CN117682972B - Organic compound containing sulfonamide group and fluorinated group and application thereof - Google Patents
Organic compound containing sulfonamide group and fluorinated group and application thereof Download PDFInfo
- Publication number
- CN117682972B CN117682972B CN202410131525.2A CN202410131525A CN117682972B CN 117682972 B CN117682972 B CN 117682972B CN 202410131525 A CN202410131525 A CN 202410131525A CN 117682972 B CN117682972 B CN 117682972B
- Authority
- CN
- China
- Prior art keywords
- ether
- lithium
- carbonate
- lithium metal
- electrolyte
- 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.)
- Active
Links
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 27
- 125000000565 sulfonamide group Chemical group 0.000 title claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 93
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims description 47
- 239000000654 additive Substances 0.000 claims description 41
- 230000000996 additive effect Effects 0.000 claims description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 229910003002 lithium salt Inorganic materials 0.000 claims description 23
- 159000000002 lithium salts Chemical class 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 14
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229910000733 Li alloy Inorganic materials 0.000 claims description 5
- 239000001989 lithium alloy Substances 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 claims description 2
- KIAMPLQEZAMORJ-UHFFFAOYSA-N 1-ethoxy-2-[2-(2-ethoxyethoxy)ethoxy]ethane Chemical compound CCOCCOCCOCCOCC KIAMPLQEZAMORJ-UHFFFAOYSA-N 0.000 claims description 2
- CAQYAZNFWDDMIT-UHFFFAOYSA-N 1-ethoxy-2-methoxyethane Chemical compound CCOCCOC CAQYAZNFWDDMIT-UHFFFAOYSA-N 0.000 claims description 2
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 claims description 2
- HYDWALOBQJFOMS-UHFFFAOYSA-N 3,6,9,12,15-pentaoxaheptadecane Chemical compound CCOCCOCCOCCOCCOCC HYDWALOBQJFOMS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 claims description 2
- 229910008365 Li-Sn Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 229910006759 Li—Sn Inorganic materials 0.000 claims description 2
- 150000005678 chain carbonates Chemical class 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- JRRDISHSXWGFRF-UHFFFAOYSA-N 1-[2-(2-ethoxyethoxy)ethoxy]-2-methoxyethane Chemical compound CCOCCOCCOCCOC JRRDISHSXWGFRF-UHFFFAOYSA-N 0.000 claims 1
- YZWVMKLQNYGKLJ-UHFFFAOYSA-N 1-[2-[2-(2-ethoxyethoxy)ethoxy]ethoxy]-2-methoxyethane Chemical compound CCOCCOCCOCCOCCOC YZWVMKLQNYGKLJ-UHFFFAOYSA-N 0.000 claims 1
- 229910000521 B alloy Inorganic materials 0.000 claims 1
- 229910000861 Mg alloy Inorganic materials 0.000 claims 1
- 229910020923 Sn-O Inorganic materials 0.000 claims 1
- BVWQQMASDVGFGI-UHFFFAOYSA-N ethene propyl hydrogen carbonate Chemical compound C(CC)OC(O)=O.C=C BVWQQMASDVGFGI-UHFFFAOYSA-N 0.000 claims 1
- 239000004210 ether based solvent Substances 0.000 claims 1
- LCLOXRAKDJBSMN-UHFFFAOYSA-N pentyl hydrogen carbonate Chemical compound CCCCCOC(O)=O LCLOXRAKDJBSMN-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 27
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 210000001787 dendrite Anatomy 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 206010067484 Adverse reaction Diseases 0.000 abstract description 6
- 230000006838 adverse reaction Effects 0.000 abstract description 6
- 230000006698 induction Effects 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 238000007614 solvation Methods 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000002000 Electrolyte additive Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 24
- 210000004027 cell Anatomy 0.000 description 22
- 239000007795 chemical reaction product Substances 0.000 description 16
- 239000000725 suspension Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000012295 chemical reaction liquid Substances 0.000 description 14
- 229940125904 compound 1 Drugs 0.000 description 14
- 239000002243 precursor Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000012467 final product Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 229910013870 LiPF 6 Inorganic materials 0.000 description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 10
- 239000012312 sodium hydride Substances 0.000 description 10
- 229910000104 sodium hydride Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229940125782 compound 2 Drugs 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 229940126214 compound 3 Drugs 0.000 description 7
- 229940125898 compound 5 Drugs 0.000 description 7
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 7
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 7
- 239000000110 cooling liquid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010835 comparative analysis Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 2
- 125000006546 (C4-C10) cycloalkyl group Chemical group 0.000 description 1
- TXOZSRCVHASUCW-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropan-1-ol Chemical compound OC(F)CC(F)(F)F TXOZSRCVHASUCW-UHFFFAOYSA-N 0.000 description 1
- PPMCFKAXXHZLMX-UHFFFAOYSA-N 1,3-dioxocan-2-one Chemical compound O=C1OCCCCCO1 PPMCFKAXXHZLMX-UHFFFAOYSA-N 0.000 description 1
- VOGSDFLJZPNWHY-UHFFFAOYSA-N 2,2-difluoroethanol Chemical compound OCC(F)F VOGSDFLJZPNWHY-UHFFFAOYSA-N 0.000 description 1
- FETMDPWILVCFLL-UHFFFAOYSA-N 2-[2-(2-propan-2-yloxyethoxy)ethoxy]ethanol Chemical compound CC(C)OCCOCCOCCO FETMDPWILVCFLL-UHFFFAOYSA-N 0.000 description 1
- JECPJHZWLKEQFB-UHFFFAOYSA-N 2-[2-[2-(2-propan-2-yloxyethoxy)ethoxy]ethoxy]ethanol Chemical compound CC(C)OCCOCCOCCOCCO JECPJHZWLKEQFB-UHFFFAOYSA-N 0.000 description 1
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical compound OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910008410 Li-Sn-O Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910008290 Li—B Inorganic materials 0.000 description 1
- 229910006309 Li—Mg Inorganic materials 0.000 description 1
- 229910006763 Li—Sn—O Inorganic materials 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- QQUZYDCFSDMNPX-UHFFFAOYSA-N ethene;4-methyl-1,3-dioxolan-2-one Chemical compound C=C.CC1COC(=O)O1 QQUZYDCFSDMNPX-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000006341 heptafluoro n-propyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- NDYAAZRKZRTLQC-UHFFFAOYSA-N n,n-diethylsulfamoyl chloride Chemical compound CCN(CC)S(Cl)(=O)=O NDYAAZRKZRTLQC-UHFFFAOYSA-N 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000003313 weakening effect Effects 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
- Secondary Cells (AREA)
Abstract
The invention provides an organic compound containing a sulfonamide group and a fluorinated group and application thereof, and particularly relates to the technical field of lithium metal batteries. The structure of the organic compound containing the sulfonyl amino group and the fluorinated group is shown as the following formula; The organic compound is used as an electrolyte additive in the preparation of a lithium battery, and has two functional groups, namely a sulfonamide group and a fluorinated group, so that the solvation structure of Li + can be effectively regulated, the formation of an SEI interface film is promoted, and meanwhile, the organic compound can be subjected to preferential reduction decomposition on the surface of a lithium metal negative electrode through a strong electron-withdrawing induction effect, so that the interface film formed on the surface of the negative electrode is effectively regulated and controlled, and a uniform, compact and high-ion-conductivity interface film is formed on the surface of the lithium metal negative electrode, so that the cycle performance of the lithium metal battery is improved, and the electrochemical adverse reaction caused by the growth of lithium dendrites in the lithium metal battery is weakened.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to an organic compound containing sulfonamide groups and fluorinated groups and application thereof.
