KR20140018255A - 2차 배터리 전지용 바인더 - Google Patents
2차 배터리 전지용 바인더 Download PDFInfo
- Publication number
- KR20140018255A KR20140018255A KR1020137022700A KR20137022700A KR20140018255A KR 20140018255 A KR20140018255 A KR 20140018255A KR 1020137022700 A KR1020137022700 A KR 1020137022700A KR 20137022700 A KR20137022700 A KR 20137022700A KR 20140018255 A KR20140018255 A KR 20140018255A
- Authority
- KR
- South Korea
- Prior art keywords
- silicon
- binder
- maleic anhydride
- polymer
- copolymer
- 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.)
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- 239000011230 binding agent Substances 0.000 title claims abstract description 214
- 239000000203 mixture Substances 0.000 claims abstract description 142
- 239000002131 composite material Substances 0.000 claims abstract description 133
- 229920000642 polymer Polymers 0.000 claims abstract description 132
- 150000003839 salts Chemical class 0.000 claims abstract description 109
- 229920001577 copolymer Polymers 0.000 claims abstract description 92
- 239000007772 electrode material Substances 0.000 claims abstract description 86
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 72
- 239000011976 maleic acid Chemical group 0.000 claims abstract description 58
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 51
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000178 monomer Substances 0.000 claims abstract description 50
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical group OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 36
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011734 sodium Substances 0.000 claims abstract description 32
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Chemical group OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 29
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Chemical group OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 29
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001252 acrylic acid derivatives Chemical group 0.000 claims abstract description 20
- 150000002688 maleic acid derivatives Chemical group 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 116
- 239000011263 electroactive material Substances 0.000 claims description 110
- 229910052710 silicon Inorganic materials 0.000 claims description 100
- 239000010703 silicon Substances 0.000 claims description 100
- 239000002245 particle Substances 0.000 claims description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 65
- 230000015572 biosynthetic process Effects 0.000 claims description 64
- 239000002904 solvent Substances 0.000 claims description 53
- 239000000758 substrate Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 35
- 229910002804 graphite Inorganic materials 0.000 claims description 31
- 239000010439 graphite Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 159000000000 sodium salts Chemical class 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 17
- 239000012634 fragment Substances 0.000 claims description 16
- 239000004020 conductor Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 14
- 239000002070 nanowire Substances 0.000 claims description 13
- 239000011856 silicon-based particle Substances 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 13
- 239000011135 tin Substances 0.000 claims description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052733 gallium Inorganic materials 0.000 claims description 12
- 229910052732 germanium Inorganic materials 0.000 claims description 12
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 12
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- YYXLGGIKSIZHSF-UHFFFAOYSA-N ethene;furan-2,5-dione Chemical group C=C.O=C1OC(=O)C=C1 YYXLGGIKSIZHSF-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002210 silicon-based material Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021385 hard carbon Inorganic materials 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002121 nanofiber Substances 0.000 claims 2
- 239000002074 nanoribbon Substances 0.000 claims 2
- 239000002073 nanorod Substances 0.000 claims 2
- 239000002135 nanosheet Substances 0.000 claims 2
- WVKHCAOZIFYQEG-ODZAUARKSA-N (z)-but-2-enedioic acid;ethene Chemical group C=C.OC(=O)\C=C/C(O)=O WVKHCAOZIFYQEG-ODZAUARKSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 15
- 210000004027 cell Anatomy 0.000 description 58
- 239000000243 solution Substances 0.000 description 48
- 229910052799 carbon Inorganic materials 0.000 description 30
- 239000010410 layer Substances 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 229920002125 Sokalan® Polymers 0.000 description 22
- -1 LiC 6 Chemical compound 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 229910001416 lithium ion Inorganic materials 0.000 description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 239000002033 PVDF binder Substances 0.000 description 17
- 239000004584 polyacrylic acid Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 16
- 239000002585 base Substances 0.000 description 15
- 239000011148 porous material Substances 0.000 description 15
- 239000010405 anode material Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 239000000835 fiber Substances 0.000 description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 13
