EP4238150A1 - Organic battery - Google Patents
Organic batteryInfo
- Publication number
- EP4238150A1 EP4238150A1 EP21801549.3A EP21801549A EP4238150A1 EP 4238150 A1 EP4238150 A1 EP 4238150A1 EP 21801549 A EP21801549 A EP 21801549A EP 4238150 A1 EP4238150 A1 EP 4238150A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrode
- group
- compound
- composition
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims description 95
- 229920000642 polymer Polymers 0.000 claims description 71
- 150000001875 compounds Chemical class 0.000 claims description 61
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 52
- 150000003839 salts Chemical class 0.000 claims description 29
- 239000012528 membrane Substances 0.000 claims description 27
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 21
- 229920002313 fluoropolymer Polymers 0.000 claims description 20
- 239000004811 fluoropolymer Substances 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000002608 ionic liquid Substances 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 150000005677 organic carbonates Chemical class 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 150000004053 quinones Chemical group 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 150000007942 carboxylates Chemical group 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- QGMGHALXLXKCBD-UHFFFAOYSA-N 4-amino-n-(2-aminophenyl)benzamide Chemical group C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1N QGMGHALXLXKCBD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 239000011149 active material Substances 0.000 abstract description 7
- -1 perfluoro-2-propoxy-propyl group Chemical group 0.000 description 23
- 239000000243 solution Substances 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 14
- 239000011263 electroactive material Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N Vilsmeier-Haack reagent Natural products CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 9
- 239000011244 liquid electrolyte Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 6
- 229910010272 inorganic material Inorganic materials 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 101000666901 Oxyuranus scutellatus scutellatus Kunitz-type serine protease inhibitor taicotoxin Proteins 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000006479 redox reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 4
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910012223 LiPFe Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910006069 SO3H Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 2
- 150000004057 1,4-benzoquinones Chemical class 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910018828 PO3H2 Inorganic materials 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WFLOTYSKFUPZQB-OWOJBTEDSA-N (e)-1,2-difluoroethene Chemical group F\C=C\F WFLOTYSKFUPZQB-OWOJBTEDSA-N 0.000 description 1
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- 150000000191 1,4-naphthoquinones Chemical class 0.000 description 1
- HFNSTEOEZJBXIF-UHFFFAOYSA-N 2,2,4,5-tetrafluoro-1,3-dioxole Chemical class FC1=C(F)OC(F)(F)O1 HFNSTEOEZJBXIF-UHFFFAOYSA-N 0.000 description 1
- OHLSHRJUBRUKAN-UHFFFAOYSA-N 2,3-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1O OHLSHRJUBRUKAN-UHFFFAOYSA-N 0.000 description 1
- 150000004483 2,3-naphthoquinones Chemical class 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- IHZHYITXFSSZIZ-UHFFFAOYSA-N 2-isocyanatoethyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCN=C=O IHZHYITXFSSZIZ-UHFFFAOYSA-N 0.000 description 1
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- GXDMUOPCQNLBCZ-UHFFFAOYSA-N 3-(3-triethoxysilylpropyl)oxolane-2,5-dione Chemical compound CCO[Si](OCC)(OCC)CCCC1CC(=O)OC1=O GXDMUOPCQNLBCZ-UHFFFAOYSA-N 0.000 description 1
- GBAQKTTVWCCNHH-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propyl prop-2-enoate Chemical compound C[Si](Cl)(Cl)CCCOC(=O)C=C GBAQKTTVWCCNHH-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- ZCRUJAKCJLCJCP-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C=C ZCRUJAKCJLCJCP-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- WYTQXLFLAMZNNZ-UHFFFAOYSA-N 3-trihydroxysilylpropane-1-sulfonic acid Chemical compound O[Si](O)(O)CCCS(O)(=O)=O WYTQXLFLAMZNNZ-UHFFFAOYSA-N 0.000 description 1
- GDCRYMZNGGCWEH-UHFFFAOYSA-N 3-trihydroxysilylpropanoic acid Chemical compound OC(=O)CC[Si](O)(O)O GDCRYMZNGGCWEH-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- JPZOAVGMSDSWSW-UHFFFAOYSA-N 4,6-dichloropyrimidin-2-amine Chemical compound NC1=NC(Cl)=CC(Cl)=N1 JPZOAVGMSDSWSW-UHFFFAOYSA-N 0.000 description 1
- IHBDUARGLPMOND-UHFFFAOYSA-N 4-(2-trichlorosilylethyl)benzenesulfonyl chloride Chemical compound Cl[Si](Cl)(Cl)CCC1=CC=C(S(Cl)(=O)=O)C=C1 IHBDUARGLPMOND-UHFFFAOYSA-N 0.000 description 1
- NYIDSUMRGUILGR-UHFFFAOYSA-N 4-(2-trimethoxysilylethyl)benzenesulfonyl chloride Chemical compound CO[Si](OC)(OC)CCC1=CC=C(S(Cl)(=O)=O)C=C1 NYIDSUMRGUILGR-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- AONXMESMHBIONB-UHFFFAOYSA-N 4-isocyanatobutyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCN=C=O AONXMESMHBIONB-UHFFFAOYSA-N 0.000 description 1
- ZQNXOVPHAFNYIZ-UHFFFAOYSA-N 5-isocyanatopentyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCCN=C=O ZQNXOVPHAFNYIZ-UHFFFAOYSA-N 0.000 description 1
- HUHGKBBIOFENOY-UHFFFAOYSA-N 6-isocyanatohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCCCN=C=O HUHGKBBIOFENOY-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910014585 C2-Ce Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000282866 Euchlaena mexicana Species 0.000 description 1
- JNCMHMUGTWEVOZ-UHFFFAOYSA-N F[CH]F Chemical compound F[CH]F JNCMHMUGTWEVOZ-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 1
- 229910007157 Si(OH)3 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
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- PVLBXNICXUCXTA-UHFFFAOYSA-N [2-hydroxy-3-(3-triethoxysilylpropylamino)propyl] prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCNCC(O)COC(=O)C=C PVLBXNICXUCXTA-UHFFFAOYSA-N 0.000 description 1
- GTOVGJUKOALMTN-UHFFFAOYSA-N acetic acid;n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CO[Si](OC)(OC)CCCNCCN GTOVGJUKOALMTN-UHFFFAOYSA-N 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- KRLBTHCAZSDQCI-UHFFFAOYSA-N anthracene-1,10-dione Chemical class C1=CC=C2C=C3C(=O)C=CC=C3C(=O)C2=C1 KRLBTHCAZSDQCI-UHFFFAOYSA-N 0.000 description 1
- RGHILYZRVFRRNK-UHFFFAOYSA-N anthracene-1,2-dione Chemical class C1=CC=C2C=C(C(C(=O)C=C3)=O)C3=CC2=C1 RGHILYZRVFRRNK-UHFFFAOYSA-N 0.000 description 1
- LSOTZYUVGZKSHR-UHFFFAOYSA-N anthracene-1,4-dione Chemical class C1=CC=C2C=C3C(=O)C=CC(=O)C3=CC2=C1 LSOTZYUVGZKSHR-UHFFFAOYSA-N 0.000 description 1
- PQJKLTRMSHJEEN-UHFFFAOYSA-N anthracene-1,5-dione Chemical class O=C1C=CC=C2C=C3C(=O)C=CC=C3C=C21 PQJKLTRMSHJEEN-UHFFFAOYSA-N 0.000 description 1
- LAXLIRXGCCAXHW-UHFFFAOYSA-N anthracene-1,7-dione Chemical class C1=CC(=O)C2=CC3=CC(=O)C=CC3=CC2=C1 LAXLIRXGCCAXHW-UHFFFAOYSA-N 0.000 description 1
- RSAFJKGIUBIAJP-UHFFFAOYSA-N anthracene-2,3-dione Chemical class C1=CC=CC2=CC3=CC(=O)C(=O)C=C3C=C21 RSAFJKGIUBIAJP-UHFFFAOYSA-N 0.000 description 1
- SWYXZZAQKFGYFF-UHFFFAOYSA-N anthracene-2,6-dione Chemical class O=C1C=CC2=CC3=CC(=O)C=CC3=CC2=C1 SWYXZZAQKFGYFF-UHFFFAOYSA-N 0.000 description 1
- RLISRKPLQXUHMV-UHFFFAOYSA-N anthracene-2,9-dione Chemical class C1=CC=C2C(=O)C3=CC(=O)C=CC3=CC2=C1 RLISRKPLQXUHMV-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
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- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002704 decyl 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])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- VUWZPRWSIVNGKG-UHFFFAOYSA-N fluoromethane Chemical compound F[CH2] VUWZPRWSIVNGKG-UHFFFAOYSA-N 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- JXLQREJGIDQFJP-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)acetamide Chemical compound CO[Si](OC)(OC)CCCNC(C)=O JXLQREJGIDQFJP-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 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
- UBVMBXTYMSRUDX-UHFFFAOYSA-N n-prop-2-enyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCC=C UBVMBXTYMSRUDX-UHFFFAOYSA-N 0.000 description 1
- UKYHUQYCBBUNIA-UHFFFAOYSA-N naphthalene-1,5-dione Chemical class O=C1C=CC=C2C(=O)C=CC=C21 UKYHUQYCBBUNIA-UHFFFAOYSA-N 0.000 description 1
- MMMBIWJLWVIRIS-UHFFFAOYSA-N naphthalene-1,7-dione Chemical class C1=CC(=O)C2=CC(=O)C=CC2=C1 MMMBIWJLWVIRIS-UHFFFAOYSA-N 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
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001282 organosilanes Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-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
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000002000 scavenging effect Effects 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
- 125000001339 silanediyl group Chemical group [H][Si]([H])(*)* 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- KEIBTGABMNALIT-UHFFFAOYSA-N triethoxy(2-isocyanatoethyl)silane Chemical compound CCO[Si](OCC)(OCC)CCN=C=O KEIBTGABMNALIT-UHFFFAOYSA-N 0.000 description 1
- ASUUSZXVXTVKDD-UHFFFAOYSA-N triethoxy(4-isocyanatobutyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCN=C=O ASUUSZXVXTVKDD-UHFFFAOYSA-N 0.000 description 1
- IWQBIRQQKBICKW-UHFFFAOYSA-N triethoxy(5-isocyanatopentyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCN=C=O IWQBIRQQKBICKW-UHFFFAOYSA-N 0.000 description 1
- QKJDKLUGDDTSNP-UHFFFAOYSA-N triethoxy(6-isocyanatohexyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCCN=C=O QKJDKLUGDDTSNP-UHFFFAOYSA-N 0.000 description 1
- BOTMPGMIDPRZGP-UHFFFAOYSA-N triethoxy(isocyanatomethyl)silane Chemical compound CCO[Si](OCC)(OCC)CN=C=O BOTMPGMIDPRZGP-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
Definitions
- the present invention pertains to an electrode-forming composition, to use of said electrode-forming composition in a process for the manufacture of an electrode comprising an organic active material, to said electrode and to a secondary battery comprising said electrode.
- Lithium batteries are electrical cells that enable reversible storage of electrical energy, which can be recuperated when it is required.
- Existing technology of lithium batteries rely on lithium exchange between at least one host structure which is typically an inorganic material.
- the counter-ion is specific to the crystal structure of the inorganic compound due to size restrictions in the crystal lattice, ionic conductivity, and reversibility of the redox reaction. This inherently restricts the versatility of inorganic compounds, where the same cathode material cannot be used for different series of alkali metal batteries such as lithium and sodium-ion.
- One of the biggest challenges for inorganic complexes is that they typically require extraction and synthesis techniques that are harmful to the environment. Extraction can release toxic materials that are otherwise trapped underground. Synthesis can create large amounts of heavy metal waste and often requires energy intensive processing.
- the organic active materials are less expensive and with a minor footprint in terms of environment impact.
- organic materials obtained by organic synthesis can easily be modified for improving and changing their properties.
- oligomeric or polymeric organic active materials have been developed to overcome some issues related to the thermal stability and their solubility in the liquid electrolyte.
- Li batteries have brought safety issues caused by its leakage and inherent explosive nature, e.g., combustion of the organic solvent, generating volatile gaseous species, which are flammable.
