JPWO2019218067A5 - - Google Patents
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- JPWO2019218067A5 JPWO2019218067A5 JP2020563789A JP2020563789A JPWO2019218067A5 JP WO2019218067 A5 JPWO2019218067 A5 JP WO2019218067A5 JP 2020563789 A JP2020563789 A JP 2020563789A JP 2020563789 A JP2020563789 A JP 2020563789A JP WO2019218067 A5 JPWO2019218067 A5 JP WO2019218067A5
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- 239000004020 conductor Substances 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 32
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 20
- 239000004917 carbon fiber Substances 0.000 claims description 20
- 229920003043 Cellulose fiber Polymers 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 12
- 239000011262 electrochemically active material Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- -1 aluminum cations Chemical class 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 6
- 239000012736 aqueous medium Substances 0.000 claims description 6
- 238000003490 calendering Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 239000002134 carbon nanofiber Substances 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite group Chemical group N(=O)[O-] IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 4
- 239000003880 polar aprotic solvent Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000011245 gel electrolyte Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000011244 liquid electrolyte Substances 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000005518 polymer electrolyte Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical compound CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012414 tert-butyl nitrite Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000002071 nanotube Substances 0.000 claims 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 claims 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- KVLCHQHEQROXGN-UHFFFAOYSA-N aluminium(1+) Chemical compound [Al+] KVLCHQHEQROXGN-UHFFFAOYSA-N 0.000 description 1
- 229940007076 aluminum cation Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
Description
企図される本発明の範囲から逸脱することなく、上述の実施形態のうちの１つまたは別のものに多数の修正を加えることができる。本出願で言及された参考文献、特許または科学論文文献はいずれも、それらの全体があらゆる目的で参照により本明細書に組み込まれる。
特定の実施形態では、例えば以下の項目が提供される。
（項目１）
－ 集電体として働く第１の導電性材料であり、前記第１の導電性材料の表面に、少なくとも１種の式Ｉ：
（式中、
ＦＧは親水性官能基であり、ｎは１～５の範囲の整数であるか、好ましくはｎは１～３の範囲であるか、好ましくはｎは１もしくは２であるか、またはより好ましくはｎは１である）
のアリール基がグラフトされた、第１の導電性材料と、
－ セルロース繊維を含むバインダーと、
－ 電気化学的活物質と
を含む、自立型電極であって、
前記自立型電極が第１および第２の表面を有する固体フィルムで作製され、
前記第１の導電性材料の濃度が、前記固体フィルムの前記第２の表面から前記第１の表面まで増大し、