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 12
- 229920006184 cellulose methylcellulose Polymers 0.000 description 12
- 229910003002 lithium salt Inorganic materials 0.000 description 12
- 159000000002 lithium salts Chemical class 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 150000008064 anhydrides Chemical group 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000956 alloy Substances 0.000 description 10
- 230000001351 cycling effect Effects 0.000 description 10
- 229920002521 macromolecule Polymers 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 239000011863 silicon-based powder Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 239000011149 active material Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000002800 charge carrier Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
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- 238000003756 stirring Methods 0.000 description 6
- MRAKLTZPBIBWFH-ARJAWSKDSA-N (z)-2-ethenylbut-2-enedioic acid Chemical compound OC(=O)\C=C(\C=C)C(O)=O MRAKLTZPBIBWFH-ARJAWSKDSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 229910000676 Si alloy Inorganic materials 0.000 description 5
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- 125000000524 functional group Chemical group 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
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- 229910052814 silicon oxide Inorganic materials 0.000 description 5
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
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- 125000003342 alkenyl group Chemical group 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 125000000304 alkynyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- 239000007858 starting material Substances 0.000 description 3
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- AXGOOCLYBPQWNG-UHFFFAOYSA-N 3-ethylfuran-2,5-dione Chemical compound CCC1=CC(=O)OC1=O AXGOOCLYBPQWNG-UHFFFAOYSA-N 0.000 description 2
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
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- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
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Images
Classifications
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Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1101427.1A GB2487569B (en) | 2011-01-27 | 2011-01-27 | A binder for a secondary battery cell |
| GB1101427.1 | 2011-01-27 | ||
| PCT/GB2012/050174 WO2012101450A1 (en) | 2011-01-27 | 2012-01-27 | A binder for a secondary battery cell |
Publications (1)
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| KR20140018255A true KR20140018255A (ko) | 2014-02-12 |
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| KR1020137022700A Withdrawn KR20140018255A (ko) | 2011-01-27 | 2012-01-27 | 2차 배터리 전지용 바인더 |
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| US (1) | US20140087250A1 (https=) |
| EP (1) | EP2668687A1 (https=) |
| JP (1) | JP6008875B2 (https=) |
| KR (1) | KR20140018255A (https=) |
| CN (1) | CN103460461A (https=) |
| GB (1) | GB2487569B (https=) |
| WO (1) | WO2012101450A1 (https=) |
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| KR20160019775A (ko) * | 2014-08-12 | 2016-02-22 | 삼성전자주식회사 | 고분자, 이를 포함하는 바인더 및 음극, 및 상기 음극을 포함하는 리튬전지 |
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| CN116285882B (zh) * | 2023-05-22 | 2023-10-20 | 宁德时代新能源科技股份有限公司 | 粘结剂、负极极片、电池和用电装置 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015147419A1 (ko) * | 2014-03-26 | 2015-10-01 | 전자부품연구원 | 리튬이온 이차전지용 음극 합제, 이의 제조 방법 및 이를 갖는 리튬이온 이차 전지 |
| KR20160019775A (ko) * | 2014-08-12 | 2016-02-22 | 삼성전자주식회사 | 고분자, 이를 포함하는 바인더 및 음극, 및 상기 음극을 포함하는 리튬전지 |
| US10593992B2 (en) | 2014-10-15 | 2020-03-17 | Tokyo University Of Science Foundation | Negative electrode for potassium ion secondary batteries, negative electrode for potassium ion capacitors, potassium ion secondary battery, potassium ion capacitor, and binder for negative electrodes of potassium ion secondary batteries or negative electrodes of potassium ion capacitors |
| KR20180035892A (ko) * | 2015-08-06 | 2018-04-06 | 주식회사 쿠라레 | 비수 전해질 전지 전극용 슬러리 조성물, 그리고, 그것을 사용한 비수 전해질 전지 정극 및 비수 전해질 전지 |
| US10644307B2 (en) | 2015-08-06 | 2020-05-05 | Kuraray Co., Ltd. | Slurry composition for non aqueous electrolyte battery electrode, and non aqueous electrolyte battery positive electrode and non aqueous electrolyte battery using same |
| US10326140B2 (en) | 2016-09-21 | 2019-06-18 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte battery, battery pack, and vehicle |
| US12148930B2 (en) | 2018-09-05 | 2024-11-19 | Lg Energy Solution Ltd. | Negative electrode and secondary battery including the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103460461A (zh) | 2013-12-18 |
| GB2487569B (en) | 2014-02-19 |
| EP2668687A1 (en) | 2013-12-04 |
| JP2014510362A (ja) | 2014-04-24 |
| GB2487569A (en) | 2012-08-01 |
| US20140087250A1 (en) | 2014-03-27 |
| WO2012101450A1 (en) | 2012-08-02 |
| GB201101427D0 (en) | 2011-03-16 |
| JP6008875B2 (ja) | 2016-10-19 |
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