- organic electrodes comprising an organic active material, hereinafter referred to as organic electrodes, suitable for use in secondary batteries free from liquid electrolytes.
- the organic electrode of the invention is obtainable by applying one or more layers of the electrode-forming composition of the invention directly onto a metal collector.
- composition (C1) comprising:
- liquid medium comprising at least one organic carbonate or at least one ionic liquid
- solvent (S) different from said medium (L), wherein the compound (EA) comprises an organic molecule or polymer exhibiting either n-type, p-type or bipolar redox behaviour.
- composition (C1) of the invention advantageously further comprises at least one conductive compound [compound (C)].
- the present invention pertains to the use of the electrode-forming composition [composition (C1)] of the invention in a process for the manufacture of an electrode [electrode (E)], said process comprising:
- step (iii) applying the composition (C1) provided in step (ii) onto the metal substrate provided in step (i) thereby providing an assembly comprising a metal substrate coated with at least one layer (L1) consisting of said composition (C1);
- step (iv) drying the assembly provided in step (iii) to evaporate the at least one solvent (S) thereby providing an electrode [electrode (E)].
- the electrode (E) of the invention is particularly suitable for use in secondary batteries.
- the secondary battery of the invention is preferably an alkaline or an alkaline-earth secondary battery.
- the secondary battery of the invention is more preferably a lithium secondary battery.
- the present invention provides a secondary battery comprising: - a positive electrode,
- Figure 1 shows the voltage (V) of the cell of Example 1 in function of the time duration (h) during the successive charges and discharges at C/10 rate and 22°C, between 1.5 and 3.5V.
- Figure 2 shows the capacity of the cell of Example 1 during the cycling at C/10 rate and 22°C.
- Figure 3 shows the voltage (V) of the cell of Example 2 in function of the time duration (h) during the successive charges and discharges at C/100 rate and 22°C, between 2 and 4V.
- Figure 4 shows the capacity of the cell of Example 2 during the cycling at C/100 rate and 22°C.
- partially fluorinated fluoropolymer is intended to denote a polymer comprising recurring units derived from at least one fluorinated monomer and, optionally, at least one hydrogenated monomer, wherein at least one of said fluorinated monomer and said hydrogenated monomer comprises at least one hydrogen atom.
- fluorinated monomer it is hereby intended to denote an ethylenically unsaturated monomer comprising at least one fluorine atom.
- hydrophilic monomer it is hereby intended to denote an ethylenically unsaturated monomer comprising at least one hydrogen atom and free from fluorine atoms.
- fluorinated monomer is understood to mean that the polymer (FF) may comprise recurring units derived from one or more than one fluorinated monomers.
- fluorinated monomers is understood, for the purposes of the present invention, both in the plural and the singular, that is to say that they denote both one or more than one fluorinated monomers as defined above.
- the term “at least one hydrogenated monomer” is understood to mean that the polymer (FF) may comprise recurring units derived from one or more than one hydrogenated monomers.
- the expression “hydrogenated monomers” is understood, for the purposes of the present invention, both in the plural and the singular, that is to say that they denote both one or more than one hydrogenated monomers as defined above.
- the polymer (FF) typically comprises recurring units derived from at least one fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one hydrogenated monomer different from said functional hydrogenated monomer comprising at least one carboxylic acid end group.
- the polymer (FF) is typically obtainable by polymerization of at least one fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one hydrogenated monomer different from said functional hydrogenated monomer comprising at least one carboxylic acid end group.
- fluorinated monomer comprise at least one hydrogen atom, it is designated as hydrogen-containing fluorinated monomer.
- fluorinated monomer is designated as per(halo)fluorinated monomer.
- the fluorinated monomer may further comprise one or more other halogen atoms (Cl, Br, I).
- Non-limiting examples of suitable fluorinated monomers include, notably, the followings:
- fluoroolefins such as vinylidene fluoride, vinyl fluoride, 1 ,2-difluoroethylene and trifluoroethylene;
- chloro- and/or bromo- and/or iodo-C2-Ce fluoroolefins such as chlorotrifluoroethylene
- CF2 CFORfi wherein Rfi is a Ci-Ce fluoro- or perfluoroalkyl, e.g. CF3, C2F5, C3F7 ;
- - CF2 CFOXO (per)fluoro-oxyalkylvinylethers wherein Xo is a C1-C12 alkyl group, a C1-C12 oxyalkyl group or a C1-C12 (per)fluorooxyalkyl group having one or more ether groups, such as perfluoro-2-propoxy-propyl group;
- - (per)fluoroalkylvinylethers of formula CF2 CFOCF2ORf2 wherein Rf2 is a Ci-Ce fluoro- or perfluoroalkyl group, e.g. CF3, C2F5, C3F7 or a Ci-Ce (per)fluorooxyalkyl group having one or more ether groups such as -C2F5- O-CF3;
- - functional (per)fluoro-oxyalkylvinylethers of formula CF2 CFOYo wherein Yo is a C1-C12 alkyl group or (per)fluoroalkyl group, a C1-C12 oxyalkyl group or a C1-C12 (per)fluorooxyalkyl group having one or more ether groups and Yo comprising a carboxylic or sulfonic acid group, in its acid, acid halide or salt form;
- the polymer (FF) is either a partially fluorinated fluoropolymer comprising recurring units derived from at least one hydrogen-containing fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one fluorinated monomer different from said hydrogen-containing fluorinated monomer or it is a partially fluorinated fluoropolymer comprising recurring units derived from at least one hydrogen-containing fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group, optionally, at least one fluorinated monomer different from said hydrogencontaining fluorinated monomer and, optionally, at least one hydrogenated monomer different from said functional hydrogenated monomer comprising at least one carboxylic acid end group.
- the fluorinated monomer be a per(halo)fluorinated monomer such as, for instance, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene or a perfluoroalkylvinylether
- the polymer (FF) is a partially fluorinated fluoropolymer comprising recurring units derived from at least one per(halo)fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group, at least one hydrogenated monomer different from said functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one fluorinated monomer different from said per(halo)fluorinated monomer.
- the polymer (FF) may be amorphous or semi-crystalline.
- amorphous is hereby intended to denote a polymer (FF) having a heat of fusion of less than 5 J/g, preferably of less than 3 J/g, more preferably of less than 2 J/g, as measured according to ASTM D-3418-08.
- FF polymer having a heat of fusion of from 10 to 90 J/g, preferably of from 30 to 60 J/g, more preferably of from 35 to 55 J/g, as measured according to ASTM D3418-08.
- the polymer (FF) is preferably semi-crystalline.
- the polymer (FF) comprises preferably at least 0.01 % by moles, more preferably at least 0.05% by moles, even more preferably at least 0.1 % by moles of recurring units derived from at least one functional hydrogenated monomer comprising at least one carboxylic acid end group.
- the polymer (FF) comprises preferably at most 10% by moles, more preferably at most 5% by moles, even more preferably at most 2% by moles, of recurring units derived from at least one functional hydrogenated monomer comprising at least one carboxylic acid end group.
- Determination of average mole percentage of recurring units derived from at least one functional hydrogenated monomer comprising at least one carboxylic acid end group in the polymer (FF) can be performed by any suitable method. Mention can be notably made of acid-base titration methods or NMR methods.
- the polymer (FF) is preferably a partially fluorinated fluoropolymer comprising recurring units derived from vinylidene fluoride (VDF), at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one fluorinated monomer different from VDF [polymer (FF-1)].
- VDF vinylidene fluoride
- FF-1 fluorinated monomer different from VDF
- the polymer (FF-1) preferably comprises recurring units derived from:
- VDF vinylidene fluoride
- VFi vinyl fluoride
- CFE chlorotrifluoroethylene
- HFP hexafluoropropylene
- TFE tetrafluoroethylene
- TrFE trifluoroethylene
- PMVE perfluoromethylvinylether
- the functional hydrogenated monomer comprising at least one carboxylic acid end group is preferably selected from the group consisting of (meth)acrylic monomers of formula (I): wherein each of Ri, R2 and R3, equal to or different from each other, is independently a hydrogen atom or a C1-C3 hydrocarbon group.
- Non-limiting examples of functional hydrogenated monomers comprising at least one carboxylic acid end group include, notably, acrylic acid (AA) and methacrylic acid.
- the polymer (FF) is advantageously a linear polymer [polymer (FFL)] comprising linear sequences of recurring units derived from at least one fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one hydrogenated monomer different from said functional hydrogenated monomer comprising at least one carboxylic acid end group.
- the polymer (FF) is thus typically distinguishable from graft polymers.
- the polymer (FF) is advantageously a random polymer [polymer (FFR)] comprising linear sequences of randomly distributed recurring units derived from at least one fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one hydrogenated monomer different from said functional hydrogenated monomer comprising at least one carboxylic acid end group.
- FFR random polymer
- randomly distributed recurring units is intended to denote the percent ratio between the average number of sequences of at least one functional hydrogenated monomers (%), said sequences being comprised between two recurring units derived from at least one fluorinated monomer, and the total average number of recurring units derived from at least one functional hydrogenated monomer (%).
- each of the recurring units derived from at least one functional hydrogenated monomer is isolated, that is to say that a recurring unit derived from a functional hydrogenated monomer is comprised between two recurring units of at least one fluorinated monomer, the average number of sequences of at least one functional hydrogenated monomer equals the average total number of recurring units derived from at least one functional hydrogenated monomer, so that the fraction of randomly distributed recurring units derived from at least one functional hydrogenated monomer is 100%: this value corresponds to a perfectly random distribution of recurring units derived from at least one functional hydrogenated monomer.
- the polymer (FF) is thus typically distinguishable from block polymers.
- the polymer (FF) is typically obtainable by emulsion polymerization or suspension polymerization.
- organic electro-active compound [compound (EA)] is intended to denote a compound that comprises an organic molecule or polymer exhibiting either n-type, p-type or bipolar-type redox behaviour.
- Organic materials suitable for use in organic electrodes are commonly grouped based on the role they perform in the redox reaction: p-type materials lead during the redox reaction to anionic charge compensation/release, n-type materials plays with cation as counter-ion, while bipolar-type materials used both type of charges compensation (p- type reaction with anion) or (n-type reaction with cation) depending on the applied voltage.
- Suitable compounds (EA) are selected from the group consisting of: a) n-type materials such as
- - imide groups for example, polyimide groups
- p-type materials such as:
- conjugated carbonyl group means 2 carbonyl groups conjugated via one or more double bonds, such a group being able to be represented schematically by the following simplified formula (I):
- Redox compounds corresponding to the specificities mentioned above can be quinone compounds, which designate hydrocarbon compounds comprising one or more benzene rings, on the one or more hydrogen atoms are replaced by two oxygen atoms thus each forming a double bond with a carbon atom, such compounds thus comprising two conjugated carbonyl groups capable of scavenging electrons.
- the redox compounds of the family of quinone compounds have the particular advantage of being of low environmental impact, of being often inexpensive and can be of biological origin (certain quinone compounds found in plants, fungi, bacteria even in some animals).
- the quinone compounds can be chosen from benzoquinone compounds (such as 1 ,4-benzoquinone compounds, 1 ,2- benzoquinone compounds), naphthoquinone compounds (such as 1 ,4- naphthoquinone compounds, compounds 1 , 2-naphthoquinones, 1 ,5- naphthoquinone compounds, 1 ,7-naphthoquinone compounds, 2,3- naphthoquinone compounds, 2,6-naphthoquinone compounds) and anthraquinone compounds (such as 9,10- compounds) anthraquinones, 1 ,2-anthraquinone compounds, 1 ,4-anthraquinone compounds, 1 ,10- anthraquinone compounds, 2,9-anthraquinone compounds, 1 ,5- anthraquinone compounds, 1 ,7-anthraquinone compounds, 2,3- anthra
- it may be a benzoquinone compound in enolate form substituted with at least one carboxylate group, and even more specifically a 1 ,4-benzoquinone compound substituted with at least one carboxylate group (for example, two carboxylate groups) and optionally another substituent such as those defined above, an example of this type corresponding to the following formula (VI):
- X 1 to X 4 represent, independently of one another, a cation and X 5 and X 6 represent, independently of each other, a hydrogen atom or a group -SO3H, a particular compound corresponding to this specificity being that of the following formula (VII): with M representing a divalent cation, such as a magnesium cation, M establishing a bridge between the oxygen atom of the carboxylate group and the oxygen atom of the enolate group.
