JP2016154086A - 配位構造体及び蓄電デバイス - Google Patents
配位構造体及び蓄電デバイス Download PDFInfo
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- JP2016154086A JP2016154086A JP2015031478A JP2015031478A JP2016154086A JP 2016154086 A JP2016154086 A JP 2016154086A JP 2015031478 A JP2015031478 A JP 2015031478A JP 2015031478 A JP2015031478 A JP 2015031478A JP 2016154086 A JP2016154086 A JP 2016154086A
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- coordination
- storage device
- coordination structure
- anions
- organic compound
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- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 29
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 230000005611 electricity Effects 0.000 claims description 21
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000005412 pyrazyl group Chemical group 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 230000003252 repetitive effect Effects 0.000 abstract 2
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- 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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Abstract
【解決手段】本発明の蓄電デバイスは、正極と、配位構造体を含む負極と、正極と負極との間に介在しアニオンを伝導するイオン伝導媒体と、を備え、アニオンの移動により充放電するものである。この配位構造体は、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag及びCdから選ばれる1以上の金属イオンと、窒素を含み金属イオンに配位する2以上の非イオン性配位部位を有する有機化合物と、を含み、金属イオンに有機化合物が配位した繰返し構造を備え、繰返し構造内にアニオンを吸蔵及び放出するものである。
【選択図】なし
Description
Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag及びCdから選ばれる1以上の金属イオンと、窒素を含み前記金属イオンに配位する2以上の非イオン性配位部位を有する有機化合物と、を含み、前記金属イオンに前記有機化合物が配位した繰返し構造を備え、前記繰返し構造内にアニオンを吸蔵及び放出するものである。
正極と、
上述した配位構造体を含む負極と、
前記正極と前記負極との間に介在し前記アニオンを伝導するイオン伝導媒体と、を備え、前記アニオンの移動により充放電するものである。
テトラフルオロホウ酸銅(II)を0.99gと、4,4’−ビピリジンを0.65gと、水50mLとを加えて、150℃、72時間加熱した。生成物をろ過し、エタノールで洗浄後、乾燥し得られた粉末を実施例1の配位構造体材料とした(式(6))。
テトラフルオロホウ酸銅(II)を0.71gと、1,2−ジ−4−ピリジルエチレンを1.09gと、水を50mLとを加えて、150℃、72時間加熱した。生成物をろ過し、エタノールで洗浄後、乾燥し得られた粉末を実施例2の配位構造体材料とした(式(7))。
理学Mercury70(Mo−Kα)を用いて、単結晶X線構造解析を行った。この構造解析では、特定の結晶ピークを示しており、実施例1,2の粉末は、結晶構造を有するものと推察された。測定により得られた格子定数を表1に示した。この結果より、実施例1の配位構造体は、図1に示す構造を有する3次元構造体であるものと推察された。また、実施例2の配位構造体は、図2に示す構造を有する3次元構造体であるものと推察された。なお、実施例1のCu−bpy配位構造体は、空間群P21/cに帰属される単斜晶型の結晶構造を有することがわかった。また、実施例2のCu−dpe配位構造体は、空間群P-1に帰属される三斜晶型の結晶構造を有することがわかった。
Thermo Nicolet製AVATAR360 FT−IRを用いて、IRスペクトル測定を行った。図3は、実施例1、2の配位構造体のIR測定結果である。図3に示すように、1050cm-1にBF4 -と考えられる吸収が観察された。この結果から、配位構造体の内部において、アニオン(BF4 -)が、金属イオンに配位せずに存在しているものと推察された。
正極を作製した。まず、正極活物質としてのグラファイト(OMAL,0.95g)とポリテトラフルオロエチレン(PTFE,0.5g)とを混合し、得られた混合物を0.01g取り、正極材とした。負極活物質としての上記の配位構造体(銅錯体)を0.07gと、導電材としてのカーボンブラックを0.025gと、結着材としてのPTFEを0.005g混合し、得られた混合物を0.01g取り、負極材とした。電解液としてジエチルメチル(2メトキシエチル)アンモニウム・BF4を用いた。正極材を集電体に圧着すると共に、負極材を集電体に圧着し、電解液を介してこれらの電極を対向させて、評価セルを作製した。評価セルを用いて、充放電測定を行った。3.5Vまで充電したのち、0.1Vまで放電させるサイクルを10サイクル行った。
図4は、実施例1の評価セルの充放電測定結果である。図5は、実施例2の評価セルの充放電測定結果である。図4、5に示すように、実施例、1、2は、充放電することができることがわかった。このため、実施例1,2の配位構造体は、アニオンを可逆的に容易に移動させることができることがわかった。
Claims (7)
- Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ag及びCdから選ばれる1以上の金属イオンと、窒素を含み前記金属イオンに配位する2以上の非イオン性配位部位を有する有機化合物と、を含み、前記金属イオンに前記有機化合物が配位した繰返し構造を備え、前記繰返し構造内にアニオンを吸蔵及び放出する、配位構造体。
- 前記繰返し構造は、前記有機化合物の前記非イオン性配位部位が4配位四面体型に前記金属イオンに配位した構造である、請求項1に記載の配位構造体。
- 前記有機化合物は、含窒素複素環を有する官能基を前記非イオン性配位部位として備えている、請求項1又は2に記載の配位構造体。
- 前記有機化合物は、ピリジル基、ピリミジル基及びピラジル基のうち1以上を有する、請求項3に記載の配位構造体。
- 前記金属イオンは、Cu(I)、Cu(II)、Co(II)及びAg(I)のうち1以上である、請求項1〜4のいずれか1項に記載の配位構造体。
- 前記アニオンは、BF4 -、PF6 -及びCF3SO3 -のうち1以上を含む、請求項1〜5のいずれか1項に記載の配位構造体。
- 正極と、
請求項1〜6のいずれか1項に記載の配位構造体を含む負極と、
前記正極と前記負極との間に介在し前記アニオンを伝導するイオン伝導媒体と、を備え、前記アニオンの移動により充放電する、蓄電デバイス。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US10879015B2 (en) | 2017-12-08 | 2020-12-29 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Viologen compound, method for producing the same, negative electrode active material, and electricity storage device |
JP2021072412A (ja) * | 2019-11-01 | 2021-05-06 | 株式会社豊田中央研究所 | 金属有機構造体、蓄電デバイス用電極、蓄電デバイス及び金属有機構造体の製造方法 |
JP2021166132A (ja) * | 2020-04-06 | 2021-10-14 | 株式会社豊田中央研究所 | 蓄電デバイス |
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