前記電気化学的活物質の濃度が、前記固体フィルムの前記第１の表面から前記第２の表面まで増大する、
自立型電極。
（項目２）
第２の導電性材料をさらに含み、前記第２の導電性材料の濃度が、前記固体フィルムの前記第１の表面から前記第２の表面まで増大する、項目１に記載の自立型電極。
（項目３）
前記第１の導電性材料が炭素繊維を含む、項目１または２に記載の自立型電極。
（項目４）
前記炭素繊維が気相成長炭素繊維（ＶＧＣＦ）である、項目３に記載の自立型電極。
（項目５）
前記第１の表面が、前記第１の導電性材料を主に含む、項目１～４のいずれか一項に記載の自立型電極。
（項目６）
前記セルロース繊維が未改質セルロース繊維である、項目１～５のいずれか一項に記載の自立型電極。
（項目７）
前記セルロース繊維がアルミニウムカチオンを含まない、項目１～６のいずれか一項に記載の自立型電極。
（項目８）
前記セルロース繊維の平均長が、５ｎｍから５ｍｍの間、または２５０ｎｍから３ｍｍの間、または５００ｎｍから３ｍｍの間、または１μｍから３ｍｍの間、または１００μｍから３ｍｍの間、または２５０μｍから３ｍｍの間、または５００μｍから３ｍｍの間、または７５０μｍから２．５ｍｍの間、または１ｍｍから２．５ｍｍの間である、項目１～７のいずれか一項に記載の自立型電極。
（項目９）
前記セルロース繊維の平均長が０．５ｍｍから３ｍｍの間である、項目８に記載の自立型電極。
（項目１０）
前記第２の表面が、前記電気化学的活物質、および存在する場合、前記第２の導電性材料を主に含む、項目１～９のいずれか一項に記載の自立型電極。
（項目１１）
前記電気化学的活物質が、コアシェル構造の、炭素層でコーティングされた粒子の形態である、項目１～１０のいずれか一項に記載の自立型電極。
（項目１２）
前記炭素層に、項目１に記載の少なくとも１種の式Ｉのアリール基がグラフトされた、項目１１に記載の自立型電極。
（項目１３）
前記電気化学的活物質が、金属酸化物粒子、リチウム化金属酸化物粒子、金属リン酸塩粒子、リチウム化金属リン酸塩粒子、炭素系材料および活性有機材料から選択される、項目１～１２のいずれか一項に記載の自立型電極。
（項目１４）
前記金属が、チタン（Ｔｉ）、鉄（Ｆｅ）、マンガン（Ｍｎ）、バナジウム（Ｖ）、ニッケル（Ｎｉ）、コバルト（Ｃｏ）およびこれらのうちの少なくとも２つの組合せから選択される遷移金属である、項目１３に記載の自立型電極。
（項目１５）
正極である、項目１～１４のいずれか一項に記載の自立型電極。
（項目１６）
前記電気化学的活物質が、リチウム化リン酸鉄粒子（ＬｉＦｅＰＯ
４
）を含む、項目１５に記載の自立型電極。
（項目１７）
前記電気化学的活物質が、ピロメリット酸二無水物（ＰＭＤＡ）、１，４，５，８－ナフタレンテトラカルボン酸二無水物（ＮＴＣＤＡ）または３，４，９，１０－ペリレンテトラカルボン酸二無水物（ＰＴＣＤＡ）を含む、項目１５に記載の自立型電極。
（項目１８）
前記電気化学的活物質が、３，４，９，１０－ペリレンテトラカルボン酸二無水物（ＰＴＣＤＡ）を含む、項目１７に記載の自立型電極。
（項目１９）
負極である、項目１～１４のいずれか一項に記載の自立型電極。
（項目２０）
前記電気化学的活物質が、チタン酸リチウム（Ｌｉ
４
Ｔｉ
５
Ｏ
１２
）粒子を含む、項目１９に記載の自立型電極。
（項目２１）
前記電気化学的活物質が炭素系材料を含む、項目１９に記載の自立型電極。
（項目２２）
前記炭素系材料がグラフェンまたはグラファイトである、項目２１に記載の自立型電極。
（項目２３）
前記炭素系材料がグラファイトである、項目２１または２２に記載の自立型電極。
（項目２４）
前記第２の導電性材料に、項目１に記載の少なくとも１種の式Ｉのアリール基がグラフトされた、項目２～２３のいずれか一項に記載の自立型電極。
（項目２５）
前記第２の導電性材料が、カーボンブラック、アセチレンブラック、グラファイト、グラフェン、炭素繊維、炭素ナノ繊維、カーボンナノチューブおよびこれらのうちの少なくとも２つの組合せから選択される、項目２～２４のいずれか一項に記載の自立型電極。
（項目２６）
前記第２の導電性材料が、アセチレンブラック、炭素繊維、カーボンナノチューブおよびこれらのうちの少なくとも２つの組合せから選択される、項目２５に記載の自立型電極。
（項目２７）
前記第２の導電性材料が炭素繊維を含む、項目２６に記載の自立型電極。
（項目２８）
前記第２の導電性材料が、炭素繊維とアセチレンブラックの組合せを含む、項目２７に記載の自立型電極。
（項目２９）
前記第２の導電性材料が、炭素繊維とカーボンナノチューブの組合せを含む、項目２７に記載の自立型電極。
（項目３０）
前記炭素繊維が、気相成長炭素繊維（ＶＧＣＦ）である、項目２５～２９のいずれか一項に記載の自立型電極。
（項目３１）
前記炭素繊維が、少なくとも５０重量％の濃度で前記組合せに存在する、項目２５～３０のいずれか一項に記載の自立型電極。
（項目３２）
前記親水性官能基が、カルボン酸またはスルホン酸官能基である、項目１～３１のいずれか一項に記載の自立型電極。
（項目３３）
前記式Ｉのアリール基が、ｐ－安息香酸またはｐ－ベンゼンスルホン酸である、項目３２に記載の自立型電極。
（項目３４）
項目１～３３のいずれか一項に記載の自立型電極を製造するための方法であって、以下のステップ：
（ａ）第１の導電性材料に少なくとも１種の式Ｉのアリール基をグラフトするステップと、
（ｂ）セルロース繊維を含む水性混合物に、ステップ（ａ）で得られた改質された前記第１の導電性材料を分散して、第１の水性分散液を得るステップと、
（ｃ）前記第１の水性分散液を濾過膜上で濾過し、フィルムを得るステップと、
（ｄ）電気化学的活物質、および必要に応じて第２の導電性材料を水性媒体に分散し、第２の水性分散液を得るステップと、
