JP2018065886A - Sulfur-containing resin - Google Patents
Sulfur-containing resin Download PDFInfo
- Publication number
- JP2018065886A JP2018065886A JP2016203411A JP2016203411A JP2018065886A JP 2018065886 A JP2018065886 A JP 2018065886A JP 2016203411 A JP2016203411 A JP 2016203411A JP 2016203411 A JP2016203411 A JP 2016203411A JP 2018065886 A JP2018065886 A JP 2018065886A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- sulfur
- propylene
- group
- substituted
- 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.)
- Granted
Links
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 118
- 239000011593 sulfur Substances 0.000 title claims abstract description 118
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229920005989 resin Polymers 0.000 title claims abstract description 54
- 239000011347 resin Substances 0.000 title claims abstract description 54
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 34
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 24
- -1 dithiol compound Chemical class 0.000 claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 125000002993 cycloalkylene group Chemical group 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- CNDCQWGRLNGNNO-UHFFFAOYSA-N 2-(2-sulfanylethoxy)ethanethiol Chemical compound SCCOCCS CNDCQWGRLNGNNO-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000002411 thermogravimetry Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003273 ketjen black Substances 0.000 description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000002482 conductive additive Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000004663 dialkyl amino group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- JLQNHALFVCURHW-UHFFFAOYSA-N cyclooctasulfur Chemical compound S1SSSSSSS1 JLQNHALFVCURHW-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- BLBBMBKUUHYSMI-UHFFFAOYSA-N furan-2,3,4,5-tetrol Chemical compound OC=1OC(O)=C(O)C=1O BLBBMBKUUHYSMI-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- SLLFVLKNXABYGI-UHFFFAOYSA-N 1,2,3-benzoxadiazole Chemical compound C1=CC=C2ON=NC2=C1 SLLFVLKNXABYGI-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 1
- KTZQTRPPVKQPFO-UHFFFAOYSA-N 1,2-benzoxazole Chemical compound C1=CC=C2C=NOC2=C1 KTZQTRPPVKQPFO-UHFFFAOYSA-N 0.000 description 1
- CIISBYKBBMFLEZ-UHFFFAOYSA-N 1,2-oxazolidine Chemical compound C1CNOC1 CIISBYKBBMFLEZ-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- XWIYUCRMWCHYJR-UHFFFAOYSA-N 1h-pyrrolo[3,2-b]pyridine Chemical compound C1=CC=C2NC=CC2=N1 XWIYUCRMWCHYJR-UHFFFAOYSA-N 0.000 description 1
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 1
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 1
- HFTVJMFWJUFBNO-UHFFFAOYSA-N 5h-pyrrolo[2,3-b]pyrazine Chemical compound C1=CN=C2NC=CC2=N1 HFTVJMFWJUFBNO-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 229920006361 Polyflon Polymers 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
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- 238000005504 petroleum refining Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- OWECKHSCCDVJCN-UHFFFAOYSA-N quinazoline;quinoxaline Chemical compound N1=CN=CC2=CC=CC=C21.N1=CC=NC2=CC=CC=C21 OWECKHSCCDVJCN-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
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- 238000006479 redox reaction Methods 0.000 description 1
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- 230000007017 scission Effects 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical compound C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、分子状硫黄（Ｓ８）とジチオール化合物をジスルフィド−チオール交換反応させて得られる含硫黄樹脂と、当該含硫黄樹脂を含む正極及び当該正極を備える二次電池に関する。 The present invention relates to a sulfur-containing resin obtained by subjecting molecular sulfur (S 8 ) and a dithiol compound to a disulfide-thiol exchange reaction, a positive electrode including the sulfur-containing resin, and a secondary battery including the positive electrode.
石油精製時の回収等で生産される硫黄は、硫酸等の工業製品、ゴム等の添加剤、肥料等の多岐にわたる用途に使用される。しかし、これらの用途で消費される硫黄の量は、硫黄の生産量を下回っており、余剰の硫黄の保管が問題となっている。そこで、硫黄の新たな用途が検討され、硫黄が二次電池の正極の材料として利用されるようになった。硫黄の理論電池容量は、リチウム二次電池の正極活物質として通常使用されているＬｉＣｏＯ２の理論電池容量より大きい。そのため、リチウム又はナトリウムが負極の材料とされ、硫黄が正極活物質とされる二次電池が数多く報告されている。このうち、ナトリウム−硫黄電池は実用化されているが、硫黄正極の活性が高められるよう、その動作温度が３００℃と高温になる必要があり、電池デバイス自体の大きさとも相俟って、通常の環境下で使用され難い。更に、硫黄正極を備える二次電池の充放電が繰り返されると、硫黄が電解液中に溶出して電池を構成する金属と化学反応し金属硫化物を生成するため、電池容量が低下し、二次電池の寿命は短かった。 Sulfur produced by recovery during petroleum refining is used for a wide variety of applications such as industrial products such as sulfuric acid, additives such as rubber, and fertilizers. However, the amount of sulfur consumed in these applications is below the amount of sulfur produced, and storage of excess sulfur is a problem. Then, the new use of sulfur was examined and sulfur came to be utilized as a material of the positive electrode of a secondary battery. The theoretical battery capacity of sulfur is larger than the theoretical battery capacity of LiCoO 2 that is usually used as a positive electrode active material for lithium secondary batteries. Therefore, many secondary batteries in which lithium or sodium is used as a negative electrode material and sulfur is used as a positive electrode active material have been reported. Among these, the sodium-sulfur battery has been put into practical use, but its operating temperature needs to be as high as 300 ° C. so that the activity of the sulfur positive electrode can be increased, coupled with the size of the battery device itself, It is difficult to use under normal environment. Furthermore, when charging / discharging of the secondary battery including the sulfur positive electrode is repeated, sulfur is eluted into the electrolyte solution and chemically reacts with the metal constituting the battery to generate metal sulfide, so that the battery capacity is reduced. The life of the secondary battery was short.
そこで、含硫黄材料の、金属硫化物の電解液への溶出が抑制された正極活物質としての使用が提案され、分子状硫黄（Ｓ８）とビニル化合物とのラジカル重合（逆加硫）によって合成された含硫黄材料が検討された（例えば、非特許文献１参照）。更に、特定のジアリル化合物又は炭素数５〜２０のアルキル基を有する特定のモノアリル化合物と分子状硫黄（Ｓ８）が混合され加熱されて得られる含硫黄ポリマーが正極の材料として使用される二次電池（例えば、特許文献１参照）、イオン性基を有する特定のモノアリル化合物と分子状硫黄（Ｓ８）が混合され加熱されて得られる含硫黄ポリマーが正極の材料として使用される二次電池（例えば、特許文献２参照）が検討された。 Therefore, the use of a sulfur-containing material as a positive electrode active material in which elution of metal sulfide into the electrolyte is suppressed, and radical polymerization (reverse vulcanization) between molecular sulfur (S 8 ) and a vinyl compound is proposed. Synthesized sulfur-containing materials have been studied (for example, see Non-Patent Document 1). Further, a secondary compound in which a specific diallyl compound or a specific monoallyl compound having an alkyl group having 5 to 20 carbon atoms and molecular sulfur (S 8 ) are mixed and heated to be used as a positive electrode material. Batteries (see, for example, Patent Document 1), secondary batteries in which a sulfur-containing polymer obtained by mixing and heating a specific monoallyl compound having an ionic group and molecular sulfur (S 8 ) is used as a positive electrode material ( For example, see Patent Document 2).
近年、二次電池の正極として利用可能な含硫黄材料の硫黄含有量の更なる増大が期待されている。 In recent years, a further increase in the sulfur content of sulfur-containing materials that can be used as positive electrodes for secondary batteries is expected.