Background
With the wide application of portable electronic products (such as smart phones and notebook computers), power grid storage, and electric automobiles, the need for rechargeable batteries with high energy density is urgent. Alkaline ion batteries (e.g., lithium ion batteries, sodium ion batteries, potassium ion batteries) have been considered the first candidate to be the most promising for energy crisis resolution in the past decades due to their energy density several times that of commercial lead acid batteries, especially lithium ion batteries. However, in the practical application process, the limitation of the battery system prevents the battery system from reaching the high energy density of 500-700 Wh.kg -1, so that the battery system can not meet the requirements of the related fields such as electric automobiles, electric aircrafts and the like on the high energy density battery in the future, and the development of the battery system with higher energy density is urgent.
Among a new series of developed new battery materials with high energy density, lithium metal has received a lot of attention, and when it is used as a battery negative electrode material, it is called lithium metal negative electrode (LMA), because of the characteristics of lithium itself, such as: the ultrahigh theoretical specific capacity 38360 mAh.g -1, the low electrochemical potential-3.04V (relative to a standard hydrogen electrode, SHE) and the low mass density (0.59 g.cm -3) enable the assembled Lithium Metal Battery (LMB) to have ultrahigh theoretical energy density, and be considered as a next-generation battery exceeding an alkaline ion battery, and hopefully meet the requirement of high energy density in the future.
However, LMBs has many problems to be overcome in practical applications, such as the thermodynamic instability of lithium metal itself and its ultra-high chemical activity, resulting in LMBs producing unstable interfaces, growing irregular lithium dendrites, and "dead lithium". Also, LMBs thus exhibit poor electrochemical performance during repeated cycles, including poor lifetime, lower coulombic efficiency, and capacity retention. In particular, excessive lithium dendrites can penetrate the separator, which in turn can lead to LMBs premature failure or even explosion, causing a series of safety problems.
Based on the problems existing in the prior art, and in order to meet the requirements of the fields of electric automobiles, electric aircrafts and the like on high-energy-density batteries as soon as possible, optimizing the electrolyte formula is considered to be one of the most promising commercial application methods because of the simplicity and high efficiency.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention mainly aims to provide an organic compound containing sulfonamide groups and fluorinated groups and application thereof, so as to overcome the defects in the prior art.
In order to achieve the above purpose, the invention provides the following technical scheme, namely, an organic compound containing a sulfonamido group and a fluorinated group, wherein the structural formula of the organic compound containing the sulfonamido group and the fluorinated group is shown as formula (I):
formula (I);
Wherein, R 1 is selected from any one of fluoro C 1-C8 alkyl and fluoro C 4-C10 cycloalkyl.
In some preferred embodiments, the method of preparing the organic compound comprises:
S1, providing sodium hydride suspension, wherein the solvent is tetrahydrofuran;
s2, providing a reaction liquid precursor; under the low temperature condition, adding fluoroalcohol into the sodium hydride suspension, and dropwise adding diethyl amine sulfonyl chloride under the protection of inert gas;
s3, preparing a final product, and stirring and reacting the reaction liquid precursor at room temperature to obtain a reaction product; extracting, drying and rotary steaming the reaction product to remove impurities, and then carrying out vacuum distillation to obtain a final product;
the final product is the organic compound containing sulfonamide groups and fluorinated groups.
Based on the organic compound provided by the technical scheme, another object of the invention is to provide an electrolyte, which comprises lithium salt, an organic solvent and an additive, wherein the additive comprises the organic compound containing sulfonamide groups and fluorinated groups and shown in the structural formula I.
The organic compound is used as an additive of electrolyte to be applied to a lithium metal battery, the solvation structure of Li + can be effectively regulated, the formation of an inorganic-rich SEI layer is promoted, and meanwhile, the organic compound can be subjected to preferential reduction decomposition on the surface of a lithium metal negative electrode through a strong electron-withdrawing induction effect, so that the effective regulation and control of an interfacial film formed on the surface of the negative electrode are realized, an interfacial film which is uniform, compact and high in ionic conductivity is formed on the surface of the lithium metal negative electrode, the cycle performance of the lithium metal battery is further improved, and the electrochemical adverse reaction caused by the growth of lithium dendrites in the lithium metal battery is weakened.