（ｅ）前記第２の水性分散液を、ステップ（ｃ）で得られた前記フィルム上で濾過し、前記濾過膜上に自立型電極を生産するステップと、
（ｆ）前記濾過膜から前記自立型電極を剥離するステップと
を含む、方法。
（項目３５）
ステップ（ｃ）で得られた前記フィルムが、導電性材料に富む面およびセルロース繊維に富む面を含み、前記導電性材料に富む面が前記濾過膜に面している、項目３４に記載の方法。
（項目３６）
ステップ（ｃ）で得られた前記フィルムを乾燥するステップをさらに含む、項目３４または３５に記載の方法。
（項目３７）
前記電気化学的活物質が炭素層でコーティングされた粒子の形態であり、前記方法が、ステップ（ｄ）の前に、前記炭素層に少なくとも１種の式Ｉのアリール基をグラフトするステップをさらに含む、項目３４～３６のいずれか一項に記載の方法。
（項目３８）
ステップ（ｄ）の前に、前記第２の導電性材料に少なくとも１種の式Ｉのアリール基をグラフトするステップをさらに含む、項目３４～３７のいずれか一項に記載の方法。
（項目３９）
前記自立型電極をカレンダー加工するステップをさらに含む、項目３４～３８のいずれか一項に記載の方法。
（項目４０）
前記カレンダー加工するステップが、室温から約８０℃の間の温度で実行される、項目３９に記載の方法。
（項目４１）
前記カレンダー加工するステップが、約２５℃で実行される、項目４０に記載の方法。
（項目４２）
前記カレンダー加工するステップが、約５０℃～約８０℃の範囲の温度で実行される、項目４０に記載の方法。
（項目４３）
ステップ（ｆ）の前に、セルロース繊維を含む水性混合物を、ステップ（ｅ）で得られた前記自立型電極上で直接濾過することによってセパレータを生産するステップをさらに含む、項目３４～４２のいずれか一項に記載の方法。
（項目４４）
前記方法の前記グラフトするステップが、
（ｉ）式ＩＩ：
（式中、ＦＧおよびｎは項目１～２７のいずれか一項に記載の通りである）
のアニリンとジアゾ化剤を接触させることによってアリールジアゾニウムイオンを生成することと、
（ｉｉ）ステップ（ｉ）で生成された前記アリールジアゾニウムイオンを、前記電気化学的活物質の表面上の炭素層の炭素、または前記第１もしくは第２の導電性材料と反応させることと
を含む、項目３４～４３のいずれか一項に記載の方法。
（項目４５）
前記ジアゾ化剤が、前記炭素に対して０．０１～０．０４当量、または前記炭素に対して約０．０３当量の範囲で存在する、項目４４に記載の方法。
（項目４６）
前記ジアゾ化剤が、式ＩＩの前記アニリンに対して１～４当量、または式ＩＩの前記アニリンに対して約３当量の範囲で存在する、項目４４または４５に記載の方法。
（項目４７）
前記ジアゾ化剤が亜硝酸塩または亜硝酸アルキルである、項目４４～４６のいずれか一項に記載の方法。
（項目４８）
前記亜硝酸塩が亜硝酸ナトリウム（ＮａＮＯ
２
）である、項目４７に記載の方法。
（項目４９）
前記亜硝酸アルキルが亜硝酸ｔｅｒｔ－ブチル（ｔ－ＢｕＯＮＯ）である、項目４７に記載の方法。
（項目５０）
前記アリールジアゾニウムイオンが、ステップ（ｉ）および（ｉｉ）が同時に実施されるように、ｉｎ ｓｉｔｕで生成される、項目４４～４９のいずれか一項に記載の方法。
（項目５１）
前記グラフトするステップが酸性水性媒体中で実行される、項目３４～５０のいずれか一項に記載の方法。
（項目５２）
前記酸性水性媒体が硫酸水溶液である、項目５１に記載の方法。
（項目５３）
前記グラフトするステップが極性非プロトン性溶媒中で実行される、項目３４～５０のいずれか一項に記載の方法。
（項目５４）
前記極性非プロトン性溶媒がアセトニトリルである、項目５３に記載の方法。
（項目５５）
負極、正極および電解質を含む電気化学セルであって、前記負極および正極のうちの少なくとも１つが、項目１～３３のいずれか一項に記載の自立型電極である、電気化学セル。
（項目５６）
前記負極および前記正極の両方が自立型電極である、項目５５に記載の電気化学セル。
（項目５７）
セパレータをさらに含む、項目５５または５６に記載の電気化学セル。
（項目５８）
前記セパレータが、ポリプロピレンセパレータまたはポリプロピレン－ポリエチレン－ポリプロピレン（ＰＰ／ＰＥ／ＰＰ）セパレータまたはセルロースセパレータである、項目５７に記載の電気化学セル。
（項目５９）
前記セパレータがセルロースセパレータである、項目５８に記載の電気化学セル。
（項目６０）
前記セパレータが、セルロース繊維を含む水性混合物を、前記自立型電極上で直接濾過することによって得られた、項目５９に記載の電気化学セル。
（項目６１）
前記電解質が、溶媒中のリチウム塩を含む液体電解質である、項目５５～６０のいずれか一項に記載の電気化学セル。
（項目６２）
前記電解質が、溶媒および／または溶媒和ポリマー中のリチウム塩を含むゲル電解質である、項目５５～６０のいずれか一項に記載の電気化学セル。
（項目６３）
前記電解質が、溶媒和ポリマー中のリチウム塩を含む固体ポリマー電解質である、項目５５～６０のいずれか一項に記載の電気化学セル。
（項目６４）
項目５５～６３のいずれか一項に記載の少なくとも１つの電気化学セルを含む電池。
（項目６５）
リチウムもしくはリチウムイオン電池、ナトリウムもしくはナトリウムイオン電池、またはマグネシウムもしくはマグネシウムイオン電池から選択される、項目６４に記載の電池。
（項目６６）
リチウムイオン電池である、項目６４または６５に記載の電池。
Numerous modifications can be made to one or another of the embodiments described above without departing from the intended scope of the invention. Any references, patents or scientific dissertations referred to in this application are incorporated herein by reference in their entirety for any purpose.