本発明は、このような事情に鑑みてなされており、本発明が解決しようとする課題は、硫黄含有量が大きな、二次電池の正極活物質として利用可能な含硫黄樹脂の提供である。 The present invention has been made in view of such circumstances, and a problem to be solved by the present invention is to provide a sulfur-containing resin having a large sulfur content and usable as a positive electrode active material of a secondary battery.
本発明の発明者らは、上記課題を解決するために鋭意検討した結果、ジチオール化合物と分子状硫黄（Ｓ８）を反応させて得られる含硫黄樹脂の硫黄含有量は大きく、当該含硫黄樹脂は二次電池の正極活物質として利用可能であることを見出し、本発明を完成させるに至った。 The inventors of the present invention have intensively studied to solve the above problems, and as a result, the sulfur-containing resin obtained by reacting the dithiol compound with molecular sulfur (S 8 ) has a large sulfur content, and the sulfur-containing resin Was found to be usable as a positive electrode active material for secondary batteries, and the present invention was completed.
すなわち、本発明は
［１］以下の式（１）
［２］Ｒは直鎖の炭素数１〜２０のアルキレン基、−ＣＨ２ＣＨ２ＯＣＨ２ＣＨ２ＯＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２ＯＣＨ２ＣＨ２−からなる群より選ばれるいずれか１つを表す、［１］に記載されている含硫黄樹脂、
［３］含硫黄樹脂に対する硫黄含有量が５０〜９５質量％である、［１］又は［２］に記載されている含硫黄樹脂、
［４］［１］〜［３］のいずれかに記載されている含硫黄樹脂を含有する二次電池用正極、
［５］［４］に記載されている二次電池用正極を備える二次電池、
［６］以下の式（２）
ＨＳ−Ｒ−ＳＨ （２）
（式中、Ｒは置換又は非置換の直鎖の炭素数１〜２０のアルキレン基、主鎖中に−Ｏ−を１以上有する置換若しくは非置換の直鎖又は分岐の炭素数２〜２０のアルキレン基、置換又は非置換の芳香族基、置換又は非置換の炭素数３〜７のシクロアルキレン基からなる群より選ばれるいずれか１つを表す。）で表されるジチオール化合物と分子状硫黄（Ｓ８）を反応させる、含硫黄樹脂の製造方法に関する。
That is, the present invention provides [1] the following formula (1):
[2] R is any one selected from the group consisting of a linear alkylene group having 1 to 20 carbon atoms, —CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 —, and —CH 2 CH 2 OCH 2 CH 2 —. 1 represents a sulfur-containing resin described in [1],
[3] The sulfur-containing resin described in [1] or [2], wherein the sulfur content relative to the sulfur-containing resin is 50 to 95% by mass,
[4] A positive electrode for a secondary battery containing the sulfur-containing resin described in any one of [1] to [3],
[5] A secondary battery comprising the positive electrode for a secondary battery described in [4],
[6] The following formula (2)
HS-R-SH (2)
(In the formula, R is a substituted or unsubstituted linear alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted linear or branched chain group having 2 to 20 carbon atoms having one or more —O— in the main chain. A dithiol compound represented by an alkylene group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted cycloalkylene group having 3 to 7 carbon atoms, and molecular sulfur. The present invention relates to a method for producing a sulfur-containing resin in which (S 8 ) is reacted.
本発明の含硫黄樹脂は、融解された分子状硫黄（Ｓ８）とジチオール化合物の１段階の反応で合成される。本発明の含硫黄樹脂は熱可塑性を示し、低いガラス転移温度を有しているから、その成形性は高く、本発明の含硫黄樹脂の成形体にひび割れ、切断等の破損が生じても加熱プレスにより修復される。更に、本発明の含硫黄樹脂の硫黄含有量は大きく、二次電池の正極活物質として利用可能である。 The sulfur-containing resin of the present invention is synthesized by a one-step reaction of molten molecular sulfur (S 8 ) and a dithiol compound. Since the sulfur-containing resin of the present invention exhibits thermoplasticity and has a low glass transition temperature, its moldability is high. Even if the molded product of the sulfur-containing resin of the present invention is cracked or broken, it is heated. It is repaired by pressing. Furthermore, the sulfur-containing resin of the present invention has a high sulfur content and can be used as a positive electrode active material for secondary batteries.
本発明の含硫黄樹脂は、以下の式（２）
ＨＳ−Ｒ−ＳＨ （２）
（式中、Ｒは置換又は非置換の直鎖の炭素数１〜２０のアルキレン基、主鎖中に−Ｏ−を１以上有する置換若しくは非置換の直鎖又は分岐の炭素数２〜２０のアルキレン基、置換又は非置換の芳香族基、置換又は非置換の炭素数３〜７のシクロアルキレン基からなる群より選ばれるいずれか１つを表す。）で表されるジチオール化合物と分子状硫黄（Ｓ８）を反応させて製造される。
The sulfur-containing resin of the present invention has the following formula (2)
HS-R-SH (2)
(In the formula, R is a substituted or unsubstituted linear alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted linear or branched chain group having 2 to 20 carbon atoms having one or more —O— in the main chain. A dithiol compound represented by an alkylene group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted cycloalkylene group having 3 to 7 carbon atoms, and molecular sulfur. It is produced by reacting (S 8 ).
上記「置換又は非置換の直鎖の炭素数１〜２０のアルキレン基」の「直鎖の炭素数１〜２０のアルキレン基」は、二価の飽和の炭素数１〜２０の炭素鎖である。当該アルキレン基として、具体的には、メチレン、エチレン、プロピレン、ブチレン、ペンチレン、へキシレン、ヘプチレン、オクチレン、ノニレン、デシレン、ウンデシレン、ドデシレン、トリデシレン、テトラデシレン、ペンタデシレン、ヘキサデシレン、ヘプタデシレン、オクタデシレン、ノナデシレン、イコシレン等が挙げられる。 The “linear alkylene group having 1 to 20 carbon atoms” in the above “substituted or unsubstituted linear alkylene group having 1 to 20 carbon atoms” is a divalent saturated carbon chain having 1 to 20 carbon atoms. . Specific examples of the alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, icosylene. Etc.
上記「置換又は非置換の直鎖の炭素数１〜２０のアルキレン基」の置換基は、水酸基、フッ素原子、下記に示す芳香族基、ジアルキルアミノ基、アルキルオキシカルボニル基、アルコキシ基、含窒素ヘテロ環基等である。上記ジアルキルアミノ基、アルキルオキシカルボニル基、及びアルコキシ基におけるアルキルは、直鎖又は分岐の炭素数１〜４のアルキルであり、具体的には、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、ｓ−ブチル、ｔ−ブチル、イソブチルである。上記含窒素ヘテロ環基は、具体的には、ピロリジン、ピラゾリジン、イミダゾリジン、オキサゾリジン、イソオキサゾリジン、ピペリジン、ピペラジン、モルホリン、チオモルホリン等である。 The substituent of the above-mentioned “substituted or unsubstituted linear alkylene group having 1 to 20 carbon atoms” includes a hydroxyl group, a fluorine atom, an aromatic group, a dialkylamino group, an alkyloxycarbonyl group, an alkoxy group, a nitrogen-containing group shown below. A heterocyclic group or the like; Alkyl in the dialkylamino group, alkyloxycarbonyl group, and alkoxy group is linear or branched alkyl having 1 to 4 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl. , S-butyl, t-butyl, isobutyl. Specific examples of the nitrogen-containing heterocyclic group include pyrrolidine, pyrazolidine, imidazolidine, oxazolidine, isoxazolidine, piperidine, piperazine, morpholine, thiomorpholine, and the like.