The action mechanism of the additive in the electrolyte of the invention is as follows: the organic compound of the additive containing sulfonamide groups and fluorinated groups has two groups which each contribute to the formation of a uniform, compact and high ionic conductivity interfacial film on the surface of the lithium metal negative electrode. The existence of the sulfonamide group (-NSO 2 -) enables the molecule of the additive to have a high donor number, so that the introduction of the additive into an electrolyte can adjust the solvation structure of Li +, weaken the interaction of Li + -solvent, adjust the competitive adsorption of various substances on the surface of LMA, increase the anion concentration of an EDL region on the surface of lithium metal, and thereby facilitate the formation of an SEI layer rich in inorganic phase, wherein the SEI layer rich in inorganic phase has higher mechanical strength and high interfacial energy with lithium metal, and is favorable for the lateral growth of Li deposited on the surface of lithium metal under the condition of not growing lithium dendrites. Meanwhile, fluorine atoms in fluorinated groups in the additive have a strong electron-withdrawing induction effect, and the additive is subjected to reduction decomposition on a lithium metal cathode more preferentially by the strong electron-withdrawing effect, so that interface chemistry can be regulated and controlled more effectively. Therefore, the additive can promote the formation of uniform SEI after being introduced into electrolyte, reduce the generation of lithium dendrite, improve CE value and improve battery cycle performance.
The embodiment of the invention also provides a lithium metal battery containing the electrolyte, which comprises a positive electrode material, a negative electrode material, the electrolyte and a separation film arranged between the positive electrode and the negative electrode, wherein the electrolyte is the electrolyte.
Compared with the prior art, the invention at least comprises the following beneficial effects:
By adopting the electrolyte provided by the invention, the solvation structure of Li + can be effectively regulated and the formation of an inorganic-rich SEI layer is promoted by adopting the additive which simultaneously has two functional fragments of the sulfonamide group and the fluorinated group; the lithium metal cathode surface can be subjected to preferential reduction decomposition by the strong electron-withdrawing induction effect, so that an interface film with uniform, compact and high ion conductivity can be formed on the lithium metal cathode surface, the cycle performance of the lithium metal battery is further improved, the electrochemical adverse reaction caused by lithium dendrite growth in the lithium metal battery is weakened, and the electrochemical stability of the lithium metal battery is improved.
Detailed Description
The objects, technical solutions and advantages of the embodiments of the present application will be more apparent, and the technical solutions in the embodiments of the present application will be clearly and completely described, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application.
The disclosures of all patent and non-patent documents cited in this invention are incorporated herein by reference in their entirety.
The terms "comprises," "comprising," "includes," "including," "having," "with," or any other variation thereof, as used in the present invention, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or" rather than an exclusive "or".
In addition, the use of "a" or "an" to describe elements and components described herein is for convenience only and is not to be taken in a generic sense for the scope of the invention. This description should be read to include one or at least one, and the singular also includes the plural unless it is obvious that it is meant otherwise.
The invention provides an organic compound containing a sulfonyl amino group and a fluorinated group, which has a structural formula shown in a formula (I):
formula (I);
Wherein, R 1 is selected from any one of fluoro C 1-C8 alkyl and fluoro C 4-C10 cycloalkyl.
Preferably, the preparation method of the organic compound comprises:
S1, providing sodium hydride suspension, wherein the solvent is tetrahydrofuran;
s2, providing a reaction liquid precursor; under the low temperature condition, adding fluoroalcohol into the sodium hydride suspension, and dropwise adding diethyl amine sulfonyl chloride under the protection of inert gas;
s3, preparing a final product, and stirring and reacting the reaction liquid precursor at room temperature to obtain a reaction product; extracting, drying and rotary steaming the reaction product to remove impurities, and then carrying out vacuum distillation to obtain a final product;
the final product is the organic compound containing sulfonamide groups and fluorinated groups.
In some preferred embodiments, the sodium hydride suspension has a concentration of 1mol/L.
In some preferred embodiments, the molar ratio of fluoroalcohol to diethylsulfamoyl chloride is 1:1.
In some preferred embodiments, in S3, the extraction of the reaction product comprises adding the reaction product to a saturated aqueous sodium carbonate solution and extracting with an ether to obtain an extracted product.
Specifically, the invention adopts an organic compound containing sulfonamide groups and fluorinated groups as an electrolyte additive, and realizes effective regulation and control of an interfacial film formed on the surface of a negative electrode through modification of electrolyte, so that an interfacial film with uniform, compact and high ion conductivity is formed on the surface of a lithium metal negative electrode, thereby improving the electrochemical stability of a lithium metal battery.
Some embodiments of the present invention provide an electrolyte solution including a lithium salt, an organic solvent, and an additive, where the additive includes an organic compound containing a sulfonamide group and a fluorinated group, where the organic compound is represented by structural formula i:
The electrolyte additive provided by the invention has two functional fragments, namely a sulfonamide group and a fluorinated group, the existence of the sulfonamide group can effectively adjust the solvation structure of Li +, and the formation of an SEI film layer is promoted; the latter has strong electron-withdrawing induction effect to lead the lithium metal anode surface to be reduced and decomposed preferentially. Therefore, the interface film formed on the surface of the negative electrode can be effectively regulated and controlled, so that the interface film which is uniform, compact and high in ionic conductivity can be formed on the surface of the lithium metal negative electrode, the cycle performance of the lithium metal battery is further improved, and the electrochemical adverse reaction caused by the growth of lithium dendrites in the lithium metal battery is weakened.
In some preferred embodiments, the additive is an organic compound containing both sulfonamide groups and fluorinated groups.
In some preferred embodiments, the structural formula of the additive includes at least one of the formulas (II) to (VI):
Formula (II),/> A compound of the formula (III),
(IV),/>(V),
(VI)
In some preferred embodiments, the organic compound containing sulfonamide groups and fluorinated groups of the additive used in the electrolyte of the present invention accounts for 0.1wt% to 5wt% of the sum of the mass of the lithium salt, the organic solvent and the additive.