In certain embodiments, for example, the following items are provided.
(Item 1)
-A first conductive material that acts as a current collector, and on the surface of the first conductive material, at least one type I:
(During the ceremony,
FG is a hydrophilic functional group, n is an integer in the range 1-5, preferably n is in the range 1-3, preferably n is 1 or 2, or more preferably. n is 1)
With the first conductive material grafted with the aryl group of
-With a binder containing cellulose fibers
-With electrochemical active material
Is a self-supporting electrode, including
The self-supporting electrode is made of a solid film having first and second surfaces.
The concentration of the first conductive material increases from the second surface of the solid film to the first surface.
The concentration of the electrochemically active material increases from the first surface to the second surface of the solid film.
Free-standing electrode.
(Item 2)
The self-supporting electrode according to item 1, further comprising a second conductive material, wherein the concentration of the second conductive material increases from the first surface to the second surface of the solid film.
(Item 3)
The self-supporting electrode according to item 1 or 2, wherein the first conductive material contains carbon fibers.
(Item 4)
The self-supporting electrode according to item 3, wherein the carbon fiber is a vapor phase grown carbon fiber (VGCF).
(Item 5)
The self-supporting electrode according to any one of items 1 to 4, wherein the first surface mainly contains the first conductive material.
(Item 6)
The self-standing electrode according to any one of items 1 to 5, wherein the cellulose fiber is an unmodified cellulose fiber.
(Item 7)
The self-standing electrode according to any one of items 1 to 6, wherein the cellulose fiber does not contain an aluminum cation.
(Item 8)
The average length of the cellulose fibers is between 5 nm and 5 mm, or between 250 nm and 3 mm, or between 500 nm and 3 mm, or between 1 μm and 3 mm, or between 100 μm and 3 mm, or between 250 μm and 3 mm, or The self-supporting electrode according to any one of items 1 to 7, which is between 500 μm and 3 mm, or between 750 μm and 2.5 mm, or between 1 mm and 2.5 mm.
(Item 9)
Item 8. The self-supporting electrode according to item 8, wherein the average length of the cellulose fibers is between 0.5 mm and 3 mm.