上記「主鎖中に−Ｏ−を１以上有する置換若しくは非置換の直鎖又は分岐の炭素数２〜２０のアルキレン基」として、具体的には、−エチレン−Ｏ−エチレン−、−エチレン−Ｏ−プロピレン−、−エチレン−Ｏ−ブチレン−、−エチレン−Ｏ−ペンチレン−、−エチレン−Ｏ−へキシレン−、−エチレン−Ｏ−ヘプチレン−、−エチレン−Ｏ−オクチレン−、−エチレン−Ｏ−ノニレン−、−エチレン−Ｏ−デシレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−、−エチレン−Ｏ−プロピレン−Ｏ−エチレン−、−エチレン−Ｏ−プロピレン−Ｏ−プロピレン−、−エチレン−Ｏ−プロピレン−Ｏ−ブチレン−、−エチレン−Ｏ−プロピレン−Ｏ−ペンチレン−、−エチレン−Ｏ−プロピレン−Ｏ−ヘキシレン−、−エチレン−Ｏ−プロピレン−Ｏ−ヘプチレン−、−エチレン−Ｏ−ブチレン−Ｏ−エチレン−、−エチレン−Ｏ−ペンチレン−Ｏ−エチレン−、−エチレン−Ｏ−ブチレン−Ｏ−プロピレン−、−エチレン−Ｏ−ブチレン−Ｏ−ブチレン−、−エチレン−Ｏ−ブチレン−Ｏ−ペンチレン−、−エチレン−Ｏ−ブチレン−Ｏ−ヘキシレン−、−エチレン−Ｏ−ペンチレン−Ｏ−エチレン−、−エチレン−Ｏ−ペンチレン−Ｏ−プロピレン−、−エチレン−Ｏ−ペンチレン−Ｏ−ブチレン−、−エチレン−Ｏ−ペンチレン−Ｏ−ペンチレン−、−エチレン−Ｏ−ヘキシレン−Ｏ−エチレン−、−エチレン−Ｏ−ヘキシレン−Ｏ−プロピレン−、−エチレン−Ｏ−ヘキシレン−Ｏ−ブチレン−、−エチレン−Ｏ−ヘプチレン−Ｏ−エチレン−、−エチレン−Ｏ−ヘプチレン−Ｏ−プロピレン−、−エチレン−Ｏ−オクチレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−プロピレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−ブチレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−ペンチレン−、−エチレン−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−プロピレン−、−エチレン−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−ブチレン−、−エチレン−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−ペンチレン−、−エチレン−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−プロピレン−、−エチレン−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−ブチレン−、−エチレン−Ｏ−エチレン−Ｏ−ペンチレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−ペンチレン−Ｏ−プロピレン−、−エチレン−Ｏ−エチレン−Ｏ−ヘキシレン−Ｏ−エチレン−、−エチレン−Ｏ−プロピレン−Ｏ−エチレン−Ｏ−プロピレン−、−エチレン−Ｏ−プロピレン−Ｏ−エチレン−Ｏ−ブチレン−、−エチレン−Ｏ−プロピレン−Ｏ−エチレン−Ｏ−ペンチレン−、−エチレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−エチレン−、−エチレン−Ｏ−プロピレン−Ｏ−ブチレン−Ｏ−エチレン−、−エチレン−Ｏ−プロピレン−Ｏ−ペンチレン−Ｏ−エチレン−、−エチレン−Ｏ−ブチレン−Ｏ−エチレン−Ｏ−プロピレン−、−エチレン−Ｏ−ブチレン−Ｏ−エチレン−Ｏ−ブチレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−プロピレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−ブチレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−プロピレン−Ｏ−エチレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−ブチレン−Ｏ−エチレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−、−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−Ｏ−エチレン−、−プロピレン−Ｏ−ブチレン−、−プロピレン−Ｏ−ペンチレン−、−プロピレン−Ｏ−プロピレン−Ｏ−へキシレン−、−プロピレン−Ｏ−へキシレン−、−プロピレン−Ｏ−プロピレン−Ｏ−ヘプチレン−、−プロピレン−Ｏ−ヘプチレン−、−プロピレン−Ｏ−ノニレン−、−プロピレン−Ｏ−エチレン−Ｏ−プロピレン−、−プロピレン−Ｏ−エチレン−Ｏ−ブチレン−、−プロピレン−Ｏ−エチレン−Ｏ−ペンチレン−、−プロピレン−Ｏ−エチレン−Ｏ−ヘキシレン−、−プロピレン−Ｏ−エチレン−Ｏ−ヘプチレン−、−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−、−プロピレン−Ｏ−プロピレン−Ｏ−ブチレン−、−プロピレン−Ｏ−プロピレン−Ｏ−ペンチレン−、−プロピレン−Ｏ−プロピレン−Ｏ−ヘキシレン−、−プロピレン−Ｏ−ブチレン−Ｏ−プロピレン−、−プロピレン−Ｏ−ブチレン−Ｏ−ブチレン−、−プロピレン−Ｏ−ブチレン−Ｏ−ペンチレン−、−プロピレン−Ｏ−ペンチレン−Ｏ−プロピレン−、−プロピレン−Ｏ−ペンチレン−Ｏ−ブチレン−、−プロピレン−Ｏ−ヘキシレン−Ｏ−プロピレン−、−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−、−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−、−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−Ｏ−プロピレン−、−ブチレン−Ｏ−ブチレン−、−ブチレン−Ｏ−ペンチレン−、−ブチレン−Ｏ−ヘキシレン−、−ブチレン−Ｏ−ヘプチレン−、−ブチレン−Ｏ−オクチレン−、−ブチレン−Ｏ−エチレン−Ｏ−ブチレン−、−ブチレン−Ｏ−プロピレン−Ｏ−ブチレン−、−ブチレン−Ｏ−ブチレン−Ｏ−ブチレン−、−ブチレン−Ｏ−ブチレン−Ｏ−ブチレン−Ｏ−ブチレン−、−ブチレン−Ｏ−ブチレン−Ｏ−ブチレン−Ｏ−ブチレン−Ｏ−ブチレン−、−ペンチレン−Ｏ−ペンチレン−、−ペンチレン−Ｏ−へキシレン−、−ペンチレン−Ｏ−へキシレン−、−ペンチレン−Ｏ−ヘプチレン−、−ペンチレン−Ｏ−エチレン−Ｏ−ペンチレン−、−ペンチレン−Ｏ−ペンチレン−Ｏ−ペンチレン−、−ペンチレン−Ｏ−ペンチレン−Ｏ−ペンチレン−Ｏ−ペンチレン−、−へキシレン−Ｏ−へキシレン−、−へキシレン−Ｏ−へキシレン−Ｏ−へキシレン−、−ヘプチレン−Ｏ−ヘプチレン−、−オクチレン−Ｏ−オクチレン−、−ノニレン−Ｏ−ノニレン−、−デシレン−Ｏ−デシレン−等が挙げられる。 Specific examples of the above-mentioned “substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms having one or more —O— in the main chain” include -ethylene-O-ethylene-, -ethylene- O-propylene-, -ethylene-O-butylene-, -ethylene-O-pentylene-, -ethylene-O-hexylene-, -ethylene-O-heptylene-, -ethylene-O-octylene-, -ethylene-O -Nonylene-, -ethylene-O-decylene-, -ethylene-O-ethylene-O-ethylene-, -ethylene-O-propylene-O-ethylene-, -ethylene-O-propylene-O-propylene-, -ethylene -O-propylene-O-butylene-, -ethylene-O-propylene-O-pentylene-, -ethylene-O-propylene-O-hexylene-, -ethylene-O-propyl Pyrene-O-heptylene-, -ethylene-O-butylene-O-ethylene-, -ethylene-O-pentylene-O-ethylene-, -ethylene-O-butylene-O-propylene-, -ethylene-O-butylene- O-butylene-, -ethylene-O-butylene-O-pentylene-, -ethylene-O-butylene-O-hexylene-, -ethylene-O-pentylene-O-ethylene-, -ethylene-O-pentylene-O- -Propylene-, -ethylene-O-pentylene-O-butylene-, -ethylene-O-pentylene-O-pentylene-, -ethylene-O-hexylene-O-ethylene-, -ethylene-O-hexylene-O-propylene- , -Ethylene-O-hexylene-O-butylene-, -ethylene-O-heptylene-O-ethylene-, -ethylene-O-hept Len-O-propylene-, -ethylene-O-octylene-O-ethylene-, -ethylene-O-ethylene-O-ethylene-O-ethylene-, -ethylene-O-ethylene-O-ethylene-O-propylene- , -Ethylene-O-ethylene-O-ethylene-O-butylene-, -ethylene-O-ethylene-O-ethylene-O-pentylene-, -ethylene-O-ethylene-O-propylene-O-ethylene-,- Ethylene-O-ethylene-O-propylene-O-propylene-, -ethylene-O-ethylene-O-propylene-O-butylene-, -ethylene-O-ethylene-O-propylene-O-pentylene-, -ethylene- O-ethylene-O-butylene-O-ethylene-, -ethylene-O-ethylene-O-butylene-O-propylene-, -ethylene-O-ethylene