。また、置換基Ｒはヘテロ原子やハロゲン原子を含んでも良い。また、３つのＲは各々異なっても、同一であってもかまわない。前記スルホニウムカチオンで置換基Ｒにおける、Ｒ’は水素、または置換もしくは無置換の炭素数２０以下のアルキル基などであり、複数ある場合は互いに異なっても良く、ｍは１以上５以下の整数であり、ｎは１以上２０以下の整数である。Ｒ、Ｒ’において置換された場合の置換基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ネオペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基およびｎ−デシル基などの直鎖または分岐のアルキル基、シクロヘキシル基および４−メチルシクロヘキシル基などの環状のアルキル基、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、イソブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基およびｎ−ヘキシルオキシ基等の直鎖または分岐のアルコキシ基、シクロヘキシルオキシ基などの環状のアルコキシ基、メトキシメトキシ基、メトキシエトキシ基、エトキシエトキシ基、メトキシプロポキシ基、エトキシプロポキシ基、プロポキシプロポキシ基等のアルコキシアルコキシ基、フェニル基、ｐ−トリル基、ｍ−トリル基、ｏ−トリル基、ｐ−クロロフェニル基、ｍ−クロロフェニル基およびｏ−クロロフェニル基等のアリール基、フェノキシ基、ｍ−メチルフェノキシ基、ｏ−メチルフェノキシ基、ｐ−クロロフェノキシ基、ｍ−クロロフェノキシ基、ｏ−クロロフェノキシ基およびｐ−ｎ−ブチルフェノキシ基等のアリールオキシ基、フェニルチオ基、ｐ−メチルフェニルチオ基、ｍ−メチルフェニルチオ基，ｏ−メチルフェニルチオ基、ｏ−エチルフェニルチオ基、ｐ−プロピルフェニルチオ基および２，４，６−トリメチルフェニルチオ基等のアリールチオ基、メチルカルボニルアミノ基、エチルカルボニルアミノ基、ｎ−プロピルカルボニルアミノ基、イソプロピルカルボニルアミノ基およびｎ−ブチルカルボニルアミノ基等のアルキルカルボニルアミノ基、メトキシカルボニルアミノ基、エトキシカルボニルアミノ基、ｎ−プロポキシカルボニルアミノ基、イソプロポキシカルボニルアミノ基およびｎ−ブトキシカルボニルアミノ基等のアルコキシカルボニルアミノ基、メチルカルボニル基、エチルカルボニル基、ｎ−プロピルカルボニル基、イソプロピルカルボニル基およびｎ−ブチルカルボニル基等のアルキルカルボニル基、メチルカルボキシ基、エチルカルボキシ基、ｎ−プロピルカルボキシ基、イソプロピルカルボキシ基およびｎ−ブチルカルボキシ基等のアルキルカルボキシ基、メトキシカルボキシ基、エトキシカルボキシ基、ｎ−プロポキシカルボキシ基、イソプロポキシカルボキシ基およびｎ−ブトキシカルボキシ基等のアルコキシカルボキシ基、メトキシカルボニルメトキシ基、エトキシカルボニルエトキシ基、エトキシカルボニルメトキシ基、ｎ−プロポキシカルボニルメトキシ基、イソプロポキシカルボニルメトキシ基およびｎ−ブトキシカルボニルメトキシ基等のアルコキシカルボニルアルコキシ基等を挙げることができ、これらの置換基は、ハロゲン原子やヘテロ原子が含まれていても良い。さらに、前記置換基として、シアノ基や、フッ素、塩素および臭素などのハロゲン原子も挙げることができる。 Specific examples of the sulfonium cation include a cation in which a sulfur atom is substituted with three substituents R. At least one of the three substituents R is a group containing a polymerizable functional group. The substituent R is a substituted or unsubstituted alkyl group: C n H 2n + 1 , aryl group: (R ′) n —C 6 H 5-n —, aralkyl group: (R ′) m —C 6 H 5-m -C n H 2n - , alkenyl group: R'-CH = CH-R'- , aralkenyl group: (R ') n -C 6 H 5-n -CH = CH-R'-, alkoxyalkyl Group: R′—O—C n H 2n —, acyloxyalkyl group: R′—COO—C n H 2n — and the like can be exemplified. The substituent R may contain a hetero atom or a halogen atom. The three Rs may be different or the same. R ′ in the substituent R in the sulfonium cation is hydrogen or a substituted or unsubstituted alkyl group having 20 or less carbon atoms, and when there are a plurality thereof, they may be different from each other, and m is an integer of 1 or more and 5 or less. Yes, n is an integer of 1-20. Examples of the substituent when R and R ′ are substituted include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. Group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and other linear or branched alkyl groups, cyclohexyl group and 4-methylcyclohexyl group Linear or branched alkoxy such as alkyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group and n-hexyloxy group Group, cyclic alkoxy group such as cyclohexyloxy group, methoxymethoxy group, methoxyethoxy group, ethoxy group Alkoxyalkoxy groups such as ciethoxy group, methoxypropoxy group, ethoxypropoxy group, propoxypropoxy group, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-chlorophenyl group, m-chlorophenyl group and o- Aryl such as chlorophenyl, aryl such as phenoxy, m-methylphenoxy, o-methylphenoxy, p-chlorophenoxy, m-chlorophenoxy, o-chlorophenoxy and pn-butylphenoxy Oxy group, phenylthio group, p-methylphenylthio group, m-methylphenylthio group, o-methylphenylthio group, o-ethylphenylthio group, p-propylphenylthio group and 2,4,6-trimethylphenylthio An arylthio group such as a group, a methylcarbonylamino group, Alkylcarbonylamino groups such as tilcarbonylamino group, n-propylcarbonylamino group, isopropylcarbonylamino group and n-butylcarbonylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, isopropoxycarbonyl Alkoxycarbonylamino groups such as amino group and n-butoxycarbonylamino group, alkylcarbonyl groups such as methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group and n-butylcarbonyl group, methylcarboxy group, ethyl Alkylcarboxy groups such as carboxy group, n-propylcarboxy group, isopropylcarboxy group and n-butylcarboxy group, methoxycarboxy group, ethoxy group Alkoxy group such as boxy group, n-propoxycarboxy group, isopropoxycarboxy group and n-butoxycarboxy group, methoxycarbonylmethoxy group, ethoxycarbonylethoxy group, ethoxycarbonylmethoxy group, n-propoxycarbonylmethoxy group, isopropoxycarbonyl Examples thereof include alkoxycarbonylalkoxy groups such as a methoxy group and n-butoxycarbonylmethoxy group, and these substituents may contain a halogen atom or a hetero atom. Furthermore, examples of the substituent include a cyano group and halogen atoms such as fluorine, chlorine and bromine.
前記ホスホニウムカチオンとしては、具体的には、燐原子が４つの置換基Ｒで置換されたカチオンが挙げられる。４つの置換基Ｒの内、少なくとも一つは重合性官能基を含む基である。置換基Ｒは、置換または無置換の、アルキル基：ＣnＨ2n+1、アリール基：（Ｒ’）n−Ｃ6Ｈ5-n−、アラルキル基：（Ｒ’）m−Ｃ6Ｈ5-m−ＣnＨ2n−、アルケニル基：Ｒ’−ＣＨ＝ＣＨ−Ｒ’−、アラルケニル基：（Ｒ’）n−Ｃ6Ｈ5-n−ＣＨ＝ＣＨ−Ｒ’−、アルコキシアルキル基：Ｒ’−Ｏ−ＣnＨ2n−、アシルオキシアルキル基：Ｒ’−ＣＯＯ−ＣnＨ2n−などを例示することができる。また、置換基Ｒはヘテロ原子やハロゲン原子を含んでも良い。また、４つのＲは各々異なっても、同一であってもかまわない。前記ホスホニウムカチオンで置換基Ｒにおける、Ｒ’は水素、または置換もしくは無置換の炭素数２０以下のアルキル基などであり、複数ある場合は互いに異なっても良く、ｍは１以上５以下の整数であり、ｎは１以上２０以下の整数である。Ｒ、Ｒ’において置換された場合の置換基としては、上記スルホニウムカチオンにおけるそれと同じものが挙げられる。 Specific examples of the phosphonium cation include cations in which a phosphorus atom is substituted with four substituents R. At least one of the four substituents R is a group containing a polymerizable functional group. The substituent R is a substituted or unsubstituted alkyl group: C n H 2n + 1 , aryl group: (R ′) n —C 6 H 5-n —, aralkyl group: (R ′) m —C 6 H 5-m -C n H 2n - , alkenyl group: R'-CH = CH-R'- , aralkenyl group: (R ') n -C 6 H 5-n -CH = CH-R'-, alkoxyalkyl Group: R′—O—C n H 2n —, acyloxyalkyl group: R′—COO—C n H 2n — and the like can be exemplified. The substituent R may contain a hetero atom or a halogen atom. The four Rs may be different or the same. In the substituent R in the phosphonium cation, R ′ is hydrogen or a substituted or unsubstituted alkyl group having 20 or less carbon atoms, and when there are a plurality thereof, they may be different from each other, and m is an integer of 1 or more and 5 or less. Yes, n is an integer of 1-20. Examples of the substituent when substituted in R and R ′ include the same as those in the sulfonium cation.