In some preferred embodiments, the lithium salt may be optionally selected from any one or a combination of two or more of LiClO 4、LiBF4、LiAsF6、LiPF6、LiSbF6, etc., but is not limited thereto.
Further, the lithium salt accounts for 4.5-15.5 wt% of the sum of the mass of the lithium salt, the mass of the organic solvent and the mass of the additive, and the lithium salt can provide good ion conductivity, good solubility and the like for the electrolyte.
Further, the concentration of lithium salt in the electrolyte is 1 mol.L -1~5 mol•L-1.
In some preferred embodiments, the organic solvent is selected from at least one of a chain carbonate, a cyclic carbonate, an ether solvent. For example, any one or a combination of two or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl ethyl carbonate (EMC), ethylene propylene carbonate (PEC), ethylene Carbonate (EC), propylene Carbonate (PC), fluoroethylene carbonate (FEC), butylene carbonate, pentylene carbonate, dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether, ethylpropyl ether, dimethoxyethane, diethoxyethane, methoxyethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methylethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol methylethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, polyethylene glycol methylethyl ether, and the like may be preferable.
Another aspect of the embodiments of the present invention also provides a lithium metal battery including an electrolyte, which includes a positive electrode material, a negative electrode material, an electrolyte, and a separator disposed between the positive electrode and the negative electrode, wherein the electrolyte is any one of the foregoing electrolytes.
In some preferred embodiments, the negative electrode material comprises a lithium-containing metal material comprising metallic lithium or a lithium alloy. The negative electrode material is lithium metal or lithium alloy, so that the capacity of the battery is higher, and the electrolyte comprises the organic compound additive containing sulfonamide groups and fluorinated groups, so that the formation of a uniform and compact SEI layer on the surface of the lithium negative electrode can be promoted, and the cycle performance of the battery is further improved.
Further, the lithium alloy includes any one or a combination of two or more of a Li-Sn alloy, a Li-Sn-O alloy, a Li-Mg alloy, a Li-B alloy, a Li-Al alloy, and the like, but is not limited thereto.
In summary, the additive adopted in the electrolyte provided by the invention has two functional fragments of the sulfonamide group and the fluoride group, so that the effective regulation and control of the interfacial film formed on the surface of the negative electrode are realized, the interfacial film with uniform, compact and high ion conductivity is formed on the surface of the negative electrode, the cycle performance of the lithium metal battery is further improved, and the electrochemical adverse reaction caused by the growth of lithium dendrite in the lithium metal battery is weakened.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosed composition embodiments, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety unless a particular paragraph is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
The technical scheme, implementation process and principle of the invention will be further explained through specific examples. It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. The described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Unless otherwise indicated, reagents and starting materials used in the following examples were obtained commercially, and test methods in which specific conditions were not noted were generally conducted under conventional conditions or under conditions recommended by the respective manufacturers. Further, unless otherwise indicated, the experimental methods, detection methods, and preparation methods disclosed in the present invention all employ techniques conventional in the art. These techniques are well described in the prior art.
Example 1
The formula (II) is shown as a compound 1.
This example provides a process for the preparation of compound 1 comprising the steps of:
1. 60 mL tetrahydrofuran was placed in a round bottom flask, followed by adding 60 mmol sodium hydride thereto and stirring to form a suspension;
2. Adding 40 mmol of 2-fluoroethanol into the suspension in the step 1 at the temperature of 0 ℃ to obtain a cooling liquid; under the protection of N 2, dropwise adding the diethyl amine sulfonyl chloride of 40 mmol into the cooling liquid to obtain a reaction liquid precursor;
3. Moving the flask filled with the reaction liquid precursor in the step 2 to a room temperature condition, and stirring 24 h for reaction to obtain a reaction product;
4. Adding saturated sodium carbonate aqueous solution into the reaction product in the step 3, extracting with ether to obtain an extracted product, and drying at 80 ℃ for 30min, and spin-evaporating at 60 ℃ for 30min to sufficiently remove impurities such as water and ether;
5. Finally, the product extracted in the step 4 is subjected to vacuum distillation to obtain a final product, and the final product is the compound 1.
The infrared spectrum data of the compound 1 is analyzed by ：IR(KBr,cm-1): 3240 cm-1、1406 cm-1、1330 cm-1、1210 cm-1、1175 cm-1, as follows, and a symmetrical telescopic vibration absorption peak of sulfonamide-SO 2 N-appears at 1330 and cm -1、1406 cm-1; 1175 An asymmetric telescopic vibration absorption peak of sulfonamide-SO 2 N-is arranged at cm -1; a stretching vibration peak of the N-H bond appears at the wavelength 3240 cm -1; the C-F bond stretch shock absorption peak was observed at the wavelength 1210 cm -1, confirming that the prepared material was Compound 1. The yield was found to be 36% by calculation.
Example 2
Formula (III), designated compound 2.
This example provides a process for the preparation of compound 2 comprising the steps of:
1. 60 mL tetrahydrofuran was placed in a round bottom flask, followed by adding 60 mmol sodium hydride thereto and stirring to form a suspension;
2. subsequently adding 40 mmol of 2, 2-difluoroethanol into the suspension in the step 1 at 0 ℃; under the protection of N 2, dropwise adding the diethyl amine sulfonyl chloride of 40 mmol into the cooling liquid to obtain a reaction liquid precursor;
3. The flask filled with the reaction liquid precursor in the step 2 is moved to the room temperature condition, and stirred for 24 h to react to obtain a reaction product;
4. Adding saturated sodium carbonate aqueous solution into the reaction product in the step 3, extracting with ether to obtain an extracted product, and drying at 80 ℃ for 30min, and spin-evaporating at 60 ℃ for 30min to sufficiently remove impurities such as water and ether;
5. finally, the product extracted in the step 4 is subjected to vacuum distillation to obtain a final product, namely the compound 2.