Len-O-butylene-O-butylene-, -ethylene-O-ethylene-O-pentylene-O-ethylene-, -ethylene-O-ethylene-O-pentylene-O-propylene-, -ethylene-O-ethylene- O-hexylene-O-ethylene-, -ethylene-O-propylene-O-ethylene-O-propylene-, -ethylene-O-propylene-O-ethylene-O-butylene-, -ethylene-O-propylene-O- -Ethylene-O-pentylene-, -ethylene-O-propylene-O-propylene-O-ethylene-, -ethylene-O-propylene-O-butylene-O-ethylene-, -ethylene-O-propylene-O-pentylene- O-ethylene-, -ethylene-O-butylene-O-ethylene-O-propylene-, -ethylene-O-butylene-O-ethylene- -Butylene-, -ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-, -ethylene-O-ethylene-O-ethylene-O-ethylene-O-propylene-, -ethylene-O-ethylene -O-ethylene-O-ethylene-O-butylene-, -ethylene-O-ethylene-O-ethylene-O-propylene-O-ethylene-, -ethylene-O-ethylene-O-ethylene-O-butylene-O -Ethylene-, -ethylene-O-ethylene-O-propylene-O-ethylene-O-ethylene-, -ethylene-O-ethylene-O-butylene-O-ethylene-O-ethylene-, -ethylene-O-ethylene -O-ethylene-O-ethylene-O-ethylene-O-ethylene-, -ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O Ethylene-O-ethylene-, -ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-, -ethylene-O-ethylene-O-ethylene- O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-, -ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O-ethylene-O- Ethylene-O-ethylene-O-ethylene-O-ethylene-, -propylene-O-butylene-, -propylene-O-pentylene-, -propylene-O-propylene-O-hexylene-, -propylene-O- Xylene-, -propylene-O-propylene-O-heptylene-, -propylene-O-heptylene-, -propylene-O-nonylene-, -propylene -O-ethylene-O-propylene-, -propylene-O-ethylene-O-butylene-, -propylene-O-ethylene-O-pentylene-, -propylene-O-ethylene-O-hexylene-, -propylene- O-ethylene-O-heptylene-, -propylene-O-propylene-O-propylene-, -propylene-O-propylene-O-butylene-, -propylene-O-propylene-O-pentylene-, -propylene-O- -Propylene-O-hexylene-, -propylene-O-butylene-O-propylene-, -propylene-O-butylene-O-butylene-, -propylene-O-butylene-O-pentylene-, -propylene-O-pentylene- O-propylene-, -propylene-O-pentylene-O-butylene-, -propylene-O-hexylene O-propylene-, -propylene-O-propylene-O-propylene-O-propylene-, -propylene-O-propylene-O-propylene-O-propylene-O-propylene-, -propylene-O-propylene-O- Propylene-O-propylene-O-propylene-O-propylene-,-butylene-O-butylene-,-butylene-O-pentylene-,-butylene-O-hexylene-,-butylene-O-heptylene-,-butylene- O-octylene-, -butylene-O-ethylene-O-butylene-, -butylene-O-propylene-O-butylene-, -butylene-O-butylene-O-butylene-, -butylene-O-butylene-O- Butylene-O-butylene-,-butylene-O-butylene-O-butylene-O-butylene-O-butylene-, Tylene-O-pentylene-, -pentylene-O-hexylene-, -pentylene-O-hexylene-, -pentylene-O-heptylene-, -pentylene-O-ethylene-O-pentylene-, -pentylene-O- Pentylene-O-pentylene-, -pentylene-O-pentylene-O-pentylene-O-pentylene-, -hexylene-O-hexylene-, -hexylene-O-hexylene-O-hexylene-, -heptylene -O-heptylene-, -octylene-O-octylene-, -nonylene-O-nonylene-, -decylene-O-decylene- and the like.
上記「主鎖中に−Ｏ−を１以上有する置換若しくは非置換の直鎖又は分岐の炭素数２〜２０のアルキレン基」の置換基は、上記「置換又は非置換の直鎖の炭素数１〜２０のアルキレン基」の置換基と同様である。 The substituent of the above-mentioned “substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms having one or more —O— in the main chain” is the above “substituted or unsubstituted linear carbon number of 1”. The substituent is the same as the substituent of “˜20 alkylene group”.
上記「−Ｏ−を１以上有する置換又は非置換の直鎖又は分岐の炭素数２〜２０のアルキレン基」の置換基が、水酸基、ジアルキルアミノ基、アルコキシ基、含窒素ヘテロ環基等であるとき、好ましくは、上記置換基が酸素原子に結合した炭素原子に存在しない。 The substituent of the above-mentioned “substituted or unsubstituted linear or branched alkylene group having 2 to 20 carbon atoms having at least one —O—” is a hydroxyl group, a dialkylamino group, an alkoxy group, a nitrogen-containing heterocyclic group, or the like. Sometimes, preferably, the substituent is not present on a carbon atom bonded to an oxygen atom.
上記「置換又は非置換の芳香族基」の「芳香族基」は、二価の芳香族環である。芳香族環は、単環又は多環の炭素数６〜１０のアリール基、ヘテロ原子として窒素原子、酸素原子又は硫黄原子を１〜４個有する５〜７員の単環又は多環のヘテロアリール基、及び、ベンゼン環とヘテロ原子として窒素原子、酸素原子又は硫黄原子を１〜４個有する５〜７員の複素環が縮合した縮合環からなるヘテロアリール基を包含する。 The “aromatic group” of the above “substituted or unsubstituted aromatic group” is a divalent aromatic ring. The aromatic ring is a monocyclic or polycyclic aryl group having 6 to 10 carbon atoms, a 5- to 7-membered monocyclic or polycyclic heteroaryl having 1 to 4 nitrogen atoms, oxygen atoms or sulfur atoms as heteroatoms. And a heteroaryl group composed of a condensed ring formed by condensation of a benzene ring and a 5- to 7-membered heterocycle having 1 to 4 nitrogen atoms, oxygen atoms or sulfur atoms as heteroatoms.