前記アンモニウムカチオンとしては、アミン化合物から生じうるカチオンであって、アミン化合物が、脂肪族アミン化合物、芳香族アミン化合物、含窒素複素環式アミン化合物などのすべてのアミン化合物を含むことは言うまでもなく、アミンから生じる正電荷を有するのであれば、特に限定されない。具体的には、窒素原子が４つの置換基Ｒで置換されたカチオンが挙げられる。４つの官能基Ｒの内、少なくとも一つは重合性官能基を含む基である。置換基Ｒは、置換または無置換の、アルキル基：ＣnＨ2n+1、アリール基：（Ｒ’）n−Ｃ6Ｈ5-n−、アラルキル基：（Ｒ’）m−Ｃ6Ｈ5-m−ＣnＨ2n−、アルケニル基：Ｒ’−ＣＨ＝ＣＨ−Ｒ’−、アラルケニル基：（Ｒ’）n−Ｃ6Ｈ5-n−ＣＨ＝ＣＨ−Ｒ’−、アルコキシアルキル基：Ｒ’−Ｏ−ＣnＨ2n−、アシルオキシアルキル基：Ｒ’−ＣＯＯ−ＣnＨ2n−などを例示することができる。また、置換基Ｒはヘテロ原子やハロゲン原子を含んでも良い。また、４つのＲは各々異なっても、同一であってもかまわない。前記アンモニウムカチオンで置換基Ｒにおける、Ｒ’は水素、または置換もしくは無置換の炭素数２０以下のアルキル基などであり、複数ある場合は互いに異なっても良く、ｍは１以上５以下の整数であり、ｎは１以上２０以下の整数である。Ｒ、Ｒ’において置換された場合の置換基としては、上記スルホニウムカチオンにおけるそれと同じものが挙げられる。 The ammonium cation is a cation that can be generated from an amine compound, and it goes without saying that the amine compound includes all amine compounds such as aliphatic amine compounds, aromatic amine compounds, and nitrogen-containing heterocyclic amine compounds. If it has the positive charge resulting from an amine, it will not specifically limit. Specific examples include cations in which a nitrogen atom is substituted with four substituents R. At least one of the four functional groups R is a group containing a polymerizable functional group. The substituent R is a substituted or unsubstituted alkyl group: C n H 2n + 1 , aryl group: (R ′) n —C 6 H 5-n —, aralkyl group: (R ′) m —C 6 H 5-m -C n H 2n - , alkenyl group: R'-CH = CH-R'- , aralkenyl group: (R ') n -C 6 H 5-n -CH = CH-R'-, alkoxyalkyl Group: R′—O—C n H 2n —, acyloxyalkyl group: R′—COO—C n H 2n — and the like can be exemplified. The substituent R may contain a hetero atom or a halogen atom. The four Rs may be different or the same. In the substituent R in the ammonium cation, R ′ is hydrogen or a substituted or unsubstituted alkyl group having 20 or less carbon atoms, and when there are a plurality thereof, they may be different from each other, and m is an integer of 1 or more and 5 or less. Yes, n is an integer of 1-20. Examples of the substituent when substituted in R and R ′ include the same as those in the sulfonium cation.
上記アンモニウムカチオン以外のアンモニウムカチオンとしては、ピリジニウムカチオン、ピラリジニウムカチオンおよびキノリニウムカチオンなどの芳香族アンモニウムカチオン、ピロリジウムカチオン、ピペリジニウムカチオンおよびピペラジニウムカチオンなどの脂肪族複素環式アンモニウムカチオン、モルホリンカチオンのような窒素以外のヘテロ原子を含む複素環式アンモニウムカチオン、イミダゾリウムカチオンなどの不飽和の含窒素複素環式カチオンなど、のアンモニウムカチオンも挙げることができる。さらに、上記環状のアンモニウムカチオンでは窒素の位置が異なるカチオンや、環上に置換基をもったカチオンでもよく、ヘテロ原子を含む置換基を有するカチオンでもよい。 Examples of the ammonium cation other than the ammonium cation include aromatic ammonium cations such as pyridinium cation, pyraridinium cation and quinolinium cation, and aliphatic heterocyclic ammonium such as pyrrolidinium cation, piperidinium cation and piperazinium cation. Mention may also be made of ammonium cations such as cations, heterocyclic ammonium cations containing heteroatoms other than nitrogen such as morpholine cations, and unsaturated nitrogen-containing heterocyclic cations such as imidazolium cations. Further, the cyclic ammonium cation may be a cation having a different nitrogen position, a cation having a substituent on the ring, or a cation having a substituent containing a hetero atom.
前記オニウムカチオンにおける重合性官能基としては、ラジカル重合、イオン重合、配位重合およびレドックス重合などにより重合が可能な官能基であれば、何ら限定されないが、炭素−炭素二重結合を有する基が好ましく、ラジカル重合性官能基がより好ましい。前記ラジカル重合性官能基としては、活性エネルギー線もしくは熱によりラジカル重合が可能であることがより好ましい。このような官能基としては、例えば、（メタ）アクリロイル基、（メタ）アクリロイルオキシ基、（メタ）アクリルアミド基、アリル基、ビニル基、スチリル基が挙げられるが、これらの中でも、（メタ）アクリロイルオキシ基、（メタ）アクリルアミド基、スチリル基、アリル基およびビニル基が好ましい。 The polymerizable functional group in the onium cation is not particularly limited as long as it is a functional group that can be polymerized by radical polymerization, ionic polymerization, coordination polymerization, redox polymerization, or the like, but a group having a carbon-carbon double bond is available. A radical polymerizable functional group is preferable. The radical polymerizable functional group is more preferably capable of radical polymerization by active energy rays or heat. Examples of such a functional group include (meth) acryloyl group, (meth) acryloyloxy group, (meth) acrylamide group, allyl group, vinyl group, and styryl group. Among these, (meth) acryloyl group Oxy, (meth) acrylamide, styryl, allyl and vinyl groups are preferred.