(Item 10)
The self-supporting electrode according to any one of items 1 to 9, wherein the second surface mainly contains the electrochemical active material and, if present, the second conductive material.
(Item 11)
The self-supporting electrode according to any one of items 1 to 10, wherein the electrochemical active material is in the form of particles coated with a carbon layer having a core-shell structure.
(Item 12)
The self-supporting electrode according to item 11, wherein the carbon layer is grafted with at least one aryl group of the formula I according to item 1.
(Item 13)
Items 1 to 12 in which the electrochemically active material is selected from metal oxide particles, lithium metal oxide particles, metal phosphate particles, lithium metal phosphate particles, carbon-based materials and active organic materials. The self-supporting electrode according to any one of the above.
(Item 14)
The metal is a transition metal selected from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co) and at least two combinations thereof. , Item 13. The self-supporting electrode.
(Item 15)
The self-supporting electrode according to any one of items 1 to 14, which is a positive electrode.
(Item 16)
The self-supporting electrode according to item 15, wherein the electrochemical active material contains lithium iron phosphate particles (LiFePO 4 ).
(Item 17)
The electrochemically active material is pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA) or 3,4,9,10-perylenetetracarboxylic dianhydride. The self-supporting electrode according to item 15, which comprises an anhydride (PTCDA).
(Item 18)
The self-supporting electrode according to item 17, wherein the electrochemical active material contains 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA).
(Item 19)
The self-supporting electrode according to any one of items 1 to 14, which is a negative electrode.
(Item 20)
The self-supporting electrode according to item 19, wherein the electrochemical active material contains lithium titanate (Li 4 Ti 5 O 12 ) particles.
(Item 21)
19. The self-supporting electrode according to item 19, wherein the electrochemical active material contains a carbon-based material.
(Item 22)
The self-supporting electrode according to item 21, wherein the carbon-based material is graphene or graphite.
(Item 23)
The self-supporting electrode according to item 21 or 22, wherein the carbon-based material is graphite.
(Item 24)
The self-supporting electrode according to any one of items 2 to 23, wherein at least one aryl group of the formula I according to item 1 is grafted onto the second conductive material.
(Item 25)
The second conductive material is selected from carbon black, acetylene black, graphite, graphene, carbon fiber, carbon nanofiber, carbon nanotube and at least two combinations thereof, any one of items 2 to 24. The self-supporting electrode described in the section.
(Item 26)
25. The self-supporting electrode according to item 25, wherein the second conductive material is selected from acetylene black, carbon fiber, carbon nanotubes and at least two combinations thereof.
(Item 27)
26. The self-supporting electrode according to item 26, wherein the second conductive material contains carbon fibers.
(Item 28)
27. The self-supporting electrode according to item 27, wherein the second conductive material comprises a combination of carbon fiber and acetylene black.
(Item 29)
27. The self-supporting electrode according to item 27, wherein the second conductive material comprises a combination of carbon fibers and carbon nanotubes.
(Item 30)
The self-supporting electrode according to any one of items 25 to 29, wherein the carbon fiber is a vapor phase grown carbon fiber (VGCF).
(Item 31)
The self-supporting electrode according to any one of items 25 to 30, wherein the carbon fibers are present in the combination at a concentration of at least 50% by weight.
(Item 32)
The self-supporting electrode according to any one of items 1 to 31, wherein the hydrophilic functional group is a carboxylic acid or a sulfonic acid functional group.
(Item 33)
32. The self-supporting electrode according to item 32, wherein the aryl group of the formula I is p-benzoic acid or p-benzenesulfonic acid.
(Item 34)
The method for manufacturing the self-supporting electrode according to any one of items 1 to 33, wherein the following steps:
(A) A step of grafting at least one aryl group of the formula I to the first conductive material,
(B) A step of dispersing the modified first conductive material obtained in step (a) in an aqueous mixture containing cellulose fibers to obtain a first aqueous dispersion.
(C) The step of filtering the first aqueous dispersion on a filtration membrane to obtain a film, and
(D) A step of dispersing the electrochemical active material and, if necessary, a second conductive material in an aqueous medium to obtain a second aqueous dispersion.
(E) A step of filtering the second aqueous dispersion on the film obtained in step (c) to produce a self-supporting electrode on the filter membrane.
(F) With the step of peeling the self-supporting electrode from the filter membrane
Including, how.