芳香族環として具体的には、ベンゼン、ナフタレン、アズレン、アントラセン、テトラセン、ペンタセン、フェナントレン、ピレン、ピロール、フラン、チオフェン、ピラゾール、イミダゾール、オキサゾール、チアゾール、トリアゾール、オキサジアゾール、チアジアゾール、ピリジン、ピリダジン、ピリミジン、ピラジン、トリアジン、インドール、イソインドール、ベンズオキサゾール、ベンズチアゾール、ベンゾイソキサゾール、ベンズイソチアゾール、ベンゾオキサジアゾール、ベンズチアジアゾール、ピロロピリジン、ピロロピラジン、プリン、キノリン、イソキノリン、シノリン、キナゾリン、キノキサリン等が挙げられる。 Specific examples of aromatic rings include benzene, naphthalene, azulene, anthracene, tetracene, pentacene, phenanthrene, pyrene, pyrrole, furan, thiophene, pyrazole, imidazole, oxazole, thiazole, triazole, oxadiazole, thiadiazole, pyridine, pyridazine , Pyrimidine, pyrazine, triazine, indole, isoindole, benzoxazole, benzthiazole, benzisoxazole, benzisothiazole, benzoxadiazole, benzthiadiazole, pyrrolopyridine, pyrrolopyrazine, purine, quinoline, isoquinoline, cinolin, quinazoline Quinoxaline and the like.
上記「置換又は非置換の炭素数３〜７のシクロアルキレン基」は、二価の環状アルキレン基である。上記「置換又は非置換の炭素数３〜７のシクロアルキレン基」として、具体的には、シクロプロピレン、シクロブチレン、シクロペンチレン、シクロヘキシレン、シクロヘプチレン等が挙げられる。 The “substituted or unsubstituted cycloalkylene group having 3 to 7 carbon atoms” is a divalent cyclic alkylene group. Specific examples of the “substituted or unsubstituted cycloalkylene group having 3 to 7 carbon atoms” include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene and the like.
上記「置換又は非置換の芳香族基」及び上記「置換又は非置換の炭素数３〜７のシクロアルキレン基」の置換基として、上記「置換又は非置換の直鎖の炭素数１〜２０のアルキレン基」の置換基と同様の置換基が挙げられる。 As a substituent of the above “substituted or unsubstituted aromatic group” and the above “substituted or unsubstituted cycloalkylene group having 3 to 7 carbon atoms”, the above “substituted or unsubstituted straight chain carbon number 1 to 20 carbon atoms” Substituents similar to those of the “alkylene group” can be mentioned.
本発明の含硫黄樹脂の製造方法は特定の方法に限定されない。当該製造方法の具体例は以下のとおりである。
分子状硫黄（Ｓ８）は、有機溶媒に不溶又は溶解しづらいため、本発明の含硫黄樹脂合成の第一段階は、硫黄の反応容器中での加熱による融解である。硫黄は多くの同素体（Ｓ8、Ｓ6、Ｓ１２、Ｓ１８、Ｓ２０等）を持ち、それぞれが融点を有する。硫黄の最安定な同素体は環状構造をした分子状硫黄（Ｓ８）であり、分子状硫黄（Ｓ８）は３つの結晶形（α硫黄、β硫黄及びγ硫黄）をもち、それらの融点はそれぞれ１１２．８℃、１１９．６℃、１０６．８℃である。そのため、１２０℃以上の温度での加熱が分子状硫黄（Ｓ８）の融解のために必要である。また、分子状硫黄（Ｓ８）は安定構造のα硫黄から温度の上昇とともにβ硫黄、λ硫黄、μ硫黄へと転移していき、１５９．４℃以上で環状硫黄のラジカル開裂が進み、２価のラジカルができる。このようにして、分子状硫黄（Ｓ８）は１５９．４℃以上の温度でラジカルを発生するため、融解温度は上記温度より低く設定する必要がある。分子状硫黄（Ｓ８）の融解温度は、好ましくは１２０℃〜１５５℃、より好ましくは１３５℃〜１５５℃、更に好ましくは１４５℃〜１５５℃、最も好ましくは１５０℃〜１５５℃である。
The method for producing the sulfur-containing resin of the present invention is not limited to a specific method. Specific examples of the production method are as follows.
Since molecular sulfur (S 8 ) is insoluble or difficult to dissolve in an organic solvent, the first step in the synthesis of the sulfur-containing resin of the present invention is melting of sulfur by heating in a reaction vessel. Sulfur has many allotropes (S 8 , S 6 , S 12 , S 18 , S 20, etc.), each having a melting point. The most stable allotrope of sulfur is molecular sulfur (S 8 ) having a cyclic structure, and molecular sulfur (S 8 ) has three crystal forms (α sulfur, β sulfur and γ sulfur), and their melting points are They are 112.8 ° C., 119.6 ° C. and 106.8 ° C., respectively. Therefore, heating at a temperature of 120 ° C. or higher is necessary for melting molecular sulfur (S 8 ). In addition, molecular sulfur (S 8 ) transitions from α-sulfur having a stable structure to β-sulfur, λ-sulfur and μ-sulfur as the temperature rises, and radical cleavage of cyclic sulfur proceeds at 159.4 ° C. or higher. A valent radical is formed. Thus, since molecular sulfur (S 8 ) generates radicals at a temperature of 159.4 ° C. or higher, the melting temperature must be set lower than the above temperature. The melting temperature of molecular sulfur (S 8) is preferably from 120 ° C. to 155 ° C., more preferably 135 ° C. to 155 ° C., more preferably 145 ° C. to 155 ° C., and most preferably 0.99 ° C. to 155 ° C..
次いで、上記式（２）で表されるジチオール化合物が溶融された分子状硫黄（Ｓ８）に加えられ、ジスルフィド−チオール交換反応が行われ、上記式（１）で表される本発明の含硫黄樹脂が１段階で合成される。その際、上記式（２）で表されるジチオール化合物が溶融された分子状硫黄（Ｓ８）に均一に分散されるよう、反応中、攪拌が行われてよい。 Next, the dithiol compound represented by the above formula (2) is added to the molten molecular sulfur (S 8 ), a disulfide-thiol exchange reaction is performed, and the inclusion of the present invention represented by the above formula (1) is performed. Sulfur resin is synthesized in one step. At that time, stirring may be performed during the reaction so that the dithiol compound represented by the above formula (2) is uniformly dispersed in the molten molecular sulfur (S 8 ).
上記ジスルフィド−チオール交換反応の温度は、分子状硫黄（Ｓ８）が融解している温度範囲であり、好ましくは１２０℃〜１５５℃、より好ましくは１３５℃〜１５５℃、更に好ましくは１４５℃〜１５５℃、最も好ましくは１５０℃〜１５５℃である。 The temperature of the disulfide-thiol exchange reaction is a temperature range in which molecular sulfur (S 8 ) is melted, preferably 120 ° C. to 155 ° C., more preferably 135 ° C. to 155 ° C., still more preferably 145 ° C. to 155 ° C, most preferably 150 ° C to 155 ° C.
本発明の含硫黄樹脂は、式（１）
Ｘは、１以上の正の整数を表し、各単位中のＸの数は異なっていてよい。Ｘの上限値は３２である。
The sulfur-containing resin of the present invention has the formula (1)
X represents a positive integer of 1 or more, and the number of X in each unit may be different. The upper limit of X is 32.
本発明の含硫黄樹脂は、クロロホルム、ジクロロメタン、テトラヒドロフラン、Ｎ−メチル−２−ピロリドン等の有機溶媒に可溶である。上記方法で合成された本発明の含硫黄樹脂は通常精製される必要はないが、高純度の含硫黄樹脂が必要とされる場合、反応生成物が上記有機溶媒に溶解され、ろ過されて、有機溶媒に不溶の硫黄が除かれる。また、ろ過後の溶液が、ゲルろ過クロマトグラフィー等の分子ふるいに供され、樹脂とモノマーが分離される。 The sulfur-containing resin of the present invention is soluble in organic solvents such as chloroform, dichloromethane, tetrahydrofuran and N-methyl-2-pyrrolidone. The sulfur-containing resin of the present invention synthesized by the above method does not usually need to be purified, but when a high-purity sulfur-containing resin is required, the reaction product is dissolved in the organic solvent, filtered, Insoluble sulfur in the organic solvent is removed. Moreover, the solution after filtration is used for molecular sieves, such as a gel filtration chromatography, and resin and a monomer are isolate | separated.