前記塩モノマーを構成する重合性官能基を有するオニウムカチオンの具体例として、（メタ）アクリロイルオキシエチルトリメチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリエチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリ−ｎ−プロピルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリ−ｉｓｏ−プロピルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリ−ｎ−ブチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリ−ｉｓｏ−ブチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリ−ｔｅｒｔ−ブチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリエチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルジエチル−ｎ−ヘキシルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリデシルアンモニウムカチオン、（メタ）アクリロイルオキシエチルトリオクチルアンモニウムカチオン、（メタ）アクリロイルオキシエチルドデシルジメチルアンモニウムカチオン、（メタ）アクリロイルオキシジメチルベンジルアンモニウムカチオン、（メタ）アクリロイルオキシエチルドデシルヘキシルメチルアンモニウムカチオン、ジアリルジメチルアンモニウムカチオン、ビススチリルメチルジメチルアンモニウムカチオン、ビススチリルエチルジメチルアンモニウムカチオン、（メタ）アクリルアミドエチルトリメチルアンモニウムカチオン、（メタ）アクリルアミドプロピルトリメチルアンモニウムカチオン、（メタ）アクリルアミドエチルトリエチルアンモニウムカチオン、（メタ）アクリルアミドエチルトリ−ｎ−プロピルアンモニウムカチオン、（メタ）アクリルアミドエチルトリ−ｉｓｏ−プロピルアンモニウムカチオン、（メタ）アクリルアミドエチルトリ−ｎ−ブチルアンモニウムカチオン、（メタ）アクリルアミドエチルトリ−ｉｓｏ−ブチルアンモニウムカチオン、（メタ）アクリルアミドエチルトリ−ｔｅｒｔ−ブチルアンモニウムカチオン、（メタ）アクリルアミドエチルトリエチルアンモニウムカチオン、（メタ）アクリルアミドエチルジエチル−ｎ−ヘキシルアンモニウムカチオン、（メタ）アクリルアミドエチルトリデシルアンモニウムカチオン、（メタ）アクリルアミドエチルトリオクチルアンモニウムカチオン、（メタ）アクリルアミドエチルドデシルジメチルアンモニウムカチオン、（メタ）アクリルアミドエチルドデシルヘキシルメチルアンモニウムカチオン等の各種アンモニウムカチオン、スチリルメチルメチルピロリジニウムカチオン、ビススチリルメチルピペリジニウムカチオン、Ｎ，Ｎ’−（（メタ）アクリロイルオキシエチルメチル）ピペラジニウムカチオン、（メタ）アクリルアミドエチルメチルモルホリニウムカチオン、（メタ）アクリロイルオキシエチルメチルイミダゾリウムカチオンなどが挙げられる。 Specific examples of the onium cation having a polymerizable functional group constituting the salt monomer include (meth) acryloyloxyethyltrimethylammonium cation, (meth) acryloyloxyethyltriethylammonium cation, (meth) acryloyloxyethyltri-n-propyl. Ammonium cation, (meth) acryloyloxyethyl tri-iso-propylammonium cation, (meth) acryloyloxyethyl tri-n-butylammonium cation, (meth) acryloyloxyethyl tri-iso-butylammonium cation, (meth) acryloyloxy Ethyltri-tert-butylammonium cation, (meth) acryloyloxyethyltriethylammonium cation, (meth) acryloyloxyethyl Diethyl-n-hexylammonium cation, (meth) acryloyloxyethyltridecylammonium cation, (meth) acryloyloxyethyltrioctylammonium cation, (meth) acryloyloxyethyldodecyldimethylammonium cation, (meth) acryloyloxydimethylbenzylammonium cation (Meth) acryloyloxyethyldodecylhexylmethylammonium cation, diallyldimethylammonium cation, bisstyrylmethyldimethylammonium cation, bisstyrylethyldimethylammonium cation, (meth) acrylamidoethyltrimethylammonium cation, (meth) acrylamidopropyltrimethylammonium cation, (Meth) acrylamide Rutriethylammonium cation, (meth) acrylamide ethyltri-n-propylammonium cation, (meth) acrylamideethyltri-iso-propylammonium cation, (meth) acrylamideethyltri-n-butylammonium cation, (meth) acrylamideethyltri -Iso-butylammonium cation, (meth) acrylamidoethyltri-tert-butylammonium cation, (meth) acrylamidoethyltriethylammonium cation, (meth) acrylamidoethyldiethyl-n-hexylammonium cation, (meth) acrylamidoethyltridecylammonium cation Cation, (meth) acrylamide ethyl trioctyl ammonium cation, (meth) acrylamide ethyl Various ammonium cations such as decyldimethylammonium cation, (meth) acrylamidoethyldodecylhexylmethylammonium cation, styrylmethylmethylpyrrolidinium cation, bisstyrylmethylpiperidinium cation, N, N ′-((meth) acryloyloxyethylmethyl ) Piperazinium cation, (meth) acrylamidoethylmethylmorpholinium cation, (meth) acryloyloxyethylmethylimidazolium cation, and the like.
また、本発明に用いる塩モノマーを構成する有機アニオンとしては、重合性官能基を有するアニオンであれば、特に限定されないが、例えば、アルコラートおよびフェノラートなどの水酸基含有有機化合物のプロトンが脱離したアニオン：ＲＯ-アニオン、チオレートおよびチオフェノラートなどのプロトンが脱離したアニオン：ＲＳ-アニオン、スルホン酸アニオン：ＲＳＯ3 -、カルボン酸アニオン：ＲＣＯＯ-、リン酸および亜リン酸の水酸基の一部が有機基で置換している含リン誘導体アニオン：Ｒx（ＯＲ）y（Ｏ）zＰ-、（但し、ｘ、ｙ、ｚは０以上の整数で、かつ、ｘ＋ｙ＋２ｚ＝３またはｘ＋ｙ＋２ｚ＝５）、置換ボレートアニオン：Ｒx（ＯＲ）yＢ-、（但し、ｘ、ｙは０以上の整数で、かつ、ｘ＋ｙ＝４）、置換アルミニウムアニオン：Ｒx（ＯＲ）yＡｌ-、（但し、ｘ、ｙは０以上の整数で、かつ、ｘ＋ｙ＝４）、カルボアニオン（ＥＡ）3Ｃ-、窒素アニオン（ＥＡ）2Ｎ-などが挙げられる。ＥＡは水素原子または電子吸引基を示す。 In addition, the organic anion constituting the salt monomer used in the present invention is not particularly limited as long as it is an anion having a polymerizable functional group. For example, an anion from which a proton of a hydroxyl group-containing organic compound such as alcoholate and phenolate is eliminated. : RO - anion, thiolate and anion protons such thiophenolate are eliminated: RS - anions, sulfonate anions: RSO 3 -, carboxylate anions: RCOO -, it is part of the hydroxyl groups of phosphoric acid and phosphorous acid Phosphorus-containing derivative anion substituted with an organic group: R x (OR) y (O) z P − , where x, y and z are integers of 0 or more and x + y + 2z = 3 or x + y + 2z = 5 , substituted borate anion: R x (oR) y B -, ( provided that, x, y is 0 or an integer, and, x + y = 4), substituted Al Bromide anions: R x (OR) y Al -, ( provided that, x, y is 0 or an integer, and, x + y = 4), carbanions (EA) 3 C -, nitrogen anion (EA) 2 N - etc. Is mentioned. EA represents a hydrogen atom or an electron withdrawing group.
前記有機アニオンとしては特に、スルホキシル基、カルボキシル基、ホスフォキシル基およびスルホンイミド基由来のアニオンである、ＲＳＯ3 -、ＲＣＯＯ-、ＲＰＯ3 2-、および（ＲＯ2Ｓ）2Ｎ-が好ましい。ここで、Ｒは、水素、置換または無置換の、アルキル基ＣnＨ2n+1、アリール基（Ｒ’）n−Ｃ6Ｈ5-n−、アラルキル基（Ｒ’）m−Ｃ6Ｈ5-m−ＣnＨ2n−、アルケニル基Ｒ’−ＣＨ＝ＣＨ−Ｒ’−、アラルケニル基（Ｒ’）n−Ｃ6Ｈ5-n−ＣＨ＝ＣＨ−Ｒ’−、アルコキシアルキル基Ｒ’−Ｏ−ＣnＨ2n−、アシルオキシアルキル基Ｒ’−ＣＯＯ−ＣnＨ2n−であり、これらは環構造を有していてもよく、また、ヘテロ原子を含んでもよい。このＲが分子内に２個以上ある場合は互いに同じであっても異なっていてもかまわない。ただし、置換基Ｒを一つ有するアニオンの場合はそのＲが、複数の置換基Ｒを有する場合は、少なくとも一つが、重合性官能基を含む基であり、同様に、置換基ＥＡを一つ有するアニオンの場合はそのＥＡが、複数の置換基ＥＡを有する場合は、少なくとも一つが、重合性官能基を含む基である。前記Ｒにおける、Ｒ’は水素、または置換もしくは無置換の炭素数２０以下のアルキル基などであり、複数ある場合は互いに異なっても良く、ｍは１以上５以下の整数であり、ｎは１以上２０以下の整数である。また、前述Ｒの炭素上の水素原子の一部または全部がハロゲン原子に置換されているものも含まれる。Ｒ、Ｒ’において置換された場合の置換基としては、上記スルホニウムカチオンにおけるそれと同じものが挙げられる。 As the organic anion, RSO 3 − , RCOO − , RPO 3 2− and (RO 2 S) 2 N − which are anions derived from sulfoxyl group, carboxyl group, phosphoxyl group and sulfonimide group are particularly preferable. Wherein, R represents hydrogen, a substituted or unsubstituted, alkyl group C n H 2n + 1, aryl groups (R ') n -C 6 H 5-n -, an aralkyl group (R') m -C 6 H 5-m -C n H 2n - , alkenyl R'-CH = CH-R'-, aralkenyl group (R ') n -C 6 H 5-n -CH = CH-R'-, alkoxyalkyl group R '—O—C n H 2n —, an acyloxyalkyl group R′—COO—C n H 2n —, which may have a ring structure and may contain a heteroatom. When there are two or more Rs in the molecule, they may be the same or different from each other. However, in the case of an anion having one substituent R, when R has a plurality of substituents R, at least one is a group containing a polymerizable functional group, and similarly one substituent EA In the case of an anion having EA, when the EA has a plurality of substituents EA, at least one is a group containing a polymerizable functional group. In R, R ′ is hydrogen or a substituted or unsubstituted alkyl group having 20 or less carbon atoms, and when there are a plurality thereof, they may be different from each other, m is an integer of 1 to 5, and n is 1 It is an integer of 20 or more. Also included are those in which some or all of the hydrogen atoms on the carbon of R are replaced by halogen atoms. Examples of the substituent when substituted in R and R ′ include the same as those in the sulfonium cation.