The infrared spectrum data of compound 2, compared with compound 1, lack the telescopic vibration absorption peak of the C-F bond at 1210 cm -1, and appear the characteristic absorption peak of 1330: 1330 cm -1 belonging to-CF 2 functional group, which in turn confirms that the prepared substance is compound 2. The yield was 48% by calculation.
Example 3
The formula (IV) is shown as a compound 3.
This example provides a process for the preparation of compound 3 comprising the steps of:
1. 60 mL tetrahydrofuran was placed in a round bottom flask, followed by adding 60 mmol sodium hydride thereto and stirring to form a suspension;
2. Adding 40 mmol of 2, 2-trifluoroethanol into the suspension in the step 1 at 0 ℃; under the protection of N 2, dropwise adding the diethyl amine sulfonyl chloride of 40 mmol into the cooling liquid to obtain a reaction liquid precursor;
3. The flask filled with the reaction liquid precursor in the step 2 is moved to the room temperature condition, and stirred for 24 h to react to obtain a reaction product;
4. Adding saturated sodium carbonate aqueous solution into the reaction product in the step 3, extracting with ether to obtain an extracted product, and drying at 80 ℃ for 30min, and spin-evaporating at 60 ℃ for 30min to sufficiently remove impurities such as water and ether;
5. Finally, the product extracted in the step 4 is subjected to vacuum distillation to obtain a final product, namely the compound 3.
The infrared spectrum data of compound 3, compared with compound 1, lack the telescopic vibration absorption peak of the C-F bond at 1210 cm -1, and appear the characteristic absorption peak of 1308 cm -1 belonging to-CF 3 functional group, and then confirm that the prepared substance is compound 3. The yield was found to be 43% by calculation.
Example 4
Formula (V), designated compound 4.
This example provides a process for the preparation of compound 4 comprising the steps of:
1. 60 mL tetrahydrofuran was placed in a round bottom flask, followed by adding 60 mmol sodium hydride thereto and stirring to form a suspension;
2. Adding 40 mmol of 2, 3-tetrafluoropropanol to the suspension in the step 1 at 0 ℃; under the protection of N 2, dropwise adding the diethyl amine sulfonyl chloride of 40 mmol into the cooling liquid to obtain a reaction liquid precursor;
3. The flask filled with the reaction liquid precursor in the step 2 is moved to the room temperature condition, and stirred for 24 h to react to obtain a reaction product;
4. Adding saturated sodium carbonate aqueous solution into the reaction product in the step 3, extracting with ether to obtain an extracted product, and drying at 80 ℃ for 30min, and spin-evaporating at 60 ℃ for 30min to sufficiently remove impurities such as water and ether;
5. Finally, the product extracted in the step 4 is subjected to vacuum distillation to obtain a final product, namely the compound 4.
The infrared spectrum data of compound 4 showed no extension vibration absorption peak of C-F bond at 1210 cm -1 compared with compound 1, and a characteristic absorption peak of 1330: 1330 cm -1 belonging to-CF 2 functional group, and compared with compound 2, the peak intensity was stronger and the peak area was larger, and then it was confirmed that the prepared substance was compound 4. The yield was found to be 52% by calculation.
Example 5
The formula (VI) is shown as a compound 5.
This example provides a process for the preparation of compound 5 comprising the steps of:
1. 60 mL tetrahydrofuran was placed in a round bottom flask, followed by adding 60 mmol sodium hydride thereto and stirring to form a suspension;
2. Adding 40 mmol of 2, 3-pentafluoro-1-propanol to the suspension in the step 1 at 0 ℃; under the protection of N 2, dropwise adding the diethyl amine sulfonyl chloride of 40 mmol into the cooling liquid to obtain a reaction liquid precursor;
3. The flask filled with the reaction liquid precursor in the step 2 is moved to the room temperature condition, and stirred for 24 h to react to obtain a reaction product;
4. Adding saturated sodium carbonate aqueous solution into the reaction product in the step 3, extracting with ether to obtain an extracted product, and drying at 80 ℃ for 30min, and spin-evaporating at 60 ℃ for 30min to sufficiently remove impurities such as water and ether;
5. finally, the product extracted in the step 4 is subjected to vacuum distillation to obtain a final product, namely the compound 5.
The infrared spectrum data of compound 5, compared with compound 1, lack the telescopic vibration absorption peak of C-F bond at 1210-cm -1, and characteristic absorption peaks ascribed to-CF 2 functional group and-CF 3 functional group appear at 1300-1350-cm -1, which in turn confirms that the prepared substance is compound 5. The yield was found to be 46% by calculation.
Example 6
The embodiment provides a lithium metal battery cell, which comprises the following specific steps of
(1) Preparation of electrolyte
In a vacuum glove box with the moisture content of <1 ppm under the argon atmosphere, mixing Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to the volume ratio of EC to DEC=1 to 1 to obtain a mixed organic solvent; then, a conductive lithium salt LiPF 6 (lithium hexafluorophosphate) was added to the above mixed organic solvent, and the mixture was dissolved and sufficiently stirred to obtain an electrolyte, in which LiPF 6 had a concentration of 5 mol.l -1.
The compound (compound 1) shown in the formula (II) is added into the electrolyte as an additive, and the mass percentage of the additive is 5%.
(2) Preparation of positive electrode plate
Mixing nickel cobalt lithium manganate (LiNi 0.8Co0.1Mn0.1O2, NCM 811), a conductive agent (SP) and a binder (PVDF) according to a mass ratio of 97:1.5:1.5 under a low dew point condition (-40 ℃), then adding an N-methyl pyrrolidone (NMP) solvent, and stirring at a high speed in vacuum to form positive electrode slurry of a lithium metal battery, wherein the solid content is 30%; uniformly coating the slurry on an aluminum foil current collector with the thickness of 10 mu m to prepare a pole piece; and drying the pole piece in a vacuum environment at 85 ℃, and then rolling and cutting to obtain the required positive pole piece.
(3) Preparation of negative electrode plate
In a glove box filled with argon, a lithium metal sheet is punched into a standard shape by a die cutter, and then rolled and flattened to obtain a negative plate.