(Item 35)
34. The method of item 34, wherein the film obtained in step (c) includes a surface rich in conductive material and a surface rich in cellulose fibers, and the surface rich in conductive material faces the filtration membrane. ..
(Item 36)
34. The method of item 34 or 35, further comprising the step of drying the film obtained in step (c).
(Item 37)
The electrochemically active material is in the form of particles coated with a carbon layer, wherein the method further comprises grafting the carbon layer with at least one aryl group of formula I prior to step (d). The method according to any one of items 34 to 36, including.
(Item 38)
The method of any one of items 34-37, further comprising the step of grafting at least one aryl group of formula I to the second conductive material prior to step (d).
(Item 39)
The method according to any one of items 34 to 38, further comprising a step of calendaring the self-supporting electrode.
(Item 40)
39. The method of item 39, wherein the calendaring step is performed at a temperature between room temperature and about 80 ° C.
(Item 41)
40. The method of item 40, wherein the calendaring step is performed at about 25 ° C.
(Item 42)
40. The method of item 40, wherein the calendaring step is performed at a temperature in the range of about 50 ° C to about 80 ° C.
(Item 43)
Any of items 34-42, further comprising the step of producing a separator by directly filtering the aqueous mixture containing the cellulose fibers on the self-supporting electrode obtained in step (e) prior to step (f). The method described in item 1.
(Item 44)
The grafting step of the method
(I) Equation II:
(In the formula, FG and n are as described in any one of items 1 to 27).
To generate aryldiazonium ions by contacting aniline with a diazotizing agent,
(Ii) Reacting the aryldiazonium ion generated in step (i) with the carbon of the carbon layer on the surface of the electrochemical active material or the first or second conductive material.
The method according to any one of items 34 to 43, comprising.
(Item 45)
44. The method of item 44, wherein the diazotizing agent is present in the range of 0.01 to 0.04 equivalents relative to the carbon, or about 0.03 equivalents relative to the carbon.
(Item 46)
44. The method of item 44 or 45, wherein the diazotizing agent is present in the range of 1 to 4 equivalents to the aniline of formula II, or about 3 equivalents to the aniline of formula II.
(Item 47)
The method according to any one of items 44 to 46, wherein the diazotizing agent is nitrite or alkyl nitrite.
(Item 48)
47. The method of item 47, wherein the nitrite is sodium nitrite (NaNO 2 ).
(Item 49)
47. The method of item 47, wherein the alkyl nitrite is tert-butyl nitrite (t-BuONO).
(Item 50)
The method of any one of items 44-49, wherein the aryldiazonium ion is generated in situ such that steps (i) and (ii) are carried out simultaneously.
(Item 51)
35. The method of any one of items 34-50, wherein the grafting step is performed in an acidic aqueous medium.
(Item 52)
51. The method of item 51, wherein the acidic aqueous medium is an aqueous sulfuric acid solution.
(Item 53)
35. The method of any one of items 34-50, wherein the grafting step is performed in a polar aprotic solvent.
(Item 54)
53. The method of item 53, wherein the polar aprotic solvent is acetonitrile.
(Item 55)
An electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein at least one of the negative electrode and the positive electrode is a self-standing electrode according to any one of items 1 to 33.
(Item 56)
The electrochemical cell according to item 55, wherein both the negative electrode and the positive electrode are self-supporting electrodes.
(Item 57)
55. The electrochemical cell of item 55 or 56, further comprising a separator.
(Item 58)
58. The electrochemical cell according to item 57, wherein the separator is a polypropylene separator or a polypropylene-polyethylene-polypropylene (PP / PE / PP) separator or a cellulose separator.
(Item 59)
58. The electrochemical cell according to item 58, wherein the separator is a cellulose separator.
(Item 60)
The electrochemical cell according to item 59, wherein the separator is obtained by directly filtering an aqueous mixture containing cellulose fibers on the free-standing electrode.
(Item 61)
The electrochemical cell according to any one of items 55 to 60, wherein the electrolyte is a liquid electrolyte containing a lithium salt in a solvent.
(Item 62)
The electrochemical cell according to any one of items 55 to 60, wherein the electrolyte is a gel electrolyte containing a solvent and / or a lithium salt in a solvate polymer.
(Item 63)
The electrochemical cell according to any one of items 55 to 60, wherein the electrolyte is a solid polymer electrolyte containing a lithium salt in a solvated polymer.