前記有機アニオンにおける重合性官能基としては、上記重合性官能基を有するオニウムカチオンのそれと同じものを挙げることができる。塩モノマーの場合、少なくとも２つの重合性官能基を有することになるが、それらの重合性官能基は、それぞれ同じでも異なっていてもよい。 Examples of the polymerizable functional group in the organic anion include the same ones as those of the onium cation having the polymerizable functional group. The salt monomer has at least two polymerizable functional groups, and these polymerizable functional groups may be the same or different from each other.
前記塩モノマーを構成する有機アニオンの具体例としては、２−アクリルアミド−２−メチル−１−プロパンスルホン酸、２−［（２−プロペニロキシ）メトキシ］エテンスルホン酸、３−（２−プロペニロキシ）−１−プロペン−１−スルホン酸、ビニルスルホン酸、２−ビニルベンゼンスルホン酸、３−ビニルベンゼンスルホン酸、４−ビニルベンゼンスルホン酸、４−ビニルベンジルスルホン酸、２−メチル−１−ペンテン−１−スルホン酸、１−オクテン−１−スルホン酸、４−ビニルベンゼンメタンスルホン酸、アクリル酸、メタクリル酸、２−アクリルアミド−２−メチル−１−プロパンリン酸、２−（メタ）アクリロイルオキシ−１−エタンリン酸等由来の各種アニオンが挙げられる。 Specific examples of the organic anion constituting the salt monomer include 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-[(2-propenyloxy) methoxy] ethenesulfonic acid, 3- (2-propenyloxy)- 1-propene-1-sulfonic acid, vinylsulfonic acid, 2-vinylbenzenesulfonic acid, 3-vinylbenzenesulfonic acid, 4-vinylbenzenesulfonic acid, 4-vinylbenzylsulfonic acid, 2-methyl-1-pentene-1 -Sulfonic acid, 1-octene-1-sulfonic acid, 4-vinylbenzenemethanesulfonic acid, acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-1-propanephosphoric acid, 2- (meth) acryloyloxy-1 -Various anions derived from ethane phosphate and the like.
本発明に用いる重合性官能基を有するオニウムカチオンと重合性官能基を有する有機アニオンとから構成される塩モノマーとしては、例えば、前記重合性官能基を有する有機アニオンの銀塩などの金属塩と、前記重合性官能基を有するオニウムカチオンのハロゲン化物とを反応させて合成できるが、目的の塩モノマーが得られるのであればこの合成方法に限定されない。 Examples of the salt monomer composed of an onium cation having a polymerizable functional group and an organic anion having a polymerizable functional group used in the present invention include, for example, metal salts such as silver salts of the organic anion having the polymerizable functional group, and These can be synthesized by reacting with a halide of an onium cation having a polymerizable functional group, but the synthesis method is not limited as long as the target salt monomer can be obtained.
前記塩モノマーを重合してポリマーを合成する方法としては、塩モノマーを、メタノールおよびアセトニトリルなどの有機溶媒に溶解させ、必要に応じてラジカル重合開始剤を添加し、加熱、可視・紫外領域の光を照射、あるいは、電子線などの放射線を照射することによって重合することにより、所望のポリマーが得られる。
前記ラジカル重合開始剤としては、加熱による方法の場合、例えば、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２−イソブチロニトリル）および２，２’−アゾビス（２，４−ジメチルバレロニトリル）などのアゾ系重合開始剤、ベンゾイルパーオキシド、ジクミルパーオキシドおよびジイソプロピルパーオキシカーボネートなどの過酸化物系重合開始剤などが挙げられ、重合において、例えば、３０〜１５０℃で加熱して重合する方法が適用できる。光を照射する方法の場合は、例えば、アセトフェノン、ベンゾフェノンおよび２，２−ジメトキシ−２−フェニルアセトフェノンなどがラジカル重合開始剤として挙げられる。ラジカル重合開始剤を使用する場合の添加量としては、電解質系中に含まれる全ての成分の重合性官能基のモル数に対して、０．０１〜３０ｍｏｌ％程度であることが好ましく、さらに好ましくは０．１〜２０ｍｏｌ％である。合成においては、作業性を考慮し、溶媒中で重合しても良い。
本発明における塩モノマー由来のポリマーの好ましい含有量としては、電解質中での好ましい下限値が０．１ｗｔ％、好ましい上限値が９９．８ｗｔ％であり、より好ましい下限値１ｗｔ％、より好ましい上限値９８ｗｔ％である。ここでのポリマーの含有量とは、ポリマーを添加する場合にはその添加量、塩モノマーをその他の成分と混合した状態で重合させる場合にはモノマーの含有量である。
As a method of synthesizing a polymer by polymerizing the salt monomer, the salt monomer is dissolved in an organic solvent such as methanol and acetonitrile, a radical polymerization initiator is added as necessary, and heating, light in the visible / ultraviolet region is added. The desired polymer is obtained by polymerizing by irradiating or irradiating radiation such as electron beam.
Examples of the radical polymerization initiator include a 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-isobutyronitrile), and 2,2′-azobis ( 2,4-dimethylvaleronitrile) and the like, and benzoyl peroxide, dicumyl peroxide and peroxide-based polymerization initiators such as diisopropyl peroxycarbonate. In the polymerization, for example, 30 to A method of polymerizing by heating at 150 ° C. can be applied. In the case of the method of irradiating light, for example, acetophenone, benzophenone, 2,2-dimethoxy-2-phenylacetophenone and the like are mentioned as radical polymerization initiators. The addition amount when using a radical polymerization initiator is preferably about 0.01 to 30 mol%, more preferably based on the number of moles of polymerizable functional groups of all components contained in the electrolyte system. Is 0.1 to 20 mol%. In the synthesis, polymerization may be performed in a solvent in consideration of workability.
As a preferable content of the salt monomer-derived polymer in the present invention, a preferable lower limit value in the electrolyte is 0.1 wt%, a preferable upper limit value is 99.8 wt%, a more preferable lower limit value is 1 wt%, and a more preferable upper limit value is 98 wt%. The polymer content here is the content of the polymer when added, and the content of the monomer when polymerized in a state where the salt monomer is mixed with other components.
本発明に用いるリチウム塩としては、例えば、ＬｉＰＦ6、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ3、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2およびＬｉＣ（ＣＦ3ＳＯ2）3やＬｉイオンを含有するイオン性液体などが挙げられ、これらを単独あるいは２種以上を混合して用いても良い。使用するリチウム塩の添加量は、リチウムイオン伝導性電解質中での好ましい下限値が０．１ｗｔ％、好ましい上限値が９９．８ｗｔ％であり、より好ましい下限値１ｗｔ％、より好ましい上限値９８ｗｔ％である。 Examples of the lithium salt used in the present invention include LiPF 6 , LiClO 4 , LiCF 3 SO 3 , LiBF 4 , LiAsF 6 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 and LiC ( Examples thereof include ionic liquids containing CF 3 SO 2 ) 3 and Li ions, and these may be used alone or in admixture of two or more. The addition amount of the lithium salt used is preferably 0.1 wt%, a preferred upper limit is 99.8 wt%, more preferred lower limit is 1 wt%, and a more preferred upper limit is 98 wt% in the lithium ion conductive electrolyte. It is.
本発明に用いる常温溶融塩としては、４級アンモニウムカチオンとアニオンから構成されるが、耐電圧が５．０Ｖ以上であれば、何ら限定されないが、５．３V以上であることがより好ましい。また、前記常温溶融塩のカチオン成分としては、式（１）で表される４級アンモニウムカチオンが好ましい。
Ｎ+Ｒ1Ｒ2Ｒ3Ｒ4 （１）
（式中、Ｒ1、Ｒ2、Ｒ3およびＲ4は、それぞれ、アルキル基、アルコキシアルキル基、アラルキル基、アリール基、アルケニル基、アラルケニル基を示し、同一であっても異なっていても良い。これらのいずれか一対又はそれ以上が環構造を形成していても良く、ヘテロ原子を含んでも良い。）
The room temperature molten salt used in the present invention is composed of a quaternary ammonium cation and an anion, but is not limited as long as the withstand voltage is 5.0 V or more, but more preferably 5.3 V or more. Moreover, as a cation component of the said normal temperature molten salt, the quaternary ammonium cation represented by Formula (1) is preferable.