(4) Preparation of the cell
Sequentially laminating the prepared positive plate, negative plate and polyethylene diaphragm with the thickness of 19 mu m to prepare a square cell, loading the cell into a soft package battery shell made of an aluminum plastic film, injecting the prepared electrolyte in a vacuum environment, packaging, standing, forming, degassing, aging and capacity-dividing to obtain the required soft package lithium metal cell.
Example 7
In this example, the process for preparing the soft-pack lithium metal battery cell is the same as in example 6, except that: the content of the additive compound 1 in the electrolyte in the step (1) is replaced by 2.5% from 5%.
Example 8
In this embodiment, the preparation process of the soft-pack lithium metal battery cell is the same as that of embodiment 6, and the difference is that: the content of the additive compound 1 in the electrolyte in the step (1) is replaced by 0.1% from 5%.
Example 9
In this embodiment, the preparation process of the soft-pack lithium metal battery cell is the same as that of embodiment 6, and the difference is that: the concentration of LiPF 6 in the electrolyte in step (1) was replaced with 3 mol.l -1 from 5 mol.l -1.
Example 10
In this embodiment, the preparation process of the soft-pack lithium metal battery cell is the same as that of embodiment 6, and the difference is that: the concentration of LiPF 6 in the electrolyte in step (1) was replaced with 1 mol.l -1 from 5 mol.l -1.
Example 11
In this embodiment, the preparation process of the soft-pack lithium metal battery cell is the same as that of embodiment 6, and the difference is that: the lithium salt in the electrolyte in step (1) is replaced by LiClO 4 by LiPF 6.
Example 12
In this embodiment, the preparation process of the soft-pack lithium metal battery cell is the same as that of embodiment 6, and the difference is that: the lithium salt in the electrolyte in step (1) is replaced by lithium perchlorate (LiBF 4) by LiPF 6.
Example 13
In this embodiment, the preparation process of the soft-pack lithium metal battery cell is the same as that of embodiment 6, and the difference is that: the lithium salt in the electrolyte in step (1) is replaced by lithium hexafluoroarsenate (LiAsF 6) by LiPF 6.
Example 14
In this embodiment, the preparation process of the soft-pack lithium metal battery cell is the same as that of embodiment 6, and the difference is that: the lithium salt in the electrolyte in step (1) is replaced by lithium hexafluoroantimonate (LiSbF 6) by LiPF 6.
Example 15
In this embodiment, the preparation process of the soft-pack lithium metal battery cell is the same as that of embodiment 6, and the difference is that: in the step (1), the additive in the electrolyte is replaced by a compound 2 shown in a formula III from a compound 1 shown in a formula II, and the addition amount is unchanged.
Example 16
In this embodiment, the preparation process of the soft-pack lithium metal battery cell is the same as that of embodiment 6, and the difference is that: in the step (1), the additive in the electrolyte is replaced by a compound 3 shown in a formula IV from a compound 1 shown in a formula II.
Example 17
In this embodiment, the preparation process of the soft-pack lithium metal battery cell is the same as that of embodiment 6, and the difference is that: in the step (1), the additive in the electrolyte is replaced by a compound 4 shown in a formula V from a compound 1 shown in a formula II.
Example 18
In this embodiment, the preparation process of the soft-pack lithium metal battery cell is the same as that of embodiment 6, and the difference is that: in the step (1), the additive in the electrolyte is replaced by a compound 1 shown in a formula II and a compound 5 shown in a formula VI.
Comparative example 1
(1) Preparation of electrolyte
In a vacuum glove box with a moisture content of <1 ppm under an argon atmosphere, ethylene Carbonate (EC) and diethyl carbonate (DEC) are mixed according to a volume ratio EC: dec=1:1 to obtain the required organic solvent. Then, a conductive lithium salt LiPF 6 was added to the organic solvent, and after dissolution and sufficient stirring, an electrolyte was obtained, in which the concentration of LiPF 6 was 5 mol.l -1. No additives were added in this comparative example.
(2) Preparation of positive electrode plate
Mixing nickel cobalt lithium manganate (LiNi 0.8Co0.1Mn0.1O2, NCM 811), a conductive agent (SP) and a binder (PVDF) according to a mass ratio of 97:1.5:1.5 under a low dew point condition (-40 ℃), then adding an N-methylpyrrolidone (NMP) solvent, and stirring at a high speed in vacuum to form positive electrode slurry of the lithium metal battery; uniformly coating the slurry on an aluminum foil current collector with the thickness of 10 mu m to prepare a pole piece; and drying the pole piece in a vacuum environment at 85 ℃, and then rolling and slitting to obtain the required positive pole piece.
(3) Preparation of negative electrode plate
In a glove box filled with argon, a lithium metal sheet is punched into a standard shape by a die cutter, and then rolled and flattened to obtain a negative plate.
(4) Preparation of the cell
Sequentially laminating the prepared positive plate, negative plate and polyethylene diaphragm with the thickness of 19 mu m to prepare a square cell, loading the cell into a soft package battery shell made of an aluminum plastic film, injecting the prepared electrolyte in a vacuum environment, packaging, standing, forming, degassing, aging and capacity-dividing to obtain the required soft package lithium metal cell.
Performance tests were performed on the soft-pack lithium metal battery cells prepared in examples 6 to 18 and comparative example 1, and specific test conditions thereof are as follows, and performance test results are shown in table 1.
(1) Normal temperature formation test
The lithium metal batteries of examples 6-18 and comparative example 1 were charged to 3.7 v at 25 ℃ with a constant current of 0.1C, charged to 4.2V with a constant current of 0.2C, and charged to a constant voltage of 4.2V until the current dropped to 0.05C; then the battery is discharged to 3.0V by using a constant current of 0.1C, the specific discharge capacity and the specific charge capacity are recorded, and the first efficiency of the corresponding lithium metal battery is calculated according to the specific discharge capacity and the specific charge capacity.