- M representing a divalent cation, such as a magnesium cation
- Polymers including in the backbone or at chain ends any redox-active unit based on p-type materials, n-type materials or bipolar-type material which contribute to the redox reaction by donating or accepting electrons can be suitably used as organic electro-active material (EA) in the electron composition of the present invention.
- EA organic electro-active material
- liquid medium [medium (L)] is intended to denote a medium comprising one or more substances in the liquid state at 20°C under atmospheric pressure.
- the medium (L) is typically free from one or more solvents (S).
- the choice of the medium (L) is not particularly limited provided that it is suitable for solubilising the salt (M) to provide an electrolyte solution (EL).
- the salt (M) is typically selected from the group consisting of:
- the amount of the medium (L) in the composition (C1) is typically at least 40% by weight, preferably at least 50% by weight, more preferably at least 60% by weight, based on the total weight of said medium (L) and the polymer (FF).
- composition (C1) comprising at least 50% by weight of the medium (L), based on the total weight of said medium (L) and the polymer (FF).
- the medium (L) comprises at least one organic carbonate.
- Non-limiting examples of suitable organic carbonates include, notably, ethylene carbonate, propylene carbonate, mixtures of ethylene carbonate and propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl- methyl carbonate, butylene carbonate, vinylene carbonate, fluoroethylene carbonate, fluoropropylene carbonate and mixtures thereof.
- the medium (L) comprises at least one ionic liquid and, optionally, at least one organic carbonate.
- the term ’’ionic liquid is intended to denote a compound formed by the combination of a positively charged cation and a negatively charged anion in the liquid state at temperatures below 100°C under atmospheric pressure.
- the ionic liquid typically contains:
- a positively charged cation selected from the group consisting of imidazolium, pyridinium, pyrrolidinium and piperidinium ions optionally containing one or more C1-C30 alkyl groups, and
- a negatively charged anion selected from the group consisting of halides, perfluorinated anions and borates.
- Non-limiting examples of C1-C30 alkyl groups include, notably, methyl, ethyl, propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, 2,2-dimethyl-propyl, hexyl, 2,3-dimethyl-2-butyl, heptyl, 2,2- dimethyl-3-pentyl, 2-methyl-2-hexyl, octyl, 4-methyl-3-heptyl, nonyl, decyl, undecyl and dodecyl groups.
- the positively charged cation of the ionic liquid is preferably selected from the group consisting of:
- Rn and R22 equal to or different from each other, independently represent a Ci-Cs alkyl group and R33, R44, R55 and Ree, equal to or different from each other, independently represent a hydrogen atom or a C1-C30 alkyl group, preferably a C1-C18 alkyl group, more preferably a C1- Cs alkyl group, and
- Rn and R22 equal to or different from each other, independently represent a Ci-Cs alkyl group and R33, R44, R55, Ree and R77, equal to or different from each other, independently represent a hydrogen atom or a C1-C30 alkyl group, preferably a C1-C18 alkyl group, more preferably a C1- Cs alkyl group.
- the positively charged cation of the ionic liquid is more preferably selected from the group consisting of:
- the negatively charged anion of the ionic liquid is preferably selected from the group consisting of:
- the ionic liquid even more preferably contains a pyrrolidinium cation of formula (ll-A) as defined above and a perfluorinated anion selected from the group consisting of bis(trifluoromethylsulphonyl)imide of formula (SO 2 CF 3 )2N-, hexafluorophosphate of formula PFe and tetrafluoroborate of formula BF4-.
- the electrolyte solution (EL) is typically prepared by dissolving a metal salt (M) in the liquid medium (L) so as to provide an electrolyte solution wherein the concentration of the salt is preferably 0.3 M or more, more preferably 0.7 M or more, and still more preferably 1.0 M or more. In addition, an upper limit thereof is preferably 2.5 M or less, more preferably 2.0 M or less, and still more preferably 1 .6 M or less.
- electrolyte solution consists of LiPFe and a mixture of carbonates, more preferably a mixture of ethylene carbonate, propylene carbonate and vinylene carbonate.
- the concentration of LiPFe in the medium (L) of the electrolyte solution (EL) is advantageously of about 1 M.
- the choice of the solvent (S) is not particularly limited provided that it is suitable for solubilising the polymer (FF).
- the solvent (S) is typically selected from the group consisting of:
- alcohols such as methyl alcohol, ethyl alcohol and diacetone alcohol
- ketones such as acetone, methylethylketone, methylisobutyl ketone, diisobutylketone, cyclohexanone and isophorone,
- - linear or cyclic amides such as N,N-diethylacetamide, N,N- dimethylacetamide, dimethylformamide and N-methyl-2-pyrrolidone, and
- the electrode-forming composition [composition (C1)] can comprise at least one conductive compound [compound (C)], that is to say a compound capable of imparting to the electrode, in which they are incorporated, electronic conductivity, these additives possibly being, for example, carbonaceous materials such as carbon black, carbon nanotubes, carbon fibers (in particular, carbon fibers obtained in the vapor phase known by the abbreviation VGCF), graphite in powder form, graphite fibers and mixtures thereof.
- conductive compound compound (C)]
- these additives possibly being, for example, carbonaceous materials such as carbon black, carbon nanotubes, carbon fibers (in particular, carbon fibers obtained in the vapor phase known by the abbreviation VGCF), graphite in powder form, graphite fibers and mixtures thereof.
- the organic electro-active material (EA) can be trapped into the porous structure of carbonaceous materials used as conductive compound (C).
- the Applicants have found that the cyclability of the battery is thus advantageously enhanced.
- the present invention pertains to the use of the electrode-forming composition [composition (C1)] of the invention in a process for the manufacture of an electrode [electrode (E)], said process comprising:
- step (iii) applying the composition (C1) provided in step (ii) onto the metal substrate provided in step (i) thereby providing an assembly comprising a metal substrate coated with at least one layer (L1) consisting of said composition (C1);
- step (iv) drying the assembly provided in step (iii) to evaporate the at least one solvent (S) thereby providing an electrode [electrode (E)].
- the metal substrate typically acts as a metal collector.
- the metal substrate is generally a foil, mesh or net made from a metal such as copper, aluminum, iron, stainless steel, nickel, titanium or silver.
- the composition (C1 ) is applied onto the metal substrate typically by any suitable procedures such as casting, printing and roll coating.
- step (iii) may be repeated, typically one or more times, by applying the composition (C1) provided in step (ii) onto the electrode provided in step (iv).
- drying may be performed either under atmospheric pressure or under vacuum.
- drying may be performed under modified atmosphere, e.g. under an inert gas, typically exempt notably from moisture (water vapour content of less than 0.001 % v/v).
- the drying temperature will be selected so as to effect removal by evaporation of one or more solvents (S) from the electrode (E) of the invention.
- the electrode (E) of the invention is preferably free from one or more solvents (S).
- the layer (L1) of the electrode (E) of the invention typically has a thickness comprised between 10 pm and 500 pm, preferably between 50 pm and 250 pm, more preferably between 70 pm and 150 pm.
- the electrodes (E) according to the present invention are gelled electrodes, which means that, in addition to the presence of an organic electro-active material as defined above, they comprise (or even consist of) a composite material comprising (or even consisting of) a polymeric matrix conventionally formed from one or more polymers capable of gelling on contact with a liquid electrolyte, more commonly called gelling polymer (FF), the active electrode material and optionally one or more several electronically conductive additives, such as those mentioned above, the liquid electrolyte being confined within the polymer matrix.
- FF gelling polymer
- the electrode (E) of the invention is particularly suitable for use in secondary batteries, especially in alkaline or alkaline-earth secondary batteries, more especially in lithium-ion secondary batteries, said batteries being advantageously free from liquid electrolytes while still exhibiting outstanding capacity values.
- the present invention thus provides an electrode [electrode (E)] obtainable by the process defined above, said electrode (E) comprising:
- composition (C2) comprising:
- liquid medium comprising at least one organic carbonate or at least one ionic liquid
- the electrode-forming composition (C1) of the present invention is particularly suitable for the manufacturing of positive electrodes for secondary batteries.
- the present invention thus provides a secondary battery comprising:
- the present invention pertains to a secondary battery comprising:
- the negative electrode of the secondary battery of the present invention is typically a metal substrate, preferably a foil made from a metal such as lithium or zinc.
- membrane is intended to denote a discrete, generally thin, interface which moderates permeation of chemical species in contact with it.
- This interface may be homogeneous, that is, completely uniform in structure (dense membrane), or it may be chemically or physically heterogeneous, for example containing voids, pores or holes of finite dimensions (porous membrane).
- the membrane typically comprises at least one material selected from inorganic materials and organic materials.
- Non-limiting examples of suitable organic materials include, notably, polymers, said polymers being preferably selected from the group consisting of partially fluorinated fluoropolymers.
- the membrane is advantageously free from one or more compounds (EA) as defined above.
- the membrane may further comprise at least one medium (L) as defined above and at least one salt (M) as defined above.
- the membrane comprises a fluoropolymer hybrid organic/inorganic composite, said hybrid being obtainable by a process comprising hydrolysing and/or condensing a composition comprising:
- X 4 -mAY m At least one metal compound [compound (M1)] of formula (X): X 4 -mAY m (X) wherein m is an integer from 1 to 4, A is a metal selected from the group consisting of Si, Ti and Zr, Y is a hydrolysable group and X is a hydrocarbon group, optionally comprising one or more functional groups,
- the selection of the hydrolysable group Y of the compound (M1) of formula (X) as defined above is not particularly limited provided that it enables under appropriate conditions the formation of a -O-AH bond.
- the hydrolysable group Y of the compound (M1) of formula (X) as defined above is typically selected from the group consisting of halogen atoms, preferably being a chlorine atom, hydrocarboxy groups, acyloxy groups and hydroxyl groups.
- the compound (M1) is preferably of formula (X-A): R A 4-m A(OR B ) m (X-A) wherein m is an integer from 1 to 4, and, according to certain embodiments, from 1 to 3, A is a metal selected from the group consisting of Si, Ti and Zr, R A and R B , equal to or different from each other and at each occurrence, are independently selected from C1-C18 hydrocarbon groups, wherein R A optionally comprises at least one functional group.
- Non-limiting examples of functional groups include, notably, epoxy group, carboxylic acid group (in its acid, ester, amide, anhydride, salt or halide form), sulphonic group (in its acid, ester, salt or halide form), hydroxyl group, phosphoric acid group (in its acid, ester, salt, or halide form), thiol group, amine group, quaternary ammonium group, ethylenically unsaturated group (like vinyl group), cyano group, urea group, organo- silane group, aromatic group.
- functional groups include, notably, epoxy group, carboxylic acid group (in its acid, ester, amide, anhydride, salt or halide form), sulphonic group (in its acid, ester, salt or halide form), hydroxyl group, phosphoric acid group (in its acid, ester, salt, or halide form), thiol group, amine group, quaternary ammonium group, ethylenically
- the compound (M1) of formula (X) as defined above be a functional compound (M1), it is more preferably of formula (X-B): R A ’ 4-m A(OR B ’) m (X-B) wherein m is an integer from 1 to 3, A is a metal selected from the group consisting of Si, Ti and Zr, R A ’, equal to or different from each other and at each occurrence, is a C1-C12 hydrocarbon group comprising at least one functional group and R B ’, equal to or different from each other and at each occurrence, is a C1-C5 linear or branched alkyl group, preferably R B ’ being a methyl or ethyl group.