更に、本発明の含硫黄樹脂の構造が、ＮＭＲ測定、ＧＰＣ(ゲル浸透クロマトグラフィー)測定、ＭＡＬＤＩ（マトリックス支援レーザー脱離イオン化法）／ＴＯＦＭＳ（飛行時間型質量分析計）、ＩＲ測定等の分光学的手法により確認される。 Furthermore, the structure of the sulfur-containing resin of the present invention can be measured by NMR measurement, GPC (gel permeation chromatography) measurement, MALDI (matrix-assisted laser desorption / ionization) / TOFMS (time-of-flight mass spectrometer), IR measurement, etc. Confirmed by optical technique.
本発明の含硫黄樹脂に対する硫黄含有量は、好ましくは６０〜９８質量％であり、より好ましくは７０〜９５質量％であり、更に好ましくは８０〜９５質量％である。
本発明の含硫黄樹脂の数平均分子量（Ｍｎ）は、好ましくは３００〜２００００、更に好ましくは１０００〜１００００、最も好ましくは２０００〜５０００である。また、本発明の含硫黄樹脂の数平均分子量（Ｍｎ）は、ＧＰＣによって測定され得る。
The sulfur content with respect to the sulfur-containing resin of the present invention is preferably 60 to 98% by mass, more preferably 70 to 95% by mass, and still more preferably 80 to 95% by mass.
The number average molecular weight (Mn) of the sulfur-containing resin of the present invention is preferably 300 to 20000, more preferably 1000 to 10,000, and most preferably 2000 to 5000. The number average molecular weight (Mn) of the sulfur-containing resin of the present invention can be measured by GPC.
本発明の含硫黄樹脂における、分子状硫黄（Ｓ８）と上記式（２）で表される化合物とのモル比は、好ましくは１：０．０１〜１：１００であり、より好ましくは、１：０．０５〜１：２０であり、更に好ましくは１：０．２５〜１：１０である。 In the sulfur-containing resin of the present invention, the molar ratio of molecular sulfur (S 8 ) to the compound represented by the above formula (2) is preferably 1: 0.01 to 1: 100, more preferably The ratio is 1: 0.05 to 1:20, more preferably 1: 0.25 to 1:10.
本発明の含硫黄樹脂はガラス転移温度を有する。当該ガラス転移温度は、上記式（２）で表される化合物の構造により大きく異なる。本発明の含硫黄樹脂のガラス転移温度は、好ましくは４０℃〜−５５℃、より好ましくは３０℃〜−５０℃、更に好ましくは２０℃〜−５０℃である。本発明の含硫黄ポリマーのガラス転移温度は、例えば、示差走査熱量測定（ＤＳＣ）のような周知技術によって測定され得る。
本発明の含硫黄樹脂は高い弾性を有し、建築、自動車産業等のエラストマー、ゴム材料として利用され得る。
The sulfur-containing resin of the present invention has a glass transition temperature. The glass transition temperature varies greatly depending on the structure of the compound represented by the above formula (2). The glass transition temperature of the sulfur-containing resin of the present invention is preferably 40 ° C to -55 ° C, more preferably 30 ° C to -50 ° C, still more preferably 20 ° C to -50 ° C. The glass transition temperature of the sulfur-containing polymer of the present invention can be measured by well-known techniques such as, for example, differential scanning calorimetry (DSC).
The sulfur-containing resin of the present invention has high elasticity, and can be used as an elastomer and rubber material for construction and automobile industries.
更に、本発明の含硫黄樹脂は熱可塑性を示し、導電助剤と混練され、二次電池用正極に成形され得る。導電助剤として、具体的には、気相法炭素繊維（Ｖａｐｏｒ Ｇｒｏｗｎ Ｃａｒｂｏｎ Ｆｉｂｅｒ：ＶＧＣＦ）、カーボンブラック（ＣＢ）、アセチレンブラック（ＡＢ）、ケッチェンブラック（ＫＢ）、黒鉛等の炭素粉末；アルミニウム、チタン等の正極電位において安定な金属の微粉末等が挙げられる。 Furthermore, the sulfur-containing resin of the present invention exhibits thermoplasticity and can be kneaded with a conductive additive and formed into a positive electrode for a secondary battery. Specifically, carbon powder such as vapor grown carbon fiber (VGCF), carbon black (CB), acetylene black (AB), ketjen black (KB), graphite and the like as a conductive auxiliary agent; aluminum Examples thereof include fine metal powders which are stable at a positive electrode potential such as titanium.
本発明の二次電池用正極が含有する本発明の含硫黄樹脂と導電助剤の配合割合は、本発明の含硫黄樹脂：導電助剤（質量比）として好ましくは１〜２０：１であり、より好ましくは５〜１０：１である。 The blending ratio of the sulfur-containing resin of the present invention and the conductive additive contained in the positive electrode for secondary battery of the present invention is preferably 1 to 20: 1 as the sulfur-containing resin of the present invention: conductive additive (mass ratio). More preferably, it is 5-10: 1.
本発明の二次電池用正極が成形される際、バインダーが本発明の含硫黄樹脂及び導電助剤と共に混練されてよい。バインダーの具体例として、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、スチレン−ブタジエンゴム（ＳＢＲ）、ポリイミド（ＰＩ）、ポリアミドイミド（ＰＡＩ）、カルボキシメチルセルロース（ＣＭＣ）、ポリ塩化ビニル（ＰＶＣ）、メタクリル樹脂（ＰＭＡ）、ポリアクリロニトリル（ＰＡＮ）、変性ポリフェニレンオキシド（ＰＰＯ）、ポリエチレンオキシド（ＰＥＯ）、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等が挙げられる。 When the positive electrode for a secondary battery of the present invention is molded, a binder may be kneaded together with the sulfur-containing resin and the conductive auxiliary of the present invention. Specific examples of the binder include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyimide (PI), polyamideimide (PAI), carboxymethylcellulose (CMC), polyvinyl chloride ( PVC), methacrylic resin (PMA), polyacrylonitrile (PAN), modified polyphenylene oxide (PPO), polyethylene oxide (PEO), polyethylene (PE), polypropylene (PP) and the like.
本発明の二次電池用正極を備える本発明の二次電池の負極の好ましい材料は、リチウム、マグネシウム、アルミニウム、及びナトリウムから選ばれるいずれか一つであり、より好ましい当該材料はリチウムである。 The preferable material of the negative electrode of the secondary battery of the present invention including the positive electrode for the secondary battery of the present invention is any one selected from lithium, magnesium, aluminum, and sodium, and the more preferable material is lithium.
本発明の二次電池の集電体は、二次電池用正極で一般に用いられる集電体である。本発明の二次電池の集電体として、具体的には、ステンレス箔、ステンレスメッシュ、アルミニウム箔、アルミニウムメッシュ、パンチングアルミニウムシート、アルミニウムエキスパンドシート、ステンレススチール箔、ステンレススチールメッシュ、パンチングステンレススチールシート、ステンレススチールエキスパンドシート、発泡ニッケル、ニッケル不織布、銅箔、銅メッシュ、パンチング銅シート、銅エキスパンドシート、チタン箔、チタンメッシュ、カーボン不織布、カーボン織布等が挙げられる。好ましい集電体はステンレスメッシュである。 The current collector of the secondary battery of the present invention is a current collector generally used in a positive electrode for a secondary battery. As the current collector of the secondary battery of the present invention, specifically, stainless steel foil, stainless steel mesh, aluminum foil, aluminum mesh, punched aluminum sheet, aluminum expanded sheet, stainless steel foil, stainless steel mesh, punched stainless steel sheet, Examples include stainless steel expanded sheets, foamed nickel, nickel nonwoven fabric, copper foil, copper mesh, punched copper sheet, copper expanded sheet, titanium foil, titanium mesh, carbon nonwoven fabric, and carbon woven fabric. A preferred current collector is a stainless mesh.