(2) Normal temperature cycle performance test
The lithium metal batteries of examples 6-18 and comparative example 1 were charged to 4.2V at 25 ℃ with a constant current of 0.3C, then charged to a cutoff current of 0.05C with a constant voltage of 4.2V, and then discharged to 3.0V with a constant current of 0.5C, giving a first-week discharge specific capacity and recording as C 1; the charge and discharge were repeated until the nth week, and the specific discharge capacity (designated as C n) after the lithium battery was cycled for n weeks was obtained. Capacity retention = specific discharge capacity after n weeks of cycling (C n)/specific discharge capacity at first week (C 1).
Table 1 results of performance testing of examples and comparative examples
From the results in table 1, it can be seen that:
(1) Comparison analysis of comparative example 1 and examples 6 and examples 15 to 18 show that the performance test results of examples 6 and examples 15 to 18 are significantly better than those of comparative example 1, because the additives containing both functional fragments of sulfonamide group and fluorinated group are introduced into examples 6 and examples 15 to 18. Both play a role and a contribution to the formation of a more stable and uniform SEI interface film on the surface of lithium metal to different degrees, the existence of the sulfonamide group (-NSO 2 -) effectively adjusts the anion concentration in the EDL layer near the surface of lithium metal, the existence of the group changes the solvation structure of Li +, and the anion concentration on the surface of the negative electrode of lithium metal is increased by weakening the interaction between Li + and a solvent, so that the possibility of the participation of anions in the formation of SEI is increased, and the SEI layer rich in inorganic phase is formed more favorably. The SEI layer rich in the inorganic phase has higher mechanical strength and high interfacial energy with lithium metal, and is beneficial to the lateral growth of Li deposited on the surface of the lithium metal under the condition of not growing lithium dendrites. Meanwhile, fluorine atoms in the fluorinated groups have a strong electron-withdrawing induction effect, the additive is reduced and decomposed on the lithium metal negative electrode more preferentially by the strong electron-withdrawing effect, a decomposition product is mainly LiF, and the high surface energy of LiF and lithium metal is favorable for inhibiting the growth of lithium dendrites, so that the effective regulation and control of an interface film formed on the surface of the negative electrode are realized. Therefore, after the additive is introduced into the electrolyte, the formation of a uniform SEI film can be promoted, the electrochemical adverse reaction caused by the growth of lithium dendrites in the lithium metal battery is weakened, and the battery cycle performance is improved.
(2) Comparative analysis of examples 6 and 15-18 shows that the introduction of different additives affects the battery performance to different extents. The comparison finds that the performance index is from good to bad: example 15 (compound 2) > example 17 (compound 4) > example 6 (compound 1) > example 18 (compound 5) > example 16 (compound 3). This may be related to the strong electron withdrawing inducing effect of fluorine atoms in fluorinated groups, which is too strong to be beneficial for recycling.
(3) Comparative analysis examples 6 to 8 show that the cycle performance of lithium metal decreases as the content of the additive decreases. This means that when the content of the additive is low, an SEI film cannot be uniformly formed on the surface of the lithium metal negative electrode, and a desired effect cannot be obtained.
(4) Comparing analysis example 6 with examples 9 to 10, it is known that the lithium salt concentration also affects the cycle performance of the battery. The higher the concentration of lithium salt, the more Li + can be provided, and the more excellent the performance of the corresponding lithium metal battery, the ion conductivity suitable for battery driving can be ensured. Meanwhile, compared with the analysis result of (2), the influence of the lithium salt concentration on the cycle performance is obviously larger than that of the additive concentration.
(5) Comparative analysis of examples 6 and 11 to 14 shows that the lithium salt type has little effect on the cycle performance of the battery.
Furthermore, the inventors have also conducted experiments with reference to the foregoing examples, with other starting materials, process operations, process conditions as described in this specification, for example, substituting-CF 3、-CF2CF3、-CF2CF2CF3, etc., in compounds 1-6 with a partially fluorinated or perfluorinated group of C 4-10 cycloalkyl, C 2-10 alkenyl, C 2-10 alkynyl, C 6-16 aryl, C 6-16 heteroaryl, and all obtained similar results as compounds 1-6.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in the present invention is not meant to limit the invention; each section may apply to any aspect, embodiment, or feature of the present invention.
Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present disclosure also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present disclosure also consist essentially of, or consist of, the recited process step.
Unless specifically stated otherwise, the use of the terms "comprising (include, includes, including)", "having (has, has or has)" should generally be understood to be open-ended and not limiting.
It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (5)
1. An electrolyte is characterized by comprising lithium salt, an organic solvent and an additive, wherein the additive comprises an organic compound containing a sulfonamide group and a fluorinated group and shown in a formula III,
Formula (III);
the additive accounts for 0.1-5 wt% of the sum of the mass of the lithium salt, the organic solvent and the additive.
2. The electrolyte of claim 1, wherein: the lithium salt is any one or the combination of more than two of LiClO 4、LiBF4、LiAsF6、LiPF6、LiSbF6;
the lithium salt accounts for 4.5-15.5 wt% of the sum of the mass of the lithium salt, the mass of the organic solvent and the mass of the additive;
The organic solvent is any one or the combination of more than two of chain carbonate, cyclic carbonate and ether solvents.
3. The electrolyte according to claim 1 or 2, characterized in that: the organic solvent is any one or more than two of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, ethylene propyl carbonate, ethylene carbonate, propylene carbonate, fluoroethylene carbonate, butylene carbonate, amyl carbonate, dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, ethyl propyl ether, dimethoxyethane, diethoxyethane, methoxyethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol methyl ethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether and polyethylene glycol methyl ethyl ether.
4. A lithium metal battery comprising a positive electrode material, a negative electrode material, an electrolyte, and a separator provided between the positive electrode and the negative electrode, the electrolyte being the electrolyte according to any one of claims 1 to 3.