- non-functional compounds (M1) are notably tri methoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane (TEOS), tetramethyltitanate, tetraethyltitanate, tetra-n-propyltitanate, tetraisopropyltitanate, tetra-n-butyltitanate, tetra-isobutyl titanate, tetra-tert- butyl titanate, tetra-n-pentyltitanate, tetra-n-hexyltitanate, tetraisooctyltitanate, tetra-n-lauryl titanate, tetraethylzirconate, tetra-n- propylzirconate, tetraisopropylzirconate, tetramethylt
- the membrane comprises a fluoropolymer hybrid organic/inorganic composite, at least one liquid medium [medium (L)] as defined above and at least one metal salt [salt (M)] as defined above, said hybrid being obtainable by a process comprising hydrolysing and/or condensing a composition comprising: - at least one partially fluorinated fluoropolymer comprising recurring units derived from at least one functional hydrogenated monomer comprising at least one hydroxyl end group,
- the selection of the hydrolysable group Y’ of the compound (M2) of formula (XI) as defined above is not particularly limited provided that it enables under appropriate conditions the formation of a -O-AH bond.
- the hydrolysable group Y’ of the compound (M2) of formula (XI) as defined above is typically selected from the group consisting of halogen atoms, preferably being a chlorine atom, hydrocarboxy groups, acyloxy groups and hydroxyl groups.
- the compound (M2) is preferably of formula (Xl-A):
- Non-limiting examples of suitable compounds (M2) include the followings: trimethoxysilyl methyl isocyanate, triethoxysilyl methyl isocyanate, trimethoxysilyl ethyl isocyanate, triethoxysilyl ethyl isocyanate, trimethoxysilyl propyl isocyanate, triethoxysilyl propyl isocyanate, trimethoxysilyl butyl isocyanate, triethoxysilyl butyl isocyanate, trimethoxysilyl pentyl isocyanate, triethoxysilyl pentyl isocyanate, trimethoxysilyl hexyl isocyanate and triethoxysilyl hexyl isocyanate.
- the secondary battery comprises:
- a membrane between said positive electrode and said negative electrode, a membrane, wherein at least one of the positive electrode and the negative electrode is an electrode [electrode (E)] according to the invention, and wherein the membrane is a membrane comprising a fluoropolymer hybrid organic/inorganic composite as defined above.
- the secondary battery of the present invention comprises:
- the positive electrode is an electrode [electrode (E)] according to the invention
- the negative electrode is a metal substrate, preferably a foil made from a metal such as lithium or zinc
- the membrane is a membrane comprising a fluoropolymer hybrid organic/inorganic composite as defined above.
- Polymer (1) VDF-HEA (0.4% by moles)-HFP (2.4% by moles) polymer having a viscosity of 0.11 l/g in DMF at 25°C.
- Electrolyte medium (EL-1) 1 M solution of LiPFe in ethylene carbonate (EC)Zpropylene carbonate (PC) (1/1 by volume) comprising vinylene carbonate (VC) (2% by weight).
- Polymer (EA-1) Poly(N-n-hexyl-3,4,9,10-perylene tetracarboxylic)imide (PTCI):
- DBTDL dibutyl tin dilaurate
- TEOS tetraethoxysilane.
- TSPI 3-(triethoxysilyl)propyl isocyanate.
- Intrinsic viscosity (q) [dl/g] was measured using the following equation on the basis of dropping time, at 25°C, of a solution obtained by dissolving polymer (A) in N,N-dimethylformamide at a concentration of about 0.2 g/dl using a Ubbelhode viscosimeter: where c is polymer concentration [g/dl], q r is the relative viscosity, i.e. the ratio between the dropping time of sample solution and the dropping time of solvent, r
- the polymer (1) (1.5 g) was dissolved in 8.5 g of acetone at 60°C thereby providing a solution containing 15% by weight of said polymer (1).
- the solution was homogeneous and transparent after homogenization at room temperature.
- DBTDL (0.015 g) was then added.
- the solution was homogenized at 60°C.
- TSPI (0.060 g) was added thereto.
- the quantity of DBTDL was calculated to be 10% by moles vs. TSPI.
- TSPI itself was calculated to be 1.1 % by mole vs. the polymer (1).
- the solution was kept at 60°C for about 90 min so as to let isocyanate functional groups of TSPI to react with the hydroxyl groups of the polymer (1).
- the liquid electrolyte (EL-1) was added to the solution so obtained.
- TEOS was then added thereto.
- the quantity of TEOS was calculated from the weight ratio (m(SiO2) I m(polymer(1))) assuming total conversion of TEOS into SiO . This ratio was 10%.
- n(formic acid) I n(TEOS) 7.8.
- the solution mixture was spread with a constant thickness onto a PET substrate using a tape casting machine (doctor blade) in a dry room (dew point: - 40°C). The thickness was controlled by the distance between the knife and the PET film.
- the solvent was quickly evaporated from the solution mixture and the membrane was obtained. After a few hours, the membrane was detached from the PET substrate. The membrane so obtained had a constant thickness of 45 pm.
- Example 1 Coin cell with Polymer (EA-1)
- a solution of polymer (FF-A) in acetone (10% by weight) was prepared at 60°C and then brought to room temperature.
- a composition comprising a blend of 18.7% by weight of C-ENERGY® SUPER C65 carbon black (CB) and 81.3% by weight of polymer (EA-1 ) was grinded in dry condition by using a mortar and then was added to the solution so obtained in a weight ratio of 80/20 ((CB+(EA-1))/polymer (FF-A)).
- the electrolyte medium (EL-1) was added to the mixture.
- the weight ratio [m (electrolyte) I (m(electrolyte) + m(polymer (FF-A))] x 100 was 75%.
- the solution mixture was spread with a constant thickness of 600 pm onto a metal collector using a tape casting machine (doctor blade). The thickness was controlled by the distance between the knife and the metal collector. The thickness of the wet layer of the cathode so obtained was about 340 m. After calendering the wet layer of the cathode was about 110 pm. Cathode loading was about 10.3 mg/cm 2 (0.05 mAh/cm 2 ).
- a coin cell was prepared by placing the membrane prepared according to the general procedure as detailed above between the cathode just described and a lithium metal as counter electrode.
- Example 2 Coin cell with Organic Molecule (EA-2)
- a solution of polymer (FF-A) in acetone (10% by weight) was prepared at 60°C and then brought to room temperature.
- a composition comprising a blend of 18.7% by weight of C-ENERGY® SUPER C65 carbon black (CB) and 81 .3% by weight of polymer (EA-1 ) was grinded in dry condition by using a mortar and then was added to the solution so obtained in a weight ratio of 80/20 ((CB+(EA-1))/polymer (FF-A)).
- the electrolyte medium (EL-1) was added to the mixture.
- the weight ratio [m (electrolyte) I (m(electrolyte) + m(polymer (FF-A))] x 100 was 85,7%.
- the solution mixture was spread with a constant thickness of 600pm directly onto the metal collector using a tape casting machine (doctor blade). The thickness was controlled by the distance between the knife and the metal collector. The thickness of the wet layer of the cathode so obtained was about 182 pm. Cathode loading was about 3.9 mg/cm 2 (0.39 mAh/cm 2 ).
- a coin cell was prepared by placing the membrane prepared according to the general procedure as detailed above between the cathode just described and a lithium metal as counter electrode. Trials at C/100 were run 4 cycles keeping roughly a specific capacity recovered of about 58-70 mAh/g.
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Abstract
The present invention pertains to an electrode-forming composition, to use of said electrode-forming composition in a process for the manufacture of an electrode comprising an organic active material, to said electrode and to a secondary battery comprising said electrode.
Description
Organic battery
Cross-reference to related applications
[0001] This application claims priority to European application No.
20306309.4 filed on November 2, 2020, the whole content of this application being incorporated herein by reference for all purposes.
Technical Field
[0001] The present invention pertains to an electrode-forming composition, to use of said electrode-forming composition in a process for the manufacture of an electrode comprising an organic active material, to said electrode and to a secondary battery comprising said electrode.
Background Art
[0002] Lithium batteries are electrical cells that enable reversible storage of electrical energy, which can be recuperated when it is required. Existing technology of lithium batteries rely on lithium exchange between at least one host structure which is typically an inorganic material.
[0003] These inorganic materials rely on changes in metal oxidation state for charge storage and a concomitant balancing of the charged structure with specific counter-ions.
[0004] In many cases the counter-ion is specific to the crystal structure of the inorganic compound due to size restrictions in the crystal lattice, ionic conductivity, and reversibility of the redox reaction. This inherently restricts the versatility of inorganic compounds, where the same cathode material cannot be used for different series of alkali metal batteries such as lithium and sodium-ion. One of the biggest challenges for inorganic complexes is that they typically require extraction and synthesis techniques that are harmful to the environment. Extraction can release toxic materials that are otherwise trapped underground. Synthesis can create large amounts of heavy metal waste and often requires energy intensive processing.
Moreover, the use extensively of inorganic active materials like NMC, LFP, LCO and others will be soon a case of great concern in terms of sustainability.
[0005] The need is thus felt for new alternative electrode materials.
[0006] Good alternatives to existing inorganic materials are organic molecules or electroactive polymers, which are enabling reversible redox reactions.
[0007] The organic active materials are less expensive and with a minor footprint in terms of environment impact.
[0008] In addition, organic materials obtained by organic synthesis can easily be modified for improving and changing their properties. For example, oligomeric or polymeric organic active materials have been developed to overcome some issues related to the thermal stability and their solubility in the liquid electrolyte.
[0009] In fact, one of the major problems with the use of organic molecules in Li- batteries is their solubility in organic solvents, which are typically used in liquid electrolytes for Li batteries.
[0010] Moreover, the presence of a liquid electrolyte in Li batteries has brought safety issues caused by its leakage and inherent explosive nature, e.g., combustion of the organic solvent, generating volatile gaseous species, which are flammable.
[0011] Therefore, the use of a safe battery containing no inorganic active materials is well desired for the future of this technology, while keeping the good properties of the current Li-battery technology.
Summary of invention
[0012] It has been now surprisingly found that by using the electrode-forming composition of the invention it is possible to manufacture electrodes comprising an organic active material, hereinafter referred to as organic electrodes, suitable for use in secondary batteries free from liquid electrolytes.
[0013] The organic electrode of the invention is obtainable by applying one or more layers of the electrode-forming composition of the invention directly onto a metal collector.
[0014] In a first instance, the present invention pertains to electrode-forming composition [composition (C1)] comprising:
- at least one partially fluorinated fluoropolymer comprising recurring units
derived from at least one fluorinated monomer and at least one functional hydrogenated monomer comprising at least one carboxylic acid end group [polymer (FF)],
- at least one organic electro-active compound [compound (EA)],
- at least one liquid medium [medium (L)] comprising at least one organic carbonate or at least one ionic liquid,
- at least one metal salt [salt (M)], and
- at least one solvent [solvent (S)] different from said medium (L), wherein the compound (EA) comprises an organic molecule or polymer exhibiting either n-type, p-type or bipolar redox behaviour.
[0015] The composition (C1) of the invention advantageously further comprises at least one conductive compound [compound (C)].
[0016] In a second instance, the present invention pertains to the use of the electrode-forming composition [composition (C1)] of the invention in a process for the manufacture of an electrode [electrode (E)], said process comprising:
(i) providing a metal substrate;
(ii) providing the electrode-forming composition [composition (C1)] as above defined;
(iii) applying the composition (C1) provided in step (ii) onto the metal substrate provided in step (i) thereby providing an assembly comprising a metal substrate coated with at least one layer (L1) consisting of said composition (C1); and
(iv) drying the assembly provided in step (iii) to evaporate the at least one solvent (S) thereby providing an electrode [electrode (E)].
[0017] The electrode (E) of the invention is particularly suitable for use in secondary batteries.
[0018] The secondary battery of the invention is preferably an alkaline or an alkaline-earth secondary battery.
[0019] The secondary battery of the invention is more preferably a lithium secondary battery.
[0020] In a further instance, thus, the present invention provides a secondary battery comprising:
- a positive electrode,
- a negative electrode, and
- between said positive electrode and said negative electrode, a membrane, wherein at least one of the positive electrode and the negative electrode is an electrode [electrode (E)] according to the invention.
Brief description of drawings
[0021] Figure 1 shows the the voltage (V) of the cell of Example 1 in function of the time duration (h) during the successive charges and discharges at C/10 rate and 22°C, between 1.5 and 3.5V.
[0022] Figure 2 shows the capacity of the cell of Example 1 during the cycling at C/10 rate and 22°C.