本発明の二次電池の電解質は、二次電池で一般に用いられる電解質である。本発明の二次電池の電解質として、具体的には、１，２−ジメトキシエタン、アセトニトリル、プロピレンカーボネート、エチレンカーボネート、３−メトキシプロピオニトリル、メトキシアセトニトリル、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、ブチルロラクトン、ジメトキシエタン、ジメチルカーボネート、１，３−ジオキソラン、メチルホルメート、２−メチルテトラハイドロフラン、３−メトキシ−オキサゾリデン−２−オン、スルホラン、テトラハイドロフラン、トリエチレングリコールジメチルエーテル、水等が挙げられる。これらは単独で又は２種以上混合されて使用される。好ましい電解質は１，２−ジメトキシエタンと１，３−ジオキソランが１：１（体積比）で混合されている混合物である。 The electrolyte of the secondary battery of the present invention is an electrolyte generally used in secondary batteries. Specifically, as the electrolyte of the secondary battery of the present invention, 1,2-dimethoxyethane, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene Glycol, butyrolactone, dimethoxyethane, dimethyl carbonate, 1,3-dioxolane, methyl formate, 2-methyltetrahydrofuran, 3-methoxy-oxazoliden-2-one, sulfolane, tetrahydrofurane, triethylene glycol dimethyl ether, Water etc. are mentioned. These may be used alone or in admixture of two or more. A preferred electrolyte is a mixture in which 1,2-dimethoxyethane and 1,3-dioxolane are mixed at a ratio of 1: 1 (volume ratio).
本発明の二次電池の形状は制限されない。本発明の二次電池は、コイン形、ボタン形、シート形、積層形、円筒形、偏平形、角形、電気自動車等に用いる大型二次電池であり得る。 The shape of the secondary battery of the present invention is not limited. The secondary battery of the present invention can be a large-sized secondary battery used for a coin shape, a button shape, a sheet shape, a laminated shape, a cylindrical shape, a flat shape, a square shape, an electric vehicle, and the like.
以下に、実施例により本発明をより詳細に説明するが、本発明の技術範囲は、これらに限定されない。合成された含硫黄樹脂の分析方法は以下のとおりである。 Hereinafter, the present invention will be described in more detail by way of examples. However, the technical scope of the present invention is not limited to these examples. The analysis method of the synthesized sulfur-containing resin is as follows.
（１）１Ｈ ＮＭＲ分析及び１３Ｃ ＮＭＲ分析
試料が溶媒である重水素化クロロホルムに濃度０．１Ｍとなるように溶解され、日本電子（株）製JNM-ECA（１Ｈ ＮＭＲ、１３Ｃ ＮＭＲ）により、内部標準物質としてトリメチルシランを用いて測定された。
(1) 1 H NMR analysis and 13 C NMR analysis A sample is dissolved in deuterated chloroform as a solvent to a concentration of 0.1 M, and JNM-ECA ( 1 H NMR, 13 C NMR manufactured by JEOL Ltd.) ) Was measured using trimethylsilane as an internal standard substance.
（２）示差走査熱量（ＤＳＣ）分析
（株）日立ハイテクノロジーズ製DSC7020が使用され、試料が昇温速度１０℃／ｍｉｎで加熱され、分析された。
(2) Differential scanning calorimetry (DSC) analysis DSC7020 manufactured by Hitachi High-Technologies Corporation was used, and the sample was heated at a heating rate of 10 ° C / min and analyzed.
（３）熱重量測定
（株）島津製作所製Thermo Plus Evo IIが使用され、試料樹脂が昇温速度１０℃／ｍｉｎで加熱され、分析された。
(3) Thermogravimetry Thermo Plus Evo II manufactured by Shimadzu Corporation was used, and the sample resin was heated at a heating rate of 10 ° C./min and analyzed.
実施例１
分子状硫黄（Ｓ８）（キシダ化学（株）製）３質量部とジチオール化合物であるビス（２−メルカプトエチル）エーテル（ＢＭＥＥ）（ＴＣＩ（株）製）０．８０９質量部（分子状硫黄とジチオール化合物のモル比＝２：１）がサンプル瓶に加えられ、１５５℃で５時間攪拌された。その後、反応生成物が室温になるまで放置され、固化された樹脂［Ｓ−ＢＭＥＥ（０．５）］が回収された。ＢＭＥＥ、Ｓ−ＢＭＥＥ（０．５）が試料とされ、１Ｈ ＮＭＲ分析、１３Ｃ ＮＭＲ分析及び熱重量測定が行われた。１Ｈ ＮＭＲスペクトル、１３Ｃ ＮＭＲスペクトル、熱重量測定の結果が、それぞれ、図１、図２、図３に示されている。
Example 1
Molecular sulfur (S 8 ) (manufactured by Kishida Chemical Co., Ltd.) 3 parts by mass and dithiol compound bis (2-mercaptoethyl) ether (BMEE) (manufactured by TCI Co., Ltd.) 0.809 parts by mass (molecular sulfur And a dithiol compound molar ratio = 2: 1) were added to the sample bottle and stirred at 155 ° C. for 5 hours. Thereafter, the reaction product was allowed to reach room temperature, and the solidified resin [S-BMEE (0.5)] was recovered. BMEE and S-BMEE (0.5) were used as samples, and 1 H NMR analysis, 13 C NMR analysis, and thermogravimetry were performed. The results of 1 H NMR spectrum, 13 C NMR spectrum, and thermogravimetry are shown in FIGS. 1, 2, and 3, respectively.
図１より、ＢＭＥＥの末端のＳＨ基に由来するピークが、Ｓ−ＢＭＥＥ（０．５）のスペクトルからほぼ消失していることが分かる。図２より、ＢＭＥＥの−ＣＨ２−ＣＨ２−Ｏ−ＣＨ２−ＣＨ２−骨格が、Ｓ−ＢＭＥＥ（０．５）にあることが分かった。よって、Ｓ−ＢＭＥＥ（０．５）は、上記式（１）のＲ＝−ＣＨ２−ＣＨ２−Ｏ−ＣＨ２−ＣＨ２−である含硫黄樹脂であることが分かる。なお、図１及び図２中に、溶媒に混入していたテトラヒドロキシフラン（ＴＨＦ）に由来するピークが観察された。 From FIG. 1, it can be seen that the peak derived from the SH group at the end of BMEE has almost disappeared from the spectrum of S-BMEE (0.5). From FIG. 2, it was found that the —CH 2 —CH 2 —O—CH 2 —CH 2 — skeleton of BMEE is in S-BMEE (0.5). Therefore, it turns out that S-BMEE (0.5) is a sulfur-containing resin which is R = —CH 2 —CH 2 —O—CH 2 —CH 2 — in the above formula (1). In FIGS. 1 and 2, a peak derived from tetrahydroxyfuran (THF) mixed in the solvent was observed.
図３より、Ｓ−ＢＭＥＥ（０．５）の質量が２００〜３００℃において大幅に減少したことが分かる。これは、単体硫黄に見られる挙動と同じであり、硫黄の分解（昇華）により起こったと考えられる。従って、その際に生じる「減少量＝硫黄の量」と考えられ、Ｓ−ＢＭＥＥ（０．５）の硫黄の含有量は約９４質量％と見積もられた。 From FIG. 3, it can be seen that the mass of S-BMEE (0.5) was significantly reduced at 200 to 300 ° C. This is the same as the behavior seen in elemental sulfur, and it is thought that it was caused by the decomposition (sublimation) of sulfur. Therefore, it is considered that “the amount of reduction = the amount of sulfur” generated at that time, and the sulfur content of S-BMEE (0.5) was estimated to be about 94% by mass.