(Item 64)
A battery comprising at least one electrochemical cell according to any one of items 55 to 63.
(Item 65)
The battery according to item 64, which is selected from a lithium or lithium ion battery, a sodium or sodium ion battery, or a magnesium or magnesium ion battery.
(Item 66)
The battery according to item 64 or 65, which is a lithium ion battery.
Claims (17)
（式中、
ＦＧは親水性官能基であり、ｎは１～５の範囲の整数であるか、好ましくはｎは１～３の範囲であるか、好ましくはｎは１もしくは２であるか、またはより好ましくはｎは１である）
のアリール基がグラフトされた、第１の導電性材料と、
－ セルロース繊維を含むバインダーと、
－ 電気化学的活物質と、
－ 必要に応じて第２の伝導性材料であり、前記第２の伝導性材料に、好ましくは少なくとも１種の式Ｉのアリール基がグラフトされた、第２の伝導性材料と
を含む、自立型電極であって、
前記自立型電極が第１および第２の表面を有する固体フィルムで作製され、
前記第１の導電性材料の濃度が、前記固体フィルムの前記第２の表面から前記第１の表面まで増大し、前記第１の表面が、好ましくは前記第１の導電性材料を主に含み、
前記電気化学的活物質、および存在する場合、前記第２の伝導性材料の濃度が、前記固体フィルムの前記第１の表面から前記第２の表面まで増大し、好ましくは前記第２の表面が、前記電気化学的活物質、および存在する場合、前記第２の伝導性材料を主に含む、
自立型電極。 -A first conductive material that acts as a current collector, and on the surface of the first conductive material, at least one type I:
(During the ceremony,
FG is a hydrophilic functional group, n is an integer in the range 1-5, preferably n is in the range 1-3, preferably n is 1 or 2, or more preferably. n is 1)
With the first conductive material grafted with the aryl group of
-With a binder containing cellulose fibers
-Electrochemically active material and
-A second conductive material, optionally, to which the second conductive material is preferably grafted with at least one aryl group of formula I.
Is a self-supporting electrode, including
The self-supporting electrode is made of a solid film having first and second surfaces.
The concentration of the first conductive material increases from the second surface of the solid film to the first surface, the first surface preferably predominantly containing the first conductive material. ,
The concentration of the electrochemically active material and, if present, the second conductive material increases from the first surface of the solid film to the second surface, preferably the second surface. , The electrochemically active material, and, if present, the second conductive material, predominantly.
Free-standing electrode.
（ｉｉ）負極であり、前記電気化学的活物質が、チタン酸リチウム（Ｌｉ ４ Ｔｉ ５ Ｏ １２ ）粒子または炭素系材料を含み、好ましくは前記炭素系材料がグラフェンまたはグラファイトであり、より好ましくはグラファイトである、
請求項１～４のいずれか一項に記載の自立型電極。 (I) A positive electrode , wherein the electrochemically active material is preferably lithium iron phosphate particles (LiFePO 4 ), pyromellitic acid dianhydride (PMDA), 1,4,5,8-naphthalenetetracarboxylic dians. Acid dianhydride (NTCDA) or 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) is included, more preferably the electrochemically active material is 3,4,9,10-perylenetetra. Contains carboxylic dianhydride (PTCDA); or
(Ii) The negative electrode, wherein the electrochemical active material comprises lithium titanate (Li 4 Ti 5 O 12 ) particles or a carbon-based material, preferably the carbon-based material is graphene or graphite, more preferably. Graphite ,
The self-supporting electrode according to any one of claims 1 to 4 .
（ａ）第１の導電性材料に少なくとも１種の式Ｉのアリール基をグラフトするステップと、
（ｂ）セルロース繊維を含む水性混合物に、ステップ（ａ）で得られた改質された前記第１の導電性材料を分散して、第１の水性分散液を得るステップと、
（ｃ）前記第１の水性分散液を濾過膜上で濾過し、フィルムを得るステップであって、前記フィルムが、好ましくは導電性材料に富む面およびセルロース繊維に富む面を含み、前記導電性材料に富む面が前記濾過膜に面している、ステップと、
（ｄ）電気化学的活物質、および必要に応じて第２の導電性材料を水性媒体に分散し、第２の水性分散液を得るステップと、
（ｅ）前記第２の水性分散液を、ステップ（ｃ）で得られた前記フィルム上で濾過し、前記濾過膜上に自立型電極を生産するステップと、
（ｆ）前記濾過膜から前記自立型電極を剥離するステップと
を含む、方法。 The method for manufacturing the self-supporting electrode according to any one of claims 1 to 7 , wherein the following steps:
(A) A step of grafting at least one aryl group of the formula I to the first conductive material,
(B) A step of dispersing the modified first conductive material obtained in step (a) in an aqueous mixture containing cellulose fibers to obtain a first aqueous dispersion.