[0023] Figure 3 shows the the voltage (V) of the cell of Example 2 in function of the time duration (h) during the successive charges and discharges at C/100 rate and 22°C, between 2 and 4V.
[0024] Figure 4 shows the capacity of the cell of Example 2 during the cycling at C/100 rate and 22°C.
Description of embodiments
[0025] For the purpose of the present invention, the term “partially fluorinated fluoropolymer” is intended to denote a polymer comprising recurring units derived from at least one fluorinated monomer and, optionally, at least one hydrogenated monomer, wherein at least one of said fluorinated monomer and said hydrogenated monomer comprises at least one hydrogen atom.
[0026] By the term “fluorinated monomer” it is hereby intended to denote an ethylenically unsaturated monomer comprising at least one fluorine atom.
[0027] By the term “hydrogenated monomer” it is hereby intended to denote an ethylenically unsaturated monomer comprising at least one hydrogen atom and free from fluorine atoms.
[0028] The term “at least one fluorinated monomer” is understood to mean that the polymer (FF) may comprise recurring units derived from one or more than one fluorinated monomers. In the rest of the text, the expression “
fluorinated monomers” is understood, for the purposes of the present invention, both in the plural and the singular, that is to say that they denote both one or more than one fluorinated monomers as defined above.
[0029] The term “at least one hydrogenated monomer” is understood to mean that the polymer (FF) may comprise recurring units derived from one or more than one hydrogenated monomers. In the rest of the text, the expression “hydrogenated monomers” is understood, for the purposes of the present invention, both in the plural and the singular, that is to say that they denote both one or more than one hydrogenated monomers as defined above.
[0030] The polymer (FF) typically comprises recurring units derived from at least one fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one hydrogenated monomer different from said functional hydrogenated monomer comprising at least one carboxylic acid end group.
[0031] The polymer (FF) is typically obtainable by polymerization of at least one fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one hydrogenated monomer different from said functional hydrogenated monomer comprising at least one carboxylic acid end group.
[0032] Should the fluorinated monomer comprise at least one hydrogen atom, it is designated as hydrogen-containing fluorinated monomer.
[0033] Should the fluorinated monomer be free of hydrogen atoms, it is designated as per(halo)fluorinated monomer.
[0034] The fluorinated monomer may further comprise one or more other halogen atoms (Cl, Br, I).
[0035] Non-limiting examples of suitable fluorinated monomers include, notably, the followings:
- C2-C8 perfluoroolefins such as tetrafluoroethylene and hexafluoropropylene;
- C2-C8 hydrogenated fluoroolefins such as vinylidene fluoride, vinyl fluoride, 1 ,2-difluoroethylene and trifluoroethylene;
- perfluoroalkylethylenes of formula CH2=CH-Rro wherein Rm is a Ci-Ce
perfluoroalkyl;
- chloro- and/or bromo- and/or iodo-C2-Ce fluoroolefins such as chlorotrifluoroethylene;
- (per)fluoroalkylvinylethers of formula CF2=CFORfi wherein Rfi is a Ci-Ce fluoro- or perfluoroalkyl, e.g. CF3, C2F5, C3F7 ;
- CF2=CFOXO (per)fluoro-oxyalkylvinylethers wherein Xo is a C1-C12 alkyl group, a C1-C12 oxyalkyl group or a C1-C12 (per)fluorooxyalkyl group having one or more ether groups, such as perfluoro-2-propoxy-propyl group;
- (per)fluoroalkylvinylethers of formula CF2=CFOCF2ORf2 wherein Rf2 is a Ci-Ce fluoro- or perfluoroalkyl group, e.g. CF3, C2F5, C3F7 or a Ci-Ce (per)fluorooxyalkyl group having one or more ether groups such as -C2F5- O-CF3;
- functional (per)fluoro-oxyalkylvinylethers of formula CF2=CFOYo wherein Yo is a C1-C12 alkyl group or (per)fluoroalkyl group, a C1-C12 oxyalkyl group or a C1-C12 (per)fluorooxyalkyl group having one or more ether groups and Yo comprising a carboxylic or sulfonic acid group, in its acid, acid halide or salt form;
- fluorodioxoles, preferably perfluorodioxoles.
[0036] Should the fluorinated monomer be a hydrogen-containing fluorinated monomer such as, for instance, vinylidene fluoride, trifluoroethylene or vinyl fluoride, the polymer (FF) is either a partially fluorinated fluoropolymer comprising recurring units derived from at least one hydrogen-containing fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one fluorinated monomer different from said hydrogen-containing fluorinated monomer or it is a partially fluorinated fluoropolymer comprising recurring units derived from at least one hydrogen-containing fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group, optionally, at least one fluorinated monomer different from said hydrogencontaining fluorinated monomer and, optionally, at least one hydrogenated
monomer different from said functional hydrogenated monomer comprising at least one carboxylic acid end group.
[0037] Should the fluorinated monomer be a per(halo)fluorinated monomer such as, for instance, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene or a perfluoroalkylvinylether, the polymer (FF) is a partially fluorinated fluoropolymer comprising recurring units derived from at least one per(halo)fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group, at least one hydrogenated monomer different from said functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one fluorinated monomer different from said per(halo)fluorinated monomer.
[0038] The polymer (FF) may be amorphous or semi-crystalline.
[0039] The term “amorphous” is hereby intended to denote a polymer (FF) having a heat of fusion of less than 5 J/g, preferably of less than 3 J/g, more preferably of less than 2 J/g, as measured according to ASTM D-3418-08.
[0040] The term “semi-crystalline” is hereby intended to denote a polymer (FF) having a heat of fusion of from 10 to 90 J/g, preferably of from 30 to 60 J/g, more preferably of from 35 to 55 J/g, as measured according to ASTM D3418-08.
[0041] The polymer (FF) is preferably semi-crystalline.
[0042] The polymer (FF) comprises preferably at least 0.01 % by moles, more preferably at least 0.05% by moles, even more preferably at least 0.1 % by moles of recurring units derived from at least one functional hydrogenated monomer comprising at least one carboxylic acid end group.
[0043] The polymer (FF) comprises preferably at most 10% by moles, more preferably at most 5% by moles, even more preferably at most 2% by moles, of recurring units derived from at least one functional hydrogenated monomer comprising at least one carboxylic acid end group.
[0044] Determination of average mole percentage of recurring units derived from at least one functional hydrogenated monomer comprising at least one carboxylic acid end group in the polymer (FF) can be performed by any
suitable method. Mention can be notably made of acid-base titration methods or NMR methods.
[0045] The polymer (FF) is preferably a partially fluorinated fluoropolymer comprising recurring units derived from vinylidene fluoride (VDF), at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one fluorinated monomer different from VDF [polymer (FF-1)].
[0046] The polymer (FF-1) preferably comprises recurring units derived from:
- at least 60% by moles, preferably at least 75% by moles, more preferably at least 85% by moles of vinylidene fluoride (VDF),
- from 0.01 % to 20% by moles, preferably from 0.05% to 15% by moles, more preferably from 0.1 % to 10% by moles of at least one functional hydrogenated monomer comprising at least one carboxylic acid end group, and
- optionally, from 0.1% to 15% by moles, preferably from 0.1 % to 12% by moles, more preferably from 0.1% to 10% by moles of at least one fluorinated monomer selected from vinyl fluoride (VFi), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), tetrafluoroethylene (TFE), trifluoroethylene (TrFE) and perfluoromethylvinylether (PMVE).
[0047] The functional hydrogenated monomer comprising at least one carboxylic acid end group is preferably selected from the group consisting of (meth)acrylic monomers of formula (I):
wherein each of Ri, R2 and R3, equal to or different from each other, is independently a hydrogen atom or a C1-C3 hydrocarbon group.
[0048] Non-limiting examples of functional hydrogenated monomers comprising at least one carboxylic acid end group include, notably, acrylic acid (AA) and methacrylic acid.
[0049] The polymer (FF) is advantageously a linear polymer [polymer (FFL)] comprising linear sequences of recurring units derived from at least one fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one hydrogenated monomer different from said functional hydrogenated monomer comprising at least one carboxylic acid end group.
[0050] The polymer (FF) is thus typically distinguishable from graft polymers.
[0051] The polymer (FF) is advantageously a random polymer [polymer (FFR)] comprising linear sequences of randomly distributed recurring units derived from at least one fluorinated monomer, at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one hydrogenated monomer different from said functional hydrogenated monomer comprising at least one carboxylic acid end group.
[0052] The expression “randomly distributed recurring units” is intended to denote the percent ratio between the average number of sequences of at least one functional hydrogenated monomers (%), said sequences being comprised between two recurring units derived from at least one fluorinated monomer, and the total average number of recurring units derived from at least one functional hydrogenated monomer (%).
[0053] When each of the recurring units derived from at least one functional hydrogenated monomer is isolated, that is to say that a recurring unit derived from a functional hydrogenated monomer is comprised between two recurring units of at least one fluorinated monomer, the average number of sequences of at least one functional hydrogenated monomer equals the average total number of recurring units derived from at least one functional hydrogenated monomer, so that the fraction of randomly distributed recurring units derived from at least one functional hydrogenated monomer is 100%: this value corresponds to a perfectly random distribution of recurring units derived from at least one functional hydrogenated monomer. Thus, the larger is the number of isolated recurring units derived from at least one functional hydrogenated monomer with respect to the total number of recurring units derived from at least one
functional hydrogenated monomer, the higher will be the percentage value of fraction of randomly distributed recurring units derived from at least one functional hydrogenated monomer.
[0054] The polymer (FF) is thus typically distinguishable from block polymers.
[0055] The polymer (FF) is typically obtainable by emulsion polymerization or suspension polymerization.
[0056] For the purpose of the present invention, the term “organic electro-active compound [compound (EA)]” is intended to denote a compound that comprises an organic molecule or polymer exhibiting either n-type, p-type or bipolar-type redox behaviour.
[0057] Organic materials suitable for use in organic electrodes are commonly grouped based on the role they perform in the redox reaction: p-type materials lead during the redox reaction to anionic charge compensation/release, n-type materials plays with cation as counter-ion, while bipolar-type materials used both type of charges compensation (p- type reaction with anion) or (n-type reaction with cation) depending on the applied voltage. Suitable compounds (EA) are selected from the group consisting of: a) n-type materials such as
- conjugated carbonyl groups such as quinones or anhydrides
- conjugated enolic or enolate groups;
- carboxylate groups, such as lithiated carboxylate groups; or
- disulfide groups;
- azo groups;
- imide groups (for example, polyimide groups); b) p-type materials such as:
- nitroxide groups;
- thioether groups;
- heteroaromatic groups such as polyviologenes;
- aromatic amine groups such as dianiline derivatives; c) bipolar-type materials such as hydrocarbons and conjugated nitrogen systems.
[0058] It is specified that the term “conjugated carbonyl group” means 2 carbonyl groups conjugated via one or more double bonds, such a group being able to be represented schematically by the following simplified formula (I):
[0059] It is specified that, by enolic or enolate group, is meant a group corresponding respectively to the following simplified formulas (II) and (III):
(II) (III) wherein X represents a monovalent cation such as lithium.
[0060] Redox compounds corresponding to the specificities mentioned above can be quinone compounds, which designate hydrocarbon compounds comprising one or more benzene rings, on the one or more hydrogen atoms are replaced by two oxygen atoms thus each forming a double bond with a carbon atom, such compounds thus comprising two conjugated carbonyl groups capable of scavenging electrons.
[0061] The redox compounds of the family of quinone compounds have the particular advantage of being of low environmental impact, of being often inexpensive and can be of biological origin (certain quinone compounds found in plants, fungi, bacteria even in some animals).