N + R 1 R 2 R 3 R 4 (1)
(Wherein R 1 , R 2 , R 3 and R 4 each represents an alkyl group, an alkoxyalkyl group, an aralkyl group, an aryl group, an alkenyl group or an aralkenyl group, which may be the same or different. Any one or more of these may form a ring structure and may contain a hetero atom.)
ここで、前記アンモニウムカチオンに含まれるＲ1、Ｒ2、Ｒ3、Ｒ4の基としては、アルキル基、アルコキシアルキル基、アラルキル基、アリール基、アルケニル基、アラルケニル基から選ばれる基である場合が好ましい。さらに、アルキル基、アルコキシアルキル基、アラルキル基がより好ましく、アルコキシアルキル基が最も好ましい。さらにこれらの基の具体例としては、メチル、エチル、プロピル、メトキシメチル、メトキシエチル、（メトキシエトキシ）エチル、（ヒドロキシエトキシ）エチル、（ヒドロキシエチル）メチルアミノ、メトキシ（カルボニルエチル）、ヒドロキシエチル、フェニル、ナフチル、ベンジル、オキサゾリル、モルホリニルなどの基が挙げられる。 Here, the groups R 1 , R 2 , R 3 and R 4 contained in the ammonium cation are groups selected from an alkyl group, an alkoxyalkyl group, an aralkyl group, an aryl group, an alkenyl group, and an aralkenyl group. Is preferred. Furthermore, an alkyl group, an alkoxyalkyl group, and an aralkyl group are more preferable, and an alkoxyalkyl group is most preferable. Specific examples of these groups include methyl, ethyl, propyl, methoxymethyl, methoxyethyl, (methoxyethoxy) ethyl, (hydroxyethoxy) ethyl, (hydroxyethyl) methylamino, methoxy (carbonylethyl), hydroxyethyl, And groups such as phenyl, naphthyl, benzyl, oxazolyl, morpholinyl and the like.
また、前記常温溶融塩のアニオン成分としては、式（２）で表されるアニオンが好ましい。
Ｎ（Ｒ1ＳＯ2）（Ｒ2ＳＯ2）-， Ｎ（Ｒ3ＳＯ3）- Ｃ（Ｒ4ＳＯ2）（Ｒ5ＳＯ2）（Ｒ6ＳＯ2）- （２）
（式中、Ｒ1〜Ｒ6は、それぞれ、置換もしくは無置換の、アルキル基、アルコキシアルキル基、アラルキル基、アリール基、アルケニル基、アラルケニル基から選ばれる基であり、同一であっても異なっていても良く、これらは環構造を有していてもよい。また、これらはヘテロ原子を含んでもよい。）
Moreover, as an anion component of the said normal temperature molten salt, the anion represented by Formula (2) is preferable.
N (R 1 SO 2 ) (R 2 SO 2 ) − , N (R 3 SO 3 ) − C (R 4 SO 2 ) (R 5 SO 2 ) (R 6 SO 2 ) − (2)
Wherein R 1 to R 6 are each a substituted or unsubstituted group selected from an alkyl group, an alkoxyalkyl group, an aralkyl group, an aryl group, an alkenyl group, and an aralkenyl group. And they may have a ring structure, and they may contain heteroatoms.)
ここで、前記アニオンに含まれる基としては、アルキル、アルコキシアルキル基、アラルキル基、アリール基、アルケニル基、アラルケニル基から選ばれる基である場合に耐電圧が高く好ましい。さらに、アルキル基、アルコキシアルキル基、アラルキル基がより好ましい。さらにこれらの基の具体例としては、前記常温溶融塩におけるアンモニウムカチオンと同じ基が挙げられる。また、これらの基を置換する場合の置換基は、前記塩モノマーのスルホニウムカチオンにおけるそれと同じものが挙げられ、さらには、全てがハロゲンで置換されていても良い。
使用する常温溶融塩の添加量は、リチウムイオン伝導性電解質中での好ましい下限値が０．１ｗｔ％、好ましい上限値が９９．８ｗｔ％であり、より好ましい下限値１ｗｔ％、より好ましい上限値９８ｗｔ％である。
Here, the group contained in the anion is preferably a group having a high withstand voltage when it is a group selected from an alkyl group, an alkoxyalkyl group, an aralkyl group, an aryl group, an alkenyl group, and an aralkenyl group. Furthermore, an alkyl group, an alkoxyalkyl group, and an aralkyl group are more preferable. Furthermore, specific examples of these groups include the same groups as the ammonium cations in the room temperature molten salt. Moreover, the substituent in the case of substituting these groups may be the same as that in the sulfonium cation of the salt monomer, and all may be substituted with halogen.
The addition amount of the room temperature molten salt used is preferably a lower limit of 0.1 wt% and a preferred upper limit of 99.8 wt% in the lithium ion conductive electrolyte, a more preferred lower limit of 1 wt%, and a more preferred upper limit of 98 wt. %.
本発明に用いるポリマーにおいて、前記塩モノマーに、その他のモノマーを併用することも可能である。そのようなモノマーの例としては、メチレンビスアクリルアミド、エチレングリコールジ（メタ）アクリレート、ジビニルベンゼン、ジアリルメチルアミン、ジアリルエチルアミン、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレートおよびジアリルフタレートなどの重合性官能基を複数有するモノマーや、Ｎ,Ｎ−ジメチル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、アクリル酸ステアリル、ジアセトンアクリルアミド、（メタ）アクリル酸１−アダマンチルおよび（メタ）アクリル酸２−エチルアダマンチルなどの重合性官能基を一つ有するモノマーなどが挙げられる。
本発明のイオン伝導性電解質には、上記成分の他に、可塑剤、重合開始剤、難燃性電解質溶解剤、その他の添加剤を用いることができる。
In the polymer used in the present invention, other monomers can be used in combination with the salt monomer. Examples of such monomers include polymerizable functionalities such as methylene bisacrylamide, ethylene glycol di (meth) acrylate, divinylbenzene, diallylmethylamine, diallylethylamine, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate and diallyl phthalate. Monomers having a plurality of groups, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, stearyl acrylate, diacetone acrylamide, 1-adamantyl (meth) acrylate and 2-ethyl (meth) acrylate And monomers having one polymerizable functional group such as adamantyl.
In addition to the above components, a plasticizer, a polymerization initiator, a flame retardant electrolyte solubilizer, and other additives can be used for the ion conductive electrolyte of the present invention.
本発明のイオン伝導性電解質を製造する方法としては、まず、塩モノマー、リチウム塩、常温溶融塩、必要に応じて、その他のモノマー、可塑剤、重合開始剤、その他添加剤の混合物を調製し、モノマーを重合して電解質を得ることができる。ここで、塩モノマーと任意に混合するその他の成分は、これにより合成されるポリマーの含有量が上記割合になるように添加する。前記塩モノマーを含んで得られたポリマー、リチウム塩、常温溶融塩を混合することによってもイオン伝導性電解質が得られる。この場合も、必要に応じて、その他のモノマー、可塑剤、重合開始剤、その他添加剤を使用しても良い。
前記混合方法としては、溶液混合、粉体混合、溶融混練など、公知の混合方法により行えば良い。可塑剤を使用する場合は、リチウム塩を可塑剤に溶かした溶液を、モノマーと混合しても良い。
As a method for producing the ion conductive electrolyte of the present invention, first, a salt monomer, a lithium salt, a room temperature molten salt and, if necessary, a mixture of other monomers, a plasticizer, a polymerization initiator, and other additives are prepared. The electrolyte can be obtained by polymerizing the monomer. Here, the other components optionally mixed with the salt monomer are added so that the content of the polymer synthesized thereby becomes the above ratio. An ion conductive electrolyte can also be obtained by mixing a polymer obtained by containing the salt monomer, a lithium salt, and a room temperature molten salt. Also in this case, other monomers, plasticizers, polymerization initiators, and other additives may be used as necessary.
The mixing method may be a known mixing method such as solution mixing, powder mixing, and melt kneading. When a plasticizer is used, a solution in which a lithium salt is dissolved in the plasticizer may be mixed with the monomer.