(C) The step of filtering the first aqueous dispersion on a filtration membrane to obtain a film, wherein the film preferably contains a surface rich in a conductive material and a surface rich in cellulose fibers, and is said to be conductive. The material-rich surface faces the filter membrane, the step and
(D) A step of dispersing the electrochemical active material and, if necessary, a second conductive material in an aqueous medium to obtain a second aqueous dispersion.
(E) The step of filtering the second aqueous dispersion on the film obtained in step (c) to produce a self-supporting electrode on the filtration membrane.
(F) A method comprising the step of peeling the self-supporting electrode from the filtration membrane.
ステップ（ｄ）の前に、前記第２の導電性材料に少なくとも１種の式Ｉのアリール基をグラフトするステップ；および／または
前記自立型電極をカレンダー加工するステップであって、好ましくは前記カレンダー加工するステップが、室温から約８０℃の間の温度で、もしくは約５０℃～約８０℃の範囲の温度で、もしくは約２５℃の温度で実行される、ステップ；および／または
ステップ（ｆ）の前に、セルロース繊維を含む水性混合物を、ステップ（ｅ）で得られた前記自立型電極上で直接濾過することによってセパレータを生産するステップ
をさらに含み、前記電気化学的活物質が炭素層でコーティングされた粒子の形態であり、前記方法が、ステップ（ｄ）の前に、前記炭素層に少なくとも１種の式Ｉのアリール基をグラフトするステップをさらに含む、請求項８に記載の方法。 The step of drying the film obtained in step (c) ; and / or
Prior to step (d), the second conductive material is grafted with at least one aryl group of formula I; and / or
A step of calendaring the self-supporting electrode, preferably the calendaring step is at a temperature between room temperature and about 80 ° C., or at a temperature in the range of about 50 ° C. to about 80 ° C., or about 25 ° C. Steps performed at a temperature of ° C; and / or
Prior to step (f), a separator is produced by directly filtering the aqueous mixture containing cellulose fibers on the self-supporting electrode obtained in step (e).
The electrochemically active material is in the form of particles coated with a carbon layer, wherein the method comprises at least one aryl group of formula I in the carbon layer prior to step (d). The method of claim 8 , further comprising the step of grafting .
（ｉ）式ＩＩ：
（式中、ＦＧおよびｎは請求項１～６のいずれか一項に記載の通りである）
のアニリンとジアゾ化剤を接触させることによってアリールジアゾニウムイオンを生成することと、
（ｉｉ）ステップ（ｉ）で生成された前記アリールジアゾニウムイオンを、前記電気化学的活物質の表面上の炭素層の炭素、または前記第１もしくは第２の導電性材料と反応させることと
を含み、前記アリールジアゾニウムイオンが、好ましくはステップ（ｉ）および（ｉｉ）が同時に実施されるように、ｉｎ ｓｉｔｕで生成される、請求項８または９に記載の方法。 The grafting step of the method
(I) Equation II:
(In the formula, FG and n are as described in any one of claims 1 to 6 ).
To generate aryldiazonium ions by contacting aniline with a diazotizing agent,
(Ii) Including reacting the aryldiazonium ion generated in step (i) with the carbon of the carbon layer on the surface of the electrochemical active material or the first or second conductive material. The method of claim 8 or 9 , wherein the aryldiazonium ion is produced in situ such that steps (i) and (ii) are preferably carried out simultaneously .
A battery comprising at least one electrochemical cell according to any one of claims 14 to 16 , wherein the battery is preferably a lithium or lithium ion battery, a sodium or sodium ion battery, or a magnesium or magnesium ion battery. Batteries selected from, more preferably lithium ion batteries .
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| US62/728,301 | 2018-09-07 | ||
| PCT/CA2019/050657 WO2019218067A1 (en) | 2018-05-15 | 2019-05-15 | Cellulose-based self-supporting films for use in li-ion batteries |
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