[0062] More specifically, the quinone compounds can be chosen from benzoquinone compounds (such as 1 ,4-benzoquinone compounds, 1 ,2- benzoquinone compounds), naphthoquinone compounds (such as 1 ,4- naphthoquinone compounds, compounds 1 , 2-naphthoquinones, 1 ,5- naphthoquinone compounds, 1 ,7-naphthoquinone compounds, 2,3-
naphthoquinone compounds, 2,6-naphthoquinone compounds) and anthraquinone compounds (such as 9,10- compounds) anthraquinones, 1 ,2-anthraquinone compounds, 1 ,4-anthraquinone compounds, 1 ,10- anthraquinone compounds, 2,9-anthraquinone compounds, 1 ,5- anthraquinone compounds, 1 ,7-anthraquinone compounds, 2,3- anthraquinone compounds, 2,6-anthraquinone compounds, at least one other substituent chosen from -N(CH3)2, -NH2, -OR, -OH, -SH, -CH3, -SiRs, -F, -Cl, -C2H3, -CHO, -COOCH3, -CF3, -ON, -COOH, -PO3H2, -SO3H, NO2, -COOM, -COOR, -SO3M, -COR, -C = NCHR'R ", with R, R 'and R' 'representing, independently of one another, H or an alkyl group and M representing Li, Na, K or Mg.
[0063] Other redox compounds corresponding to the specificities mentioned above can be quinone compounds in their enolate form, that is to say in which the conjugated carbonyl groups = C-CO- are transformed into -C = COX- groups (with X being a monovalent cation, such as lithium), and optionally by another substituent chosen from -N(CH3)2 , -NH2, -OR, -OH, - SH, -CH3, -SiR3, -F, -Cl, -C2H3, -CHO, -COOCH3, -CF3, -CN, -COOH, - PO3H2, -SO3H, NO2 , -COOM, -COOR, -SO3M, -COR, -C = NCHR'R ", with R, R 'and R' 'representing, independently of each other, H or an alkyl group and M representing Li, Na, K or Mg.
[0064] More specifically, it may be a benzoquinone compound in enolate form substituted with at least one carboxylate group, and even more specifically a 1 ,4-benzoquinone compound substituted with at least one carboxylate group (for example, two carboxylate groups) and optionally another substituent such as those defined above, an example of this type corresponding to the following formula (VI):
in which X1 to X4 represent, independently of one another, a cation and X5 and X6 represent, independently of each other, a hydrogen atom or a group -SO3H, a particular compound corresponding to this specificity being that of the following formula (VII):
with M representing a divalent cation, such as a magnesium cation, M establishing a bridge between the oxygen atom of the carboxylate group and the oxygen atom of the enolate group.
[0065] Polymers including in the backbone or at chain ends any redox-active unit based on p-type materials, n-type materials or bipolar-type material which contribute to the redox reaction by donating or accepting electrons can be suitably used as organic electro-active material (EA) in the electron composition of the present invention.
[0066] Some specific examples of organic electro-active compounds (EA) are for instance listed in Table 1 of Tyler B. Schon, Bryony T. McAllister, Peng-Fei Li and Dwight S. Sefero, Chem. Soc. Rev., 2016, 45, 6345.
[0067] For the purpose of the present invention, the term “liquid medium [medium (L)]” is intended to denote a medium comprising one or more substances in the liquid state at 20°C under atmospheric pressure.
[0068] The medium (L) is typically free from one or more solvents (S).
[0069] The choice of the medium (L) is not particularly limited provided that it is suitable for solubilising the salt (M) to provide an electrolyte solution (EL).
[0070] The salt (M) is typically selected from the group consisting of:
(a) Mel, Me(PF6)n, Me(BF4)n, Me(CIO4)n, Me(bis(oxalato)borate)n (“ Me(BOB)n”), MeCF3SO3, Me[N(CF3SO2)2]n, Me[N(C2F5SO2)2]n, Me[N(CF3SO2)(RpSO2)]n, wherein Rp is C2Fs, C4F9 or CF3OCF2CF2, Me(AsFe)n, Me[C(CF3SO2)3]n, Me2Sn, wherein Me is a metal, preferably a transition metal, an alkaline metal or an alkaline-earth metal, more preferably Me being Li, Na, K or Cs, even more preferably Me being Li, and n is the valence of said metal, typically n being 1 or 2,
wherein R’F is selected from the group consisting of F, CF3, CHF2, CH2F, C2HF4, C2H2F3, C2H3F2, C2FS, C3F?, C3H2FS, C3H4F3, C4F9, C4H2F?, C4H4F5, C5F11, C3FsOCF3, C2F4OCF3, C2H2F2OCF3 and CF2OCF3, and
(c) combinations thereof.
[0071] The amount of the medium (L) in the composition (C1) is typically at least 40% by weight, preferably at least 50% by weight, more preferably at least 60% by weight, based on the total weight of said medium (L) and the polymer (FF).
[0072] Very good results have been obtained using a composition (C1) comprising at least 50% by weight of the medium (L), based on the total weight of said medium (L) and the polymer (FF).
[0073] According to a first embodiment of the invention, the medium (L) comprises at least one organic carbonate.
[0074] Non-limiting examples of suitable organic carbonates include, notably, ethylene carbonate, propylene carbonate, mixtures of ethylene carbonate and propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl-
methyl carbonate, butylene carbonate, vinylene carbonate, fluoroethylene carbonate, fluoropropylene carbonate and mixtures thereof.
[0075] According to a second embodiment of the invention, the medium (L) comprises at least one ionic liquid and, optionally, at least one organic carbonate.
[0076] For the purpose of the present invention, the term ’’ionic liquid” is intended to denote a compound formed by the combination of a positively charged cation and a negatively charged anion in the liquid state at temperatures below 100°C under atmospheric pressure.
[0077] The ionic liquid typically contains:
- a positively charged cation selected from the group consisting of imidazolium, pyridinium, pyrrolidinium and piperidinium ions optionally containing one or more C1-C30 alkyl groups, and
- a negatively charged anion selected from the group consisting of halides, perfluorinated anions and borates.
[0078] Non-limiting examples of C1-C30 alkyl groups include, notably, methyl, ethyl, propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, 2,2-dimethyl-propyl, hexyl, 2,3-dimethyl-2-butyl, heptyl, 2,2- dimethyl-3-pentyl, 2-methyl-2-hexyl, octyl, 4-methyl-3-heptyl, nonyl, decyl, undecyl and dodecyl groups.
[0079] The positively charged cation of the ionic liquid is preferably selected from the group consisting of:
- a pyrrolidinium cation of formula (VIII):
wherein Rn and R22, equal to or different from each other, independently represent a Ci-Cs alkyl group and R33, R44, R55 and Ree, equal to or different from each other, independently represent a hydrogen atom or a C1-C30 alkyl group, preferably a C1-C18 alkyl group, more preferably a C1- Cs alkyl group, and
- a piperidinium cation of formula (IX):
wherein Rn and R22, equal to or different from each other, independently represent a Ci-Cs alkyl group and R33, R44, R55, Ree and R77, equal to or different from each other, independently represent a hydrogen atom or a C1-C30 alkyl group, preferably a C1-C18 alkyl group, more preferably a C1- Cs alkyl group.
[0080] The positively charged cation of the ionic liquid is more preferably selected from the group consisting of:
- a pyrrolidinium cation of formula (Vlll-A):
(Vlll-A)
- a piperidinium cation of formula (IX-A):
[0081] The negatively charged anion of the ionic liquid is preferably selected from the group consisting of:
- bis(trifluoromethylsulphonyl)imide of formula (SC^CFs N-,
- hexafluorophosphate of formula PFe-,
- tetrafluoroborate of formula BF4-, and
- oxaloborate of formula:
[0082] The ionic liquid even more preferably contains a pyrrolidinium cation of formula (ll-A) as defined above and a perfluorinated anion selected from the group consisting of bis(trifluoromethylsulphonyl)imide of formula (SO2CF3)2N-, hexafluorophosphate of formula PFe and tetrafluoroborate of formula BF4-.
[0083] The electrolyte solution (EL) is typically prepared by dissolving a metal salt (M) in the liquid medium (L) so as to provide an electrolyte solution wherein the concentration of the salt is preferably 0.3 M or more, more preferably 0.7 M or more, and still more preferably 1.0 M or more. In addition, an upper limit thereof is preferably 2.5 M or less, more preferably 2.0 M or less, and still more preferably 1 .6 M or less.
[0084] In a preferred embodiment, electrolyte solution (EL) consists of LiPFe and a mixture of carbonates, more preferably a mixture of ethylene carbonate, propylene carbonate and vinylene carbonate.
[0085] The concentration of LiPFe in the medium (L) of the electrolyte solution (EL) is advantageously of about 1 M.
[0086] The choice of the solvent (S) is not particularly limited provided that it is suitable for solubilising the polymer (FF).
[0087] The solvent (S) is typically selected from the group consisting of:
- alcohols such as methyl alcohol, ethyl alcohol and diacetone alcohol,
- ketones such as acetone, methylethylketone, methylisobutyl ketone, diisobutylketone, cyclohexanone and isophorone,
- linear or cyclic esters such as isopropyl acetate, n-butyl acetate, methyl acetoacetate, dimethyl phthalate and y-butyrolactone,
- linear or cyclic amides such as N,N-diethylacetamide, N,N-
dimethylacetamide, dimethylformamide and N-methyl-2-pyrrolidone, and
- dimethyl sulfoxide.
[0088] In addition to at least one organic electro-active compound (EA) as defined above, the electrode-forming composition [composition (C1)] can comprise at least one conductive compound [compound (C)], that is to say a compound capable of imparting to the electrode, in which they are incorporated, electronic conductivity, these additives possibly being, for example, carbonaceous materials such as carbon black, carbon nanotubes, carbon fibers (in particular, carbon fibers obtained in the vapor phase known by the abbreviation VGCF), graphite in powder form, graphite fibers and mixtures thereof.
[0089] In one embodiment of the present invention, the organic electro-active material (EA) can be trapped into the porous structure of carbonaceous materials used as conductive compound (C). The Applicants have found that the cyclability of the battery is thus advantageously enhanced.
[0090] In a second instance, the present invention pertains to the use of the electrode-forming composition [composition (C1)] of the invention in a process for the manufacture of an electrode [electrode (E)], said process comprising:
(i) providing a metal substrate;
(ii) providing the electrode-forming composition [composition (C1)] as above defined;
(iii) applying the composition (C1) provided in step (ii) onto the metal substrate provided in step (i) thereby providing an assembly comprising a metal substrate coated with at least one layer (L1) consisting of said composition (C1); and
(iv) drying the assembly provided in step (iii) to evaporate the at least one solvent (S) thereby providing an electrode [electrode (E)].
[0091] The metal substrate typically acts as a metal collector.
[0092] The metal substrate is generally a foil, mesh or net made from a metal such as copper, aluminum, iron, stainless steel, nickel, titanium or silver.
[0093] Under step (iii) of the process of the invention, the composition (C1 ) is applied onto the metal substrate typically by any suitable procedures such as casting, printing and roll coating.
[0094] Optionally, step (iii) may be repeated, typically one or more times, by applying the composition (C1) provided in step (ii) onto the electrode provided in step (iv).
[0095] Under step (iv) of the process of the invention, drying may be performed either under atmospheric pressure or under vacuum. Alternatively, drying may be performed under modified atmosphere, e.g. under an inert gas, typically exempt notably from moisture (water vapour content of less than 0.001 % v/v).
[0096] The drying temperature will be selected so as to effect removal by evaporation of one or more solvents (S) from the electrode (E) of the invention.
[0097] The electrode (E) of the invention is preferably free from one or more solvents (S).
[0098] The layer (L1) of the electrode (E) of the invention typically has a thickness comprised between 10 pm and 500 pm, preferably between 50 pm and 250 pm, more preferably between 70 pm and 150 pm.
[0099] The electrodes (E) according to the present invention are gelled electrodes, which means that, in addition to the presence of an organic electro-active material as defined above, they comprise (or even consist of) a composite material comprising (or even consisting of) a polymeric matrix conventionally formed from one or more polymers capable of gelling on contact with a liquid electrolyte, more commonly called gelling polymer (FF), the active electrode material and optionally one or more several electronically conductive additives, such as those mentioned above, the liquid electrolyte being confined within the polymer matrix.
[00100] The electrode (E) of the invention is particularly suitable for use in secondary batteries, especially in alkaline or alkaline-earth secondary batteries, more especially in lithium-ion secondary batteries, said batteries being advantageously free from liquid electrolytes while still exhibiting outstanding capacity values.