本発明のイオン伝導性電解質の製造において、モノマー、リチウム塩、常温溶融塩、必要に応じて難燃性電解質溶解剤、可塑剤、重合開始剤、その他添加剤を混合し、液状またはペースト状の混合物を調製するが、常温溶融塩、難燃性電解質溶解剤にリチウム塩を溶かした溶液と、モノマーとを混合しても良い。
前記可塑剤としては、例えば、エチレンカーボネートおよびプロピレンカーボネートなどの環状炭酸エステル、エチルメチルカーボネートおよびジエチルカーボネートなどの鎖状炭酸エステルなどが挙げられ、これらは、それらの混合物を添加することができる。
前記難燃性電解質塩溶解剤としては、自己消火性を示し、かつ、電解質塩が共存した状態で電解質塩を溶解するのに寄与する化合物が挙げられ、一般に非水電解質電池用電解液に添加される難燃性溶媒が利用でき、リン酸エステル、ハロゲン化合物およびフォスファゼンなどが挙げられる。
In the production of the ion conductive electrolyte of the present invention, a monomer, a lithium salt, a room temperature molten salt, and a flame retardant electrolyte solubilizer, a plasticizer, a polymerization initiator, and other additives are mixed as necessary to form a liquid or paste. Although a mixture is prepared, a monomer in which a solution obtained by dissolving a lithium salt in a room temperature molten salt or a flame retardant electrolyte dissolving agent may be mixed.
Examples of the plasticizer include cyclic carbonates such as ethylene carbonate and propylene carbonate, and chain carbonates such as ethyl methyl carbonate and diethyl carbonate, and a mixture thereof can be added thereto.
Examples of the flame retardant electrolyte salt solubilizer include compounds that exhibit self-extinguishing properties and contribute to dissolving the electrolyte salt in the presence of the electrolyte salt, and are generally added to the electrolyte for non-aqueous electrolyte batteries. Flame retardant solvents, such as phosphate esters, halogen compounds and phosphazenes.
さらに、電池製造における電解質の作製方法について具体例を示して説明するが、電解質の作製方法は何ら限定されない。
上記で調製した混合物は、液状またはペースト状のように均質な形態をとるものが好ましい。但し、実際にリチウムイオン伝導性電解質を製造する際に、調製後から重合による硬化が完了するまでの間、乳化、エマルジョン、コロイド、コアセルベートなどの溶液状態を維持可能であれば、混合物の濁度が高くても利用可能である。
上記で調製した混合物は、電極を備えた所定のセル若しくは型枠に注液し、加熱あるいはエネルギー線照射などの方法でモノマーを重合し、硬化させることにより、イオン伝導性電解質を得ることができる。
調製した混合物の粘度が高く作業しにくい場合は、調製した混合物を、テトラヒドロフラン、メタノールおよびアセトニトリルなどの低沸点の希釈溶媒で希釈したものを重合し、硬化させた後に、それらの希釈溶媒を除去する方法、または、希釈溶媒を電池に使用する電解液に、溶媒置換する方法などの公知であるセルの作製方法を用いても良い。
また、セルの構成によっては注液以外にも、調製した混合物をキャスト法や固相重合法など公知の方法によってリチウムイオン伝導性電解質を得ることができる。
Furthermore, although a specific example is shown and demonstrated about the preparation method of the electrolyte in battery manufacture, the preparation method of electrolyte is not limited at all.
The mixture prepared above preferably has a homogeneous form such as liquid or paste. However, when the lithium ion conductive electrolyte is actually produced, the turbidity of the mixture can be maintained as long as the solution state such as emulsification, emulsion, colloid, coacervate can be maintained after the preparation until the curing by polymerization is completed. Can be used even if the price is high.
The mixture prepared above is poured into a predetermined cell or mold having an electrode, and the monomer is polymerized and cured by a method such as heating or energy ray irradiation, whereby an ion conductive electrolyte can be obtained. .
If the prepared mixture is highly viscous and difficult to work with, the diluted mixture is diluted with a low-boiling dilution solvent such as tetrahydrofuran, methanol, and acetonitrile. After curing and curing, the diluted solvent is removed. A known method for producing a cell such as a solvent replacement method may be used for the method or an electrolytic solution that uses a diluting solvent for a battery.
Further, depending on the configuration of the cell, in addition to the injection, a lithium ion conductive electrolyte can be obtained by a known method such as a cast method or a solid phase polymerization method using the prepared mixture.
本発明の二次電池は、上記で得られたイオン伝導性電解質を構成要素とするものであり、前記イオン伝導性電解質の他に正極及び負極などを組み合わせて製造することができる。
本発明の電池で用いられる正極に使用される活物質としては、エネルギー密度が高く、リチウムイオンの可逆的な脱挿入に優れたリチウムを含有する遷移金属酸化物が好ましく、例えば、ＬｉＣｏＯ2などのリチウムコバルト酸化物、ＬｉＭｎ2Ｏ4などのリチウムマンガン酸化物、ＬｉＮｉＯ2などのリチウムニッケル酸化物、これら酸化物の混合物およびＬｉＮｉＯ2のニッケルの一部をコバルトやマンガンに置換したものなどが挙げられる。負極活物質としては、リチウムイオンを挿入、脱離させることのできる材料であれば限定されないが、金属リチウムや炭素系材料などが挙げられ、炭素材料としては、例えば、天然黒鉛、人造黒鉛、メソカーボンマイクロビーズおよびグラファイトなどが挙げられる。
The secondary battery of the present invention comprises the ion conductive electrolyte obtained above as a constituent element, and can be manufactured by combining a positive electrode and a negative electrode in addition to the ion conductive electrolyte.
The active material used for the positive electrode used in the battery of the present invention is preferably a transition metal oxide containing lithium having a high energy density and excellent reversible lithium ion insertion / extraction, such as LiCoO 2 . Examples include lithium cobalt oxide, lithium manganese oxide such as LiMn 2 O 4 , lithium nickel oxide such as LiNiO 2 , a mixture of these oxides, and a part of nickel in LiNiO 2 substituted with cobalt or manganese. . The negative electrode active material is not limited as long as it is a material that can insert and desorb lithium ions, and examples thereof include metallic lithium and carbon-based materials. Examples of the carbon material include natural graphite, artificial graphite, and meso Examples thereof include carbon micro beads and graphite.
本発明の高分子固体電解質を用いた二次電池を製造する方法の例としては、まず、上記ＬｉＣｏＯ2などの正極活物質、黒鉛などの導電剤、ポリ（ビニリデンフルオライド）などの結着剤を混合して正極合剤を調製し、この正極合剤をＮ−メチル−２−ピロリドン中に分散させて、スラリー状の正極合剤とする。この正極合剤を、厚み２０μｍのアルミニウム箔などからなる正極集電体の両面に均一に塗布し、乾燥後、ロールプレス機で圧縮成形することで正極が得られる。 Examples of a method for producing a secondary battery using the polymer solid electrolyte of the present invention include a positive electrode active material such as LiCoO 2 , a conductive agent such as graphite, and a binder such as poly (vinylidene fluoride). Are mixed to prepare a positive electrode mixture, and the positive electrode mixture is dispersed in N-methyl-2-pyrrolidone to obtain a slurry-like positive electrode mixture. This positive electrode mixture is uniformly applied to both surfaces of a positive electrode current collector made of an aluminum foil having a thickness of 20 μm, etc., dried, and then compression molded with a roll press to obtain a positive electrode.
次に、黒鉛粉末などの負極活物質と、ポリ（ビニリデンフルオライド）などの結着剤を混合して、負極合剤を調製し、この負極合剤をＮ−メチル−２−ピロリドン中に分散させてスラリー状の負極合剤とする。この負極合剤を、厚み１５μｍの銅箔などからなる負極集電体の両面に均一に塗布し、乾燥後、ロールプレス機で圧縮成形することで負極が得られる。
上記のようにして得た、正極とイオン伝導性電解質と負極を貼り合わせ単層セルとし、このセルをポリエステルフィルム−アルミニウムフィルム−変性ポリオレフィンフィルムの三層構造のラミネートフィルムからなる外装体に挿入し封止して、二次電池が得られる。
Next, a negative electrode active material such as graphite powder and a binder such as poly (vinylidene fluoride) are mixed to prepare a negative electrode mixture, and this negative electrode mixture is dispersed in N-methyl-2-pyrrolidone. To make a slurry-like negative electrode mixture. This negative electrode mixture is uniformly applied to both surfaces of a negative electrode current collector made of a copper foil having a thickness of 15 μm, etc., dried, and then compression molded with a roll press to obtain a negative electrode.