実施例２
分子状硫黄（Ｓ８）（キシダ化学（株）製）１質量部とジチオール化合物である３、６−ジオキサ−１、８−オクタンジチオール（ＤＯＤＴ）（ＴＣＩ（株）製）０．３５６質量部（分子状硫黄とジチオール化合物のモル比＝２：１）がサンプル瓶に加えられ、１５５℃で５時間攪拌された。その後、反応生成物が室温になるまで放置され、固化された樹脂［Ｓ−ＤＯＤＴ（０．５）］が回収された。分子状硫黄（Ｓ８）、Ｓ−ＤＯＤＴ（０．５）が試料とされ、ＤＳＣ分析及び熱重量測定が行われた。ＤＳＣチャート、熱重量測定の結果が、それぞれ、図４、図５に示されている。
Example 2
1 part by mass of molecular sulfur (S 8 ) (manufactured by Kishida Chemical Co., Ltd.) and 3,56-dioxa-1,8-octanedithiol (DODT) which is a dithiol compound (manufactured by TCI) 0.356 parts by mass (Molecular sulfur to dithiol compound molar ratio = 2: 1) was added to the sample bottle and stirred at 155 ° C. for 5 hours. Thereafter, the reaction product was left to reach room temperature, and the solidified resin [S-DODT (0.5)] was recovered. Molecular sulfur (S 8), S-DODT (0.5) is the sample, DSC analysis and thermogravimetric analysis were performed. The results of DSC chart and thermogravimetry are shown in FIGS. 4 and 5, respectively.
図４より、Ｓ−ＤＯＤＴ（０．５）は、分子状硫黄（Ｓ８）の融点より低い融点を有し、ガラス転移温度も有する、上記式（１）のＲ＝−ＣＨ２−ＣＨ２−Ｏ−ＣＨ２−ＣＨ２−Ｏ−ＣＨ２−ＣＨ２−である含硫黄樹脂であることが分かる。
図５より、Ｓ−ＤＯＤＴ（０．５）の質量が２００〜３００℃において大幅に減少したことが分かる。Ｓ−ＤＯＤＴ（０．５）の硫黄の含有量は約９２質量％と見積もられた。
From FIG. 4, S = DODT (0.5) has a melting point lower than that of molecular sulfur (S 8 ) and also has a glass transition temperature, and R = —CH 2 —CH 2 of the above formula (1). -O-CH 2 -CH 2 -O- CH 2 -CH 2 - which can be seen that the sulfur-containing resin is.
From FIG. 5, it can be seen that the mass of S-DODT (0.5) was significantly reduced at 200 to 300 ° C. The sulfur content of S-DODT (0.5) was estimated to be about 92% by mass.
実施例３
実施例１で製造されたＳ−ＢＭＥＥ（０．５）８質量部、ケッチェンブラック（ライオン（株）製EC600JD）１質量部及びＰＴＦＥ（（株）ダイキン製ポリフロンＰＴＦＥファインパウダー）が混練され、正極が成形された。リチウムビス（トリフルオロメタンスルホニル）アミド（ＬｉＴＦＳＡ）が１、２−ジメトキシエタン（ＤＭＥ）と１、３−ジオキソラン（ＤＯＸ）が体積比１：１で混合されている溶媒に溶解されている電解液（濃度１Ｍ）と当該正極が使用される、図６に示されるようなコインセル型二次電池が作製された。更に、正極の材料が実施例１で製造されたＳ−ＢＭＥＥ（０．５）９質量部及びケッチェンブラック（ライオン（株）製EC600JD）１質量部とされる以外、上記コインセル型二次電池と同様にされてコインセル型二次電池が作製された。これら２つのコインセル型二次電池のサイクリックボルタンメトリー（ＣＶ）が、電気化学測定システム（北斗電工（株）製ＨＺ−５０００）が使用され、電位走査範囲０．８〜３．０Ｖ、走査速度５ｍＶｓ−１として測定された。結果が図７に示されている。
Example 3
8 parts by mass of S-BMEE (0.5) produced in Example 1, 1 part by mass of Ketjen Black (Lion Corporation EC600JD) and PTFE (Daikin Polyflon PTFE fine powder) were kneaded, A positive electrode was formed. An electrolytic solution in which lithium bis (trifluoromethanesulfonyl) amide (LiTFSA) is dissolved in a solvent in which 1,2-dimethoxyethane (DME) and 1,3-dioxolane (DOX) are mixed at a volume ratio of 1: 1 ( A coin cell type secondary battery as shown in FIG. 6 in which the positive electrode was used at a concentration of 1 M) was produced. Further, the coin cell type secondary battery except that the material of the positive electrode is 9 parts by mass of S-BMEE (0.5) manufactured in Example 1 and 1 part by mass of Ketjen Black (EC600JD manufactured by Lion Corporation). In the same manner as above, a coin cell type secondary battery was produced. Cyclic voltammetry (CV) of these two coin cell type secondary batteries uses an electrochemical measurement system (HZ-5000 manufactured by Hokuto Denko Co., Ltd.), potential scanning range 0.8 to 3.0 V, scanning speed 5 mVs. Measured as -1 . The result is shown in FIG.
図７より、正極の材料として、含硫黄樹脂及びケッチェンブラックと共にバインダーであるＰＴＦＥが使用されていない二次電池は、正極の材料としてＰＴＦＥが使用されている二次電池と同様の電気化学的酸化−還元反応を示した。 As shown in FIG. 7, the secondary battery in which PTFE as a binder is not used as a positive electrode material together with a sulfur-containing resin and ketjen black is similar to the secondary battery in which PTFE is used as a positive electrode material. An oxidation-reduction reaction was shown.
本発明の含硫黄樹脂は、電池材料、特に二次電池の正極材料として利用可能である。 The sulfur-containing resin of the present invention can be used as a battery material, particularly as a positive electrode material for a secondary battery.
Claims (6)
ＨＳ−Ｒ−ＳＨ （２）
（式中、Ｒは置換又は非置換の直鎖の炭素数１〜２０のアルキレン基、主鎖中に−Ｏ−を１以上有する置換若しくは非置換の直鎖又は分岐の炭素数２〜２０のアルキレン基、置換又は非置換の芳香族基、置換又は非置換の炭素数３〜７のシクロアルキレン基からなる群より選ばれるいずれか１つを表す。）で表されるジチオール化合物と分子状硫黄（Ｓ８）を反応させる、含硫黄樹脂の製造方法。 The following formula (2)
HS-R-SH (2)
(In the formula, R is a substituted or unsubstituted linear alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted linear or branched chain group having 2 to 20 carbon atoms having one or more —O— in the main chain. A dithiol compound represented by an alkylene group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted cycloalkylene group having 3 to 7 carbon atoms, and molecular sulfur. A method for producing a sulfur-containing resin, in which (S 8 ) is reacted.
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| JP2018065980A (en) * | 2016-10-17 | 2018-04-26 | 国立大学法人山口大学 | Sulfur-containing polymer |
| WO2019189899A1 (en) | 2018-03-29 | 2019-10-03 | 日本放送協会 | Image encoding device, image decoding device, and program |
| KR102678156B1 (en) | 2021-06-02 | 2024-06-24 | 포항공과대학교 산학협력단 | Fast-Charging, High-Energy, Flexible Lithium-Sulfur Batteries Based on Hierarchically Ordered Sulfur Particles and preparation method thereof |
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| KR102678156B1 (en) | 2021-06-02 | 2024-06-24 | 포항공과대학교 산학협력단 | Fast-Charging, High-Energy, Flexible Lithium-Sulfur Batteries Based on Hierarchically Ordered Sulfur Particles and preparation method thereof |
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