[00101] The present invention thus provides an electrode [electrode (E)] obtainable by the process defined above, said electrode (E) comprising:
- a metal substrate, and
- directly adhered onto said metal substrate, at least one layer [layer (L1)] consisting of a composition [composition (C2)] comprising:
- at least one partially fluorinated fluoropolymer comprising recurring units derived from at least one fluorinated monomer and at least one functional hydrogenated monomer comprising at least one carboxylic acid end group [polymer (FF)],
- at least one organic electro-active compound [compound (EA)],
- at least one liquid medium [medium (L)] comprising at least one organic carbonate or at least one ionic liquid,
- optionally at least one conductive compound [compound (C)], and
- at least one metal salt [salt (M)].
[00102] The electrode-forming composition (C1) of the present invention is particularly suitable for the manufacturing of positive electrodes for secondary batteries.
[00103] The present invention thus provides a secondary battery comprising:
- a positive electrode,
- a negative electrode, and
- between said positive electrode and said negative electrode, a membrane, wherein at least one of the positive electrode and the negative electrode is an electrode [electrode (E)] according to the invention.
[00104] In particular, the present invention pertains to a secondary battery comprising:
- a positive electrode,
- a negative electrode, and
- between said positive electrode and said negative electrode, a membrane, wherein the positive electrode is an electrode [electrode (E)] according to the invention.
[00105] In one preferred embodiment of the present invention, the negative electrode of the secondary battery of the present invention is typically a metal substrate, preferably a foil made from a metal such as lithium or zinc.
[00106] For the purpose of the present invention, the term “membrane” is intended to denote a discrete, generally thin, interface which moderates permeation of chemical species in contact with it. This interface may be homogeneous, that is, completely uniform in structure (dense membrane), or it may be chemically or physically heterogeneous, for example containing voids, pores or holes of finite dimensions (porous membrane).
[00107] The membrane typically comprises at least one material selected from inorganic materials and organic materials.
[00108] Non-limiting examples of suitable organic materials include, notably, polymers, said polymers being preferably selected from the group consisting of partially fluorinated fluoropolymers.
[00109] The membrane is advantageously free from one or more compounds (EA) as defined above.
[00110] The membrane may further comprise at least one medium (L) as defined above and at least one salt (M) as defined above.
[00111] According to a first embodiment of the invention, the membrane comprises a fluoropolymer hybrid organic/inorganic composite, said hybrid being obtainable by a process comprising hydrolysing and/or condensing a composition comprising:
- at least one partially fluorinated fluoropolymer,
- at least one metal compound [compound (M1)] of formula (X): X4-mAYm (X) wherein m is an integer from 1 to 4, A is a metal selected from the group consisting of Si, Ti and Zr, Y is a hydrolysable group and X is a hydrocarbon group, optionally comprising one or more functional groups,
- at least one ionic liquid as defined above, and
- at least one metal salt [salt (M)] as defined above.
[00112] The selection of the hydrolysable group Y of the compound (M1) of formula (X) as defined above is not particularly limited provided that it
enables under appropriate conditions the formation of a -O-AH bond. The hydrolysable group Y of the compound (M1) of formula (X) as defined above is typically selected from the group consisting of halogen atoms, preferably being a chlorine atom, hydrocarboxy groups, acyloxy groups and hydroxyl groups.
[00113] In case the compound (M1) of formula (X) as defined above comprises at least one functional group on group X, it will be designated as functional compound (M1); in case none of groups X of the compound (M1) of formula (X) as defined above comprise a functional group, the compound (M1) of formula (X) as defined above will be designated as non-functional compound (M1).
[00114] The compound (M1) is preferably of formula (X-A): RA 4-mA(ORB)m (X-A) wherein m is an integer from 1 to 4, and, according to certain embodiments, from 1 to 3, A is a metal selected from the group consisting of Si, Ti and Zr, RA and RB, equal to or different from each other and at each occurrence, are independently selected from C1-C18 hydrocarbon groups, wherein RA optionally comprises at least one functional group.
[00115] Non-limiting examples of functional groups include, notably, epoxy group, carboxylic acid group (in its acid, ester, amide, anhydride, salt or halide form), sulphonic group (in its acid, ester, salt or halide form), hydroxyl group, phosphoric acid group (in its acid, ester, salt, or halide form), thiol group, amine group, quaternary ammonium group, ethylenically unsaturated group (like vinyl group), cyano group, urea group, organo- silane group, aromatic group.
[00116] Should the compound (M1) of formula (X) as defined above be a functional compound (M1), it is more preferably of formula (X-B): RA’4-mA(ORB’)m (X-B) wherein m is an integer from 1 to 3, A is a metal selected from the group consisting of Si, Ti and Zr, RA’, equal to or different from each other and at each occurrence, is a C1-C12 hydrocarbon group comprising at least one functional group and RB’, equal to or different from each other and at each
occurrence, is a C1-C5 linear or branched alkyl group, preferably RB’ being a methyl or ethyl group.
[00117] Examples of functional compounds (M1) are notably vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrismethoxyethoxysilane of formula CH2=CHSi(OC2H4OCH3)3, 2-(3,4-epoxycyclohexylethyltrimethoxysilane) of formula:
glycidoxypropylmethyldiethoxysilane of formula:
glycidoxypropyltrimethoxysilane of formula:
methacryloxypropyltrimethoxysilane of formula:
aminoethylaminpropylmethyldimethoxysilane of formula: H3
H2NC2H4NHC3H6Si(OCH3)2 aminoethylaminpropyltrimethoxysilane of formula:
H2NC2H4NHC3H6Si(OCH3)3
3-aminopropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3- chloroisobutyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3- mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, n-(3- acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (3- acryloxypropyl)dimethylmethoxysilane, (3- acryloxypropyl)methyldichlorosilane, (3- acryloxypropyl)methyldimethoxysilane, 3-(n- allylamino)propyltrimethoxysilane, 2-(4- chlorosulfonylphenyl)ethyltrimethoxysilane, 2-(4- chlorosulphonylphenyl)ethyl trichlorosilane, carboxyethylsilanetriol, and its
sodium salts, triethoxysilylpropylmaleamic acid of formula:
3-(trihydroxysilyl)-1-propane-sulphonic acid of formula HOSO2- CH2CH2CH2-Si(OH)3, N-(trimethoxysilylpropyl)ethylene-diamine triacetic acid, and its sodium salts, 3-(triethoxysilyl)propylsuccinic anhydride of formula: o /C H2C H2C H2Si(OC2H5)3
° J o acetamidopropyltrimethoxysilane of formula H3C-C(O)NH-CH2CH2CH2- Si(OCH3)3, alkanolamine titanates of formula Ti(A)x(OR)y, wherein A is an amine-substitued alkoxy group, e.g. OCH2CH2NH2, R is an alkyl group, and x and y are integers such that x+y = 4.
[00118] Examples of non-functional compounds (M1) are notably tri methoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane (TEOS), tetramethyltitanate, tetraethyltitanate, tetra-n-propyltitanate, tetraisopropyltitanate, tetra-n-butyltitanate, tetra-isobutyl titanate, tetra-tert- butyl titanate, tetra-n-pentyltitanate, tetra-n-hexyltitanate, tetraisooctyltitanate, tetra-n-lauryl titanate, tetraethylzirconate, tetra-n- propylzirconate, tetraisopropylzirconate, tetra-n-butyl zirconate, tetra-sec- butyl zirconate, tetra-tert-butyl zirconate, tetra-n-pentyl zirconate, tetra-tert- pentyl zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-n- octyl zirconate, tetra-n-stearyl zirconate.
[00119] According to a second embodiment of the invention, the membrane comprises a fluoropolymer hybrid organic/inorganic composite, at least one liquid medium [medium (L)] as defined above and at least one metal salt [salt (M)] as defined above, said hybrid being obtainable by a process comprising hydrolysing and/or condensing a composition comprising: - at least one partially fluorinated fluoropolymer comprising recurring units derived from at least one functional hydrogenated monomer comprising at
least one hydroxyl end group,
- at least one metal compound [compound (M2)] of formula (XI): X'wA’Y'm’ (XI) wherein m’ is an integer from 1 to 3, A’ is a metal selected from the group consisting of Si, Ti and Zr, Y’ is a hydrolysable group and X’ is a hydrocarbon group comprising at least one -N=C=O functional group,
- optionally, at least one metal compound [compound (M1)] of formula (XI) as defined above,
- at least one liquid medium [medium (L)] as defined above, and
- at least one metal salt [salt (M)] as defined above.
[00120] The selection of the hydrolysable group Y’ of the compound (M2) of formula (XI) as defined above is not particularly limited provided that it enables under appropriate conditions the formation of a -O-AH bond. The hydrolysable group Y’ of the compound (M2) of formula (XI) as defined above is typically selected from the group consisting of halogen atoms, preferably being a chlorine atom, hydrocarboxy groups, acyloxy groups and hydroxyl groups.
[00121] The compound (M2) is preferably of formula (Xl-A):
RC4.mA’(ORD)m’ (Xl-A) wherein m’ is an integer from 1 to 3, A’ is a metal selected from the group consisting of Si, Ti and Zr, Rc, equal to or different from each other and at each occurrence, is a C1-C12 hydrocarbon group comprising at least one - N=C=O functional group and RD, equal to or different from each other and at each occurrence, is a C1-C5 linear or branched alkyl group, preferably RD being a methyl or ethyl group.
[00122] The compound (M2) is more preferably of formula (Xl-B): O=C=N-RC’-A’-(ORD’)3 (Xl-B) wherein A’ is a metal selected from the group consisting of Si, Ti and Zr, Rc’, equal to or different from each other and at each occurrence, is a linear or branched C1-C12 hydrocarbon group and RD’, equal to or different from each other and at each occurrence, is a C1-C5 linear or branched alkyl group, preferably RD’ being a methyl or ethyl group.
[00123] Non-limiting examples of suitable compounds (M2) include the followings: trimethoxysilyl methyl isocyanate, triethoxysilyl methyl isocyanate, trimethoxysilyl ethyl isocyanate, triethoxysilyl ethyl isocyanate, trimethoxysilyl propyl isocyanate, triethoxysilyl propyl isocyanate, trimethoxysilyl butyl isocyanate, triethoxysilyl butyl isocyanate, trimethoxysilyl pentyl isocyanate, triethoxysilyl pentyl isocyanate, trimethoxysilyl hexyl isocyanate and triethoxysilyl hexyl isocyanate.
[00124] Should the compound (M1) of formula (XI) as defined above in the membrane according to this second embodiment of the invention be a functional compound (M1), it typically comprises at least one functional group different from the -N=C=O functional group.
[00125] According to a further preferred embodiment of the invention, the secondary battery comprises:
- a positive electrode,
- a negative electrode, and
- between said positive electrode and said negative electrode, a membrane, wherein at least one of the positive electrode and the negative electrode is an electrode [electrode (E)] according to the invention, and wherein the membrane is a membrane comprising a fluoropolymer hybrid organic/inorganic composite as defined above.
[00126] Still more preferably, the secondary battery of the present invention comprises:
- a positive electrode,
- a negative electrode, and
- between said positive electrode and said negative electrode, a membrane, wherein the positive electrode is an electrode [electrode (E)] according to the invention, the negative electrode is a metal substrate, preferably a foil made from a metal such as lithium or zinc, and the membrane is a membrane comprising a fluoropolymer hybrid organic/inorganic composite as defined above.
[00127] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
[00128] The invention will be now described in more detail with reference to the following examples whose purpose is merely illustrative and not limitative of the scope of the invention.
[00129] EXPERIMENTAL PART
[00130] Polymer (FF-A): VDF-AA (0.9% by moles)-HFP (2.4% by moles) polymer having a viscosity of 0.30 l/g in DMF at 25°C.
[00131] Polymer (1): VDF-HEA (0.4% by moles)-HFP (2.4% by moles) polymer having a viscosity of 0.11 l/g in DMF at 25°C.
[00132] Electrolyte medium (EL-1): 1 M solution of LiPFe in ethylene carbonate (EC)Zpropylene carbonate (PC) (1/1 by volume) comprising vinylene carbonate (VC) (2% by weight).