The positive electrode, the ion conductive electrolyte, and the negative electrode obtained as described above are bonded to form a single-layer cell, and this cell is inserted into an outer package made of a laminate film having a three-layer structure of polyester film-aluminum film-modified polyolefin film. The secondary battery is obtained by sealing.
以下、実施例により本発明を更に詳しく説明するが、本発明はこれによって何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited at all by this.
＜塩モノマーの合成と重合＞
２−アクリルアミド−２−メチル−１−プロパンスルホン酸１０．３６ｇ（５０ｍｍｏｌ）を、メタノール５００ｍｌ／蒸留水４ｍｌに溶解し、これに炭酸銀８．２８ｇ（３０ｍｍｏｌ）を添加して、室温下で穏やかに４時間連続攪拌し、濾過後、無色透明の溶液を得た。この濾液に、１０１ｍｍｏｌのアクリロイルオキシエチルジメチルベンジルアンモニウムクロリドをメタノール１００ｍｌに溶解した溶液を滴下反応させた。反応は定量的に進行した。反応生成物である塩化銀を濾別し、無色透明のメタノール溶液を回収した。この濾液をエバポレーターで減圧濃縮し、冷暗所で終日静置することにより目的物を再結晶させ、無色透明の板状結晶を回収した。得られた塩モノマーは、1Ｈ−ＮＭＲにより生成物の確認を行い、所望の化合物が得られていることを確認した。
さらに、この塩モノマー１０ｇをメタノール３０ｍｌに溶解させ、重合開始剤としてベンゾイルパーオキシド０．０３ｇを添加し、充分脱気操作を行った後に、窒素気流下、６０℃で６０分加熱重合させた。反応液は、重合の進行に伴い増粘した。得られた反応溶液を１５００ｍｌのアセトン中に滴下すると白色の固体が析出した。これを濾別し、６０℃で２時間減圧乾燥させることによって、塩モノマーの重合体６．５ｇを回収した。
<Synthesis and polymerization of salt monomer>
10.36 g (50 mmol) of 2-acrylamido-2-methyl-1-propanesulfonic acid was dissolved in 500 ml of methanol / 4 ml of distilled water, and 8.28 g (30 mmol) of silver carbonate was added thereto. For 4 hours, and after filtration, a colorless and transparent solution was obtained. A solution prepared by dissolving 101 mmol of acryloyloxyethyldimethylbenzylammonium chloride in 100 ml of methanol was dropped into this filtrate. The reaction proceeded quantitatively. The reaction product silver chloride was removed by filtration, and a colorless and transparent methanol solution was recovered. The filtrate was concentrated under reduced pressure using an evaporator, and allowed to stand all day in a cool dark place to recrystallize the desired product, and colorless and transparent plate crystals were recovered. The obtained salt monomer confirmed the product by 1 H-NMR, and confirmed that the desired compound was obtained.
Further, 10 g of this salt monomer was dissolved in 30 ml of methanol, 0.03 g of benzoyl peroxide was added as a polymerization initiator, and after sufficient deaeration operation, the mixture was heated and polymerized at 60 ° C. for 60 minutes in a nitrogen stream. The reaction solution thickened as the polymerization progressed. The obtained reaction solution was dropped into 1500 ml of acetone to precipitate a white solid. This was separated by filtration and dried under reduced pressure at 60 ° C. for 2 hours to recover 6.5 g of a salt monomer polymer.
［実施例１］
乾燥アルゴン雰囲気（露点温度：−６０℃以下）にて、十分に乾燥した上記塩モノマー重合体２．０ｇ、リチウムビス（トリフルオロメタンスルホン）イミド２．０ｇ、ジエチルメチル（メトキシエチル）アンモニウム・ビス（トリフルオロメタンスルホン）イミド（常温溶融塩（１））１６．０ｇを混合した後、メタノールを５ｍｌ添加し、完全に溶解させた。得られた溶液を、テフロン（登録商標）シート上でキャストし、６０℃で溶媒を除去した後に、１１０℃で２時間減圧加熱し、膜状のイオン伝導性電解質（１）を得た。上記で得られたイオン伝導性電解質（１）について、交流インピーダンス法により、イオン伝導度を測定した。測定の際の周波数範囲は０．１Ｈｚ〜１０ＭＨｚ、電圧は０．１Ｖとした。イオン伝導度を測定した結果、室温（２０℃）に於けるイオン伝導度は１．３×１０-3Ｓ／ｃｍであった。
ここで用いた常温溶融塩（１）の耐電圧を調べるのに、サイクリックボルタンメトリー装置を用い、作用極として白金電極、対極として白金電極、参照極として銀／塩化銀電極を使用し、掃引速度１ｍV/秒の条件でサイクリックボルタンメトリー測定を行った。測定結果から、耐電圧は５．７Ｖであった。
また、イオン伝導性電解質（１）を用いた二次電池のサイクル特性評価を行った。正極活物質として、ＬｉＣｏＯ2を８５重量％、導電剤としての黒鉛を５重量％と、結着剤としてのポリ（ビニリデンフルオライド）を１０重量％とを混合して、正極合剤を調製し、この正極合剤を、Ｎ−メチル−２−ピロリドン中に分散させて、スラリー状の正極合剤とした。この正極合剤を、正極集電体として用いる厚み２０μｍのアルミニウム箔の両面に、均一に塗布し、乾燥後、ロールプレス機で圧縮成形することで正極を得た。
負極活物質として粉砕した黒鉛粉末を９０重量％と、結着剤としてポリ（ビニリデンフルオライド）を１０重量％とを混合して、負極合剤を調製し、この負極合剤を、Ｎ−メチル−２−ピロリドン中に分散させて、スラリー状の負極合剤とした。この負極合剤を、負極集電体として用いる厚み１５μｍの銅箔の両面に、均一に塗布し、乾燥後、ロールプレス機で圧縮成形することで負極を得た。
上記で得られた正極とイオン伝導性電解質（１）と負極を貼り合わせ単層セルとし、このセルをポリエステルフィルム−アルミニウムフィルム−変性ポリオレフィンフィルムの三層構造のラミネートフィルムからなる外装体に挿入し封止して二次電池を得た。電池の組み立て後、２５℃、５００ｍＡの定電流電圧充電を上限４．２Ｖまで２時間行い、次に５００ｍＡでの放電（１時間率放電）を終止電圧２．５Ｖまで行った。これを１サイクルとして充放電を１００サイクル行い、１サイクル目の放電容量を１００％としたときの１００サイクル目の容量維持率を求めた。１００サイクル後の容量維持率は、９７％であった。
[Example 1]
In a dry argon atmosphere (dew point temperature: −60 ° C. or lower), 2.0 g of the above-mentioned salt monomer polymer, 2.0 g of lithium bis (trifluoromethanesulfone) imide, diethylmethyl (methoxyethyl) ammonium bis ( After mixing 16.0 g of trifluoromethanesulfone) imide (room temperature molten salt (1)), 5 ml of methanol was added and completely dissolved. The obtained solution was cast on a Teflon (registered trademark) sheet, and after removing the solvent at 60 ° C., the solution was heated under reduced pressure at 110 ° C. for 2 hours to obtain a membrane-like ion conductive electrolyte (1). About the ion conductive electrolyte (1) obtained above, ion conductivity was measured by the alternating current impedance method. The frequency range during measurement was 0.1 Hz to 10 MHz, and the voltage was 0.1 V. As a result of measuring the ionic conductivity, the ionic conductivity at room temperature (20 ° C.) was 1.3 × 10 −3 S / cm.
In order to examine the withstand voltage of the room temperature molten salt (1) used here, a cyclic voltammetry apparatus was used, a platinum electrode as a working electrode, a platinum electrode as a counter electrode, a silver / silver chloride electrode as a reference electrode, and a sweep rate Cyclic voltammetry measurement was performed under the condition of 1 mV / sec. From the measurement results, the withstand voltage was 5.7V.
In addition, the cycle characteristics of the secondary battery using the ion conductive electrolyte (1) were evaluated. A positive electrode mixture was prepared by mixing 85% by weight of LiCoO 2 as a positive electrode active material, 5% by weight of graphite as a conductive agent, and 10% by weight of poly (vinylidene fluoride) as a binder. The positive electrode mixture was dispersed in N-methyl-2-pyrrolidone to obtain a slurry-like positive electrode mixture. This positive electrode mixture was uniformly applied to both surfaces of a 20 μm thick aluminum foil used as a positive electrode current collector, dried, and then compression molded with a roll press to obtain a positive electrode.