[00133] Polymer (EA-1): Poly(N-n-hexyl-3,4,9,10-perylene tetracarboxylic)imide (PTCI):
[00134] Organic molecule (EA-2) (MgLi2C8H20e) of the following formula, wherein
[00135] DBTDL: dibutyl tin dilaurate.
[00136] TEOS: tetraethoxysilane.
[00137] TSPI: 3-(triethoxysilyl)propyl isocyanate.
[00138] Preparation of Organic molecule (EA-2) (Mgl^Cs We)
[00139] 5.2 g of dihydroxyterephthalic acid were dispersed in 500 mL of water, to which 1.53 g of magnesium hydroxide were added. The suspension was stirred for 48 hours at room temperature before removing the water under reduced pressure. A beige powder was obtained with a quantitative yield.
[00140] Then, 1 g of the powder obtained above was dispersed in 25 mL of degassed water, to which 2 equivalents of lithium hydroxide were added under an inert atmosphere. The mixture was stirred for 16 hours with evaporation of the water under reduced pressure. A yellow powder was obtained with a quantitative yield. It was treated under vacuum at 235 °C for 48 hours.
[00141] Determination of intrinsic viscosity of polymer (FF) and of polymer (1)
Intrinsic viscosity (q) [dl/g] was measured using the following equation on the basis of dropping time, at 25°C, of a solution obtained by dissolving polymer (A) in N,N-dimethylformamide at a concentration of about 0.2 g/dl using a Ubbelhode viscosimeter:
where c is polymer concentration [g/dl], qr is the relative viscosity, i.e. the ratio between the dropping time of sample solution and the dropping time of solvent, r|sp is the specific viscosity, i.e. qr -1 , and I" is an experimental factor, which for polymer (FF) and for polymer (1) corresponds to 3.
[00142] General procedure for the manufacture of the membranes using the liquid electrolyte (EL-1).
The polymer (1) (1.5 g) was dissolved in 8.5 g of acetone at 60°C thereby providing a solution containing 15% by weight of said polymer (1). The solution was homogeneous and transparent after homogenization at room temperature. DBTDL (0.015 g) was then added. The solution was homogenized at 60°C. TSPI (0.060 g) was added thereto. The quantity of DBTDL was calculated to be 10% by moles vs. TSPI. TSPI itself was calculated to be 1.1 % by mole vs. the polymer (1). The solution was kept at 60°C for about 90 min so as to let isocyanate functional groups of TSPI to react with the hydroxyl groups of the polymer (1).
In the next step, the liquid electrolyte (EL-1) was added to the solution so obtained.
The weight ratio [mmedium (EL-1) / (mmedium (EL-1) + mpolymer (1))] was 80%.
After homogenization at 60°C, formic acid was added.
TEOS was then added thereto. The quantity of TEOS was calculated from the weight ratio (m(SiO2) I m(polymer(1))) assuming total conversion of TEOS into SiO . This ratio was 10%.
The quantity of formic acid was calculated from the following equation: n(formic acid) I n(TEOS) = 7.8.
All the ingredients were fed to the solution mixture so obtained under Argon atmosphere. The solution mixture was spread with a constant thickness onto a PET substrate using a tape casting machine (doctor blade) in a dry room (dew point: - 40°C). The thickness was controlled by the distance between the knife and the PET film.
The solvent was quickly evaporated from the solution mixture and the membrane was obtained. After a few hours, the membrane was detached from the PET substrate. The membrane so obtained had a constant thickness of 45 pm.
[00143] Example 1 : Coin cell with Polymer (EA-1)
[00144] Preparation of the electrode with Polymer (EA-1)
[00145] A solution of polymer (FF-A) in acetone (10% by weight) was prepared at 60°C and then brought to room temperature. A composition comprising a blend of 18.7% by weight of C-ENERGY® SUPER C65 carbon black (CB) and 81.3% by weight of polymer (EA-1 ) was grinded in dry condition by using a mortar and then was added to the solution so obtained in a weight ratio of 80/20 ((CB+(EA-1))/polymer (FF-A)). In the next step, the electrolyte medium (EL-1) was added to the mixture. The weight ratio [m (electrolyte) I (m(electrolyte) + m(polymer (FF-A))] x 100 was 75%.
[00146] Casting procedure
[00147] The solution mixture was spread with a constant thickness of 600 pm onto a metal collector using a tape casting machine (doctor blade). The thickness was controlled by the distance between the knife and the metal
collector. The thickness of the wet layer of the cathode so obtained was about 340 m. After calendering the wet layer of the cathode was about 110 pm. Cathode loading was about 10.3 mg/cm2 (0.05 mAh/cm2).
[00148] Manufacture of a lithium-metal battery
[00149] A coin cell was prepared by placing the membrane prepared according to the general procedure as detailed above between the cathode just described and a lithium metal as counter electrode.
Trials at C/10 were run 12 cycles keeping roughly a specific capacity recovered of about 29-45 mAh/g.
[00150] Example 2: Coin cell with Organic Molecule (EA-2)
[00151] A solution of polymer (FF-A) in acetone (10% by weight) was prepared at 60°C and then brought to room temperature. A composition comprising a blend of 18.7% by weight of C-ENERGY® SUPER C65 carbon black (CB) and 81 .3% by weight of polymer (EA-1 ) was grinded in dry condition by using a mortar and then was added to the solution so obtained in a weight ratio of 80/20 ((CB+(EA-1))/polymer (FF-A)). In the next step, the electrolyte medium (EL-1) was added to the mixture. The weight ratio [m (electrolyte) I (m(electrolyte) + m(polymer (FF-A))] x 100 was 85,7%.
[00152] Casting procedure
[00153] The solution mixture was spread with a constant thickness of 600pm directly onto the metal collector using a tape casting machine (doctor blade). The thickness was controlled by the distance between the knife and the metal collector. The thickness of the wet layer of the cathode so obtained was about 182 pm. Cathode loading was about 3.9 mg/cm2 (0.39 mAh/cm2).
[00154] Manufacture of a lithium-metal battery
[00155] A coin cell was prepared by placing the membrane prepared according to the general procedure as detailed above between the cathode just described and a lithium metal as counter electrode. Trials at C/100 were run 4 cycles keeping roughly a specific capacity recovered of about 58-70 mAh/g.
Claims
Claim 1. An electrode-forming composition [composition (C1 )] comprising:
- at least one partially fluorinated fluoropolymer comprising recurring units derived from at least one fluorinated monomer and at least one functional hydrogenated monomer comprising at least one carboxylic acid end group [polymer (FF)],
- at least one organic electro-active compound [compound (EA)],
- at least one liquid medium [medium (L)] comprising at least one organic carbonate or at least one ionic liquid,
- at least one metal salt [salt (M)], and
- at least one solvent [solvent (S)] different from said medium (L), wherein the compound (EA) comprises an organic molecule or polymer exhibiting either n-type, p-type or bipolar redox behaviour.
Claim 2. The composition (C1) according to claim 1 , wherein the polymer (FF) is a polymer (FF-1) comprising recurring units derived from vinylidene fluoride (VDF), at least one functional hydrogenated monomer comprising at least one carboxylic acid end group and, optionally, at least one fluorinated monomer different from VDF.
Claim 3. The composition (C1) according to claim 1 or 2, wherein the functional hydrogenated monomer comprising at least one carboxylic acid end group is selected from the group consisting of (meth)acrylic monomers of formula (I):
wherein each of Ri, R2 and R3, equal to or different from each other, is independently a hydrogen atom or a C1-C3 hydrocarbon group.
Claim 4. The composition (C1) according to anyone of the preceding claims, wherein the compound (EA) is selected from the group consisting of: d) n-type materials such as
- conjugated carbonyl groups such as quinones or anhydrides
- conjugated enolic or enolate groups;
- carboxylate groups, such as lithiated carboxylate groups; or
- disulfide groups;
- azo groups;
- imide groups (for example, polyimide groups); b) p-type materials such as:
- nitroxide groups;
- thioether groups;
- heteroaromatic groups such as polyviologenes;
- aromatic amine groups such as dianiline derivatives; c) bipolar-type materials such as hydrocarbons and conjugated nitrogen systems.
Claim 5. The composition (C1) according to anyone of the preceding claims, wherein the medium (L) comprises at least one organic carbonate.
Claim 6. The composition (C1) according to anyone of the preceding claims, wherein the composition further includes at least one conductive compound [compound (C)].
Claim 7. A process for the manufacture of an electrode [electrode (E)] , said process comprising:
(i) providing a metal substrate;
(ii) providing the electrode-forming composition [composition (C1 )] as above defined;
(iii) applying the composition (C1) provided in step (ii) onto the metal substrate provided in step (i) thereby providing an assembly comprising a metal substrate coated with at least one layer (L1) consisting of said composition (C1); and
(iv) drying the assembly provided in step (iii) to evaporate the at least one solvent (S) thereby providing an electrode [electrode (E)].
Claim 8. An electrode [electrode (E)] obtainable by the process according to claim 7, said electrode (E) comprising:
- a metal substrate, and
- directly adhered onto said metal substrate, at least one layer [layer (L1 )] consisting of a composition [composition (C2)] comprising:
- at least one partially fluorinated fluoropolymer comprising recurring units
derived from at least one fluorinated monomer and at least one functional hydrogenated monomer comprising at least one carboxylic acid end group [polymer (FF)],
- at least one organic electro-active compound [compound (EA)],
- at least one liquid medium [medium (L)] comprising at least one organic carbonate or at least one ionic liquid,
- optionally at least one conductive compound [compound (C)], and
- at least one metal salt [salt (M)].
Claim 9. A secondary battery comprising:
- a positive electrode,
- a negative electrode, and
- between said positive electrode and said negative electrode, a membrane, wherein at least one of the positive electrode and the negative electrode is an electrode [electrode (E)] according to claim 8.
Claim 10. The secondary battery according to claim 9 wherein the positive electrode is an electrode (E).
Claim 11. The secondary battery according to anyone of claims 9 or 10 wherein the negative electrode is metal substrate, preferably a foil made from a metal such as lithium or zinc.
Claim 12. The secondary battery according to anyone of claims 9 to 11 , wherein the membrane comprises, a fluoropolymer hybrid organic/inorganic composite, said hybrid being obtainable by a process comprising hydrolysing and/or condensing a composition comprising:
- at least one partially fluorinated fluoropolymer,
- at least one metal compound [compound (M1 )] of formula (X):
X4-mAYm (X) wherein m is an integer from 1 to 4, A is a metal selected from the group consisting of Si, Ti and Zr, Y is a hydrolysable group and X is a hydrocarbon group, optionally comprising one or more functional groups,
- at least one ionic liquid, and
- at least one metal salt [salt (M)].
Claim 13. The secondary battery according to any one of claims 9 to 11 , wherein the membrane comprises a fluoropolymer hybrid organic/inorganic
composite, at least one liquid medium [medium (L)] as defined above and at least one metal salt [salt (M)] as defined above, said hybrid being obtainable by a process comprising hydrolysing and/or condensing a composition comprising:
- at least one partially fluorinated fluoropolymer comprising recurring units derived from at least one functional hydrogenated monomer comprising at least one hydroxyl end group,
- at least one metal compound [compound (M2)] of formula (XI):
X'wA’Y'm’ (XI) wherein m’ is an integer from 1 to 3, A’ is a metal selected from the group consisting of Si, Ti and Zr, Y’ is a hydrolysable group and X’ is a hydrocarbon group comprising at least one -N=C=O functional group,
- optionally, at least one metal compound [compound (M1)] of formula (XI) as defined above,
- at least one liquid medium [medium (L)] as defined above, and
- at least one metal salt [salt (M)] as defined above.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20306309 | 2020-11-02 | ||
| PCT/EP2021/080103 WO2022090453A1 (en) | 2020-11-02 | 2021-10-29 | Organic battery |
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| Publication Number | Publication Date |
|---|---|
| EP4238150A1 true EP4238150A1 (en) | 2023-09-06 |
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| EP21801549.3A Pending EP4238150A1 (en) | 2020-11-02 | 2021-10-29 | Organic battery |
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| ES2934209T3 (en) * | 2016-06-14 | 2023-02-20 | Solvay | Fluoropolymer membrane for electrochemical devices |
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