A negative electrode mixture was prepared by mixing 90% by weight of pulverized graphite powder as a negative electrode active material and 10% by weight of poly (vinylidene fluoride) as a binder, and this negative electrode mixture was mixed with N-methyl. A slurry-like negative electrode mixture was prepared by dispersing in 2-pyrrolidone. This negative electrode mixture was uniformly applied to both surfaces of a 15 μm thick copper foil used as a negative electrode current collector, dried, and then compression molded with a roll press to obtain a negative electrode.
The positive electrode obtained above, the ion conductive electrolyte (1), and the negative electrode are laminated to form a single-layer cell, and this cell is inserted into an outer package made of a laminate film having a three-layer structure of polyester film-aluminum film-modified polyolefin film. The secondary battery was obtained by sealing. After the battery was assembled, constant current voltage charging at 25 ° C. and 500 mA was performed for 2 hours to an upper limit of 4.2 V, and then discharging at 500 mA (1 hour rate discharge) was performed to a final voltage of 2.5 V. Using this as one cycle, 100 cycles of charge / discharge were performed, and the capacity retention rate at the 100th cycle was determined, assuming that the discharge capacity at the first cycle was 100%. The capacity retention rate after 100 cycles was 97%.
［実施例２］
実施例1において、常温溶融塩（１）の代わりにジエチルメチル（メトキシエチル）アンモニウム・テトラフルオロボレート（常温溶融塩（２））を使用する以外は、実施例１と同様にして、膜状のイオン伝導性電解質（２）を得た。イオン伝導性電解質（２）のイオン伝導度、常温溶融塩（２）の耐電圧を測定した結果、室温（２０℃）に於けるイオン伝導度は１．５×１０-3Ｓ／ｃｍ、常温溶融塩の耐電圧は、６．０Ｖであった。また、実施例１と同様にして二次電池を作製し、１００サイクル後の容量維持率を求めたところ、９３％であった。
[Example 2]
In Example 1, in the same manner as in Example 1 except that diethylmethyl (methoxyethyl) ammonium tetrafluoroborate (room temperature molten salt (2)) was used instead of room temperature molten salt (1), An ion conductive electrolyte (2) was obtained. As a result of measuring the ion conductivity of the ion conductive electrolyte (2) and the withstand voltage of the room temperature molten salt (2), the ion conductivity at room temperature (20 ° C.) was 1.5 × 10 −3 S / cm, room temperature. The withstand voltage of the molten salt was 6.0V. A secondary battery was produced in the same manner as in Example 1, and the capacity retention rate after 100 cycles was determined to be 93%.
［実施例３］
実施例1において、常温溶融塩（１）の代わりに｛２−（メトキシエトキシ）エチル｝トリメチルアンモニウム・ビス（トリフルオロメタンスルホン）イミド（常温溶融塩（３））を使用する以外は、実施例１と同様にして、膜状のイオン伝導性電解質（３）を得た。イオン伝導性電解質（３）のイオン伝導度、常温溶融塩（３）の耐電圧を測定した結果、室温（２０℃）に於けるイオン伝導度は１．１×１０-3Ｓ／ｃｍ、常温溶融塩の耐電圧は、５．６Ｖであった。また、実施例１と同様にして二次電池を作製し、１００サイクル後の容量維持率を求めたところ、９４％であった。
[Example 3]
Example 1 is the same as Example 1 except that {2- (methoxyethoxy) ethyl} trimethylammonium bis (trifluoromethanesulfone) imide (room temperature molten salt (3)) is used instead of room temperature molten salt (1). In the same manner as above, a membrane-like ion conductive electrolyte (3) was obtained. As a result of measuring the ionic conductivity of the ion conductive electrolyte (3) and the withstand voltage of the room temperature molten salt (3), the ionic conductivity at room temperature (20 ° C.) was 1.1 × 10 −3 S / cm. The withstand voltage of the molten salt was 5.6V. A secondary battery was produced in the same manner as in Example 1, and the capacity retention rate after 100 cycles was determined to be 94%.
［比較例１］
実施例1において、常温溶融塩（１）の代わりに１−エチル−３−メチルイミダゾリウム・テトラフルオロボレート（常温溶融塩（４））を使用する以外は、実施例１と同様にして、膜状のイオン伝導性電解質（４）を得た。ここで得られたイオン伝導性電解質のイオン伝導度は、室温（２０℃）で１．３×１０-3Ｓ／ｃｍと高かったが、常温溶融塩（４）の耐電圧は、４．６Ｖと低かった。このイオン伝導性電解質（４）を用いた二次電池を実施例１と同様に作製し、１００サイクル後の容量維持率を求めたところ、６２％と低い値を示した。
[Comparative Example 1]
In Example 1, in the same manner as in Example 1 except that 1-ethyl-3-methylimidazolium tetrafluoroborate (room temperature molten salt (4)) was used instead of room temperature molten salt (1), An ion conductive electrolyte (4) was obtained. The ionic conductivity of the obtained ion conductive electrolyte was as high as 1.3 × 10 −3 S / cm at room temperature (20 ° C.), but the withstand voltage of the room temperature molten salt (4) was 4.6V. It was low. A secondary battery using this ion conductive electrolyte (4) was produced in the same manner as in Example 1, and the capacity retention rate after 100 cycles was determined to be as low as 62%.
本発明によれば、優れたイオン伝導性を示し、広い電位範囲で電気化学的に安定であり耐電圧の高いイオン伝導性電解質を提供できることから、これを用いて、性能に優れた二次電池に適用できる。また、この電解質は、キャパシタやエレクトロクロミック素子等、電気化学素子全般へも適用可能である。 According to the present invention, an ion conductive electrolyte that exhibits excellent ionic conductivity, is electrochemically stable in a wide potential range, and has a high withstand voltage can be provided. Applicable to. The electrolyte can also be applied to all electrochemical elements such as capacitors and electrochromic elements.
Claims (2)
Ｎ + Ｒ 1 Ｒ 2 Ｒ 3 Ｒ 4 （１）
（式中、Ｒ 1 、Ｒ 2 、Ｒ 3 およびＲ 4 は、それぞれ、アルキル基、アルコキシアルキル基、アラルキル基、アリール基、アルケニル基、アラルケニル基を示し、同一であっても異なっていても良い。これらのいずれか一対又はそれ以上が環構造を形成していても良く、ヘテロ原子を含んでも良い。）
Ｎ（Ｒ 1 ＳＯ 2 ）（Ｒ 2 ＳＯ 2 ） - ， Ｎ（Ｒ 3 ＳＯ 3 ） - ， Ｃ（Ｒ 4 ＳＯ 2 ）（Ｒ 5 ＳＯ 2 ）（Ｒ 6 ＳＯ 2 ） - （２）
（式中、Ｒ 1 〜Ｒ 6 は、それぞれ、置換もしくは無置換の、アルキル基、アルコキシアルキル基、アラルキル基、アリール基、アルケニル基、アラルケニル基から選ばれる基であり、同一であっても異なっていても良く、これらは環構造を有していてもよい。また、これらはヘテロ原子を含んでもよい。） In an ion conductive electrolyte including a polymer, a lithium salt, and a room temperature molten salt composed of a quaternary ammonium cation and an anion , the polymer is composed of an onium cation having a polymerizable functional group and an organic anion having a polymerizable functional group. has been synthesized include constructed salt monomer, room temperature molten salt have a minimum withstand voltage 5.0V, 4 quaternary ammonium cation component constituting the ambient temperature molten salt, by the following formula (1) An ion-conducting electrolyte , wherein the anion component is a quaternary ammonium cation represented by the anionic component constituting the room temperature molten salt selected from the group of anions represented by the following formula (2) .
N + R 1 R 2 R 3 R 4 (1)
(Wherein R 1 , R 2 , R 3 and R 4 each represents an alkyl group, an alkoxyalkyl group, an aralkyl group, an aryl group, an alkenyl group or an aralkenyl group, which may be the same or different. Any one or more of these may form a ring structure and may contain a hetero atom.)
N (R 1 SO 2 ) (R 2 SO 2 ) − , N (R 3 SO 3 ) − , C (R 4 SO 2 ) (R 5 SO 2 ) (R 6 SO 2 ) − (2)
Wherein R 1 to R 6 are each a substituted or unsubstituted group selected from an alkyl group, an alkoxyalkyl group, an aralkyl group, an aryl group, an alkenyl group, and an aralkenyl group. And they may have a ring structure, and they may contain heteroatoms.)
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