5. The lithium metal battery of claim 4, wherein: the negative electrode material comprises a lithium-containing metal material comprising metallic lithium or a lithium alloy; the lithium alloy is one or the combination of more than two of Li-Sn alloy, li-Sn-O alloy, li-Mg alloy, li-B alloy and Li-Al alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410131525.2A CN117682972B (en) | 2024-01-31 | 2024-01-31 | Organic compound containing sulfonamide group and fluorinated group and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410131525.2A CN117682972B (en) | 2024-01-31 | 2024-01-31 | Organic compound containing sulfonamide group and fluorinated group and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117682972A CN117682972A (en) | 2024-03-12 |
| CN117682972B true CN117682972B (en) | 2024-04-30 |
Family
ID=90132289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410131525.2A Active CN117682972B (en) | 2024-01-31 | 2024-01-31 | Organic compound containing sulfonamide group and fluorinated group and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117682972B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289765A (en) * | 1999-09-29 | 2001-04-04 | 默克专利股份有限公司 | Fluorinated sulfamide for low combustible solvent in electrochemical batteries |
| CN114914543A (en) * | 2022-05-09 | 2022-08-16 | 四川大学 | Electrolyte additive for efficiently inhibiting dendritic crystal, application thereof and lithium metal secondary battery |
| CN115863768A (en) * | 2023-02-22 | 2023-03-28 | 安徽盟维新能源科技有限公司 | Electrolyte and lithium metal battery containing same |
| WO2023134262A1 (en) * | 2022-01-14 | 2023-07-20 | 南方科技大学 | Non-aqueous electrolyte and secondary battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8802301B2 (en) * | 2009-11-06 | 2014-08-12 | GM Global Technology Operations LLC | Lithium ion battery electrolyte including a vitreous eutectic mixture |
| US11942599B2 (en) * | 2020-10-28 | 2024-03-26 | Enevate Corporation | Symmetrical or asymmetrical alkylsulfonyl imide or cyclic alkylene sulfonylimide salts as cathode additives, electrolyte additives, or SI anode additives for SI anode-based li-ion cells |
| US20230100910A1 (en) * | 2021-08-25 | 2023-03-30 | Uchicago Argonne, Llc | Non-flammable electrolytes |
-
2024
- 2024-01-31 CN CN202410131525.2A patent/CN117682972B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289765A (en) * | 1999-09-29 | 2001-04-04 | 默克专利股份有限公司 | Fluorinated sulfamide for low combustible solvent in electrochemical batteries |
| WO2023134262A1 (en) * | 2022-01-14 | 2023-07-20 | 南方科技大学 | Non-aqueous electrolyte and secondary battery |
| CN114914543A (en) * | 2022-05-09 | 2022-08-16 | 四川大学 | Electrolyte additive for efficiently inhibiting dendritic crystal, application thereof and lithium metal secondary battery |
| CN115863768A (en) * | 2023-02-22 | 2023-03-28 | 安徽盟维新能源科技有限公司 | Electrolyte and lithium metal battery containing same |
Non-Patent Citations (2)
| Title |
|---|
| STN检索报告;来源于Aurora Fine Chemicals等提供的产品目录;数据库REGISTRY（在线）;20160120;1-3 * |
| Unraveling Aqueous Self-Assembly of Telodendrimers to Shed Light on Their Efficacy in Drug Encapsulation;Alexandre Moquin et al.;ACS Applied Bio Materials;20190902;第2卷(第10期);4515-4526 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117682972A (en) | 2024-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101099225B1 (en) | Positive Electrode for Nonaqueous Electrolytic Secondary Battery and Method of Manufacturing the Same as well as Nonaqueous Electrolytic Secondary Battery and Method of Manufacturing the Same | |
| CA2688952A1 (en) | Nonaqueous electrolyte for use in a lithium ion cell | |
| CN107093765B (en) | Non-aqueous electrolyte and secondary battery | |
| CN111725575A (en) | High nickel lithium cell and car | |
| CN111864260B (en) | Ether gel electrolyte and preparation method and application thereof | |
| CN114552010B (en) | Additive for lithium metal battery, electrolyte and lithium metal battery | |
| CN113270586A (en) | Preparation and application of in-situ polymerization coated modified silicon-based negative electrode material | |
| CN111934015B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery containing non-aqueous electrolyte | |
| CN112151861A (en) | Battery cathode surface protection composition, electrolyte and application thereof | |
| CN114497743B (en) | Electrolyte applied to alkali metal battery and alkali metal battery thereof | |
| CN113113668B (en) | Electrolyte additive, non-aqueous electrolyte containing electrolyte additive and lithium ion battery | |
| CN115863768B (en) | Electrolyte and lithium metal battery containing same | |
| CN113711412A (en) | Electrolyte solution, electrochemical device, and electronic device | |
| CN117059894A (en) | Electrolyte and alkali metal cell | |
| CN117682972B (en) | Organic compound containing sulfonamide group and fluorinated group and application thereof | |
| EP3244472A1 (en) | Composites comprising hollow microspheres of a vanadium oxide for lithium sulfur cells | |
| CN114421015B (en) | Carbonate-based electrolyte with ether oxygen bond functional group and application thereof | |
| CN114566712B (en) | High-voltage lithium ion battery electrolyte containing lithium difluorophosphate, preparation method thereof and lithium ion battery | |
| CN113416178B (en) | Lithium battery additive amido vinyl sulfate, and preparation method and application thereof | |
| CN111682263B (en) | Application of nitrile compound in preparation of electrolyte for high-voltage battery system | |
| CN110649317B (en) | Silicon-based lithium ion battery electrolyte and lithium ion secondary battery | |
| CN115133125A (en) | Method for improving solubility of lithium salt additive and electrolyte containing lithium salt additive | |
| CN111342133A (en) | Novel non-aqueous electrolyte for lithium ion battery and lithium ion battery | |
| CN116979150A (en) | Diatomic substituted carbonate-based electrolyte and preparation method and application thereof | |
| EP4280331A1 (en) | Carbonate-based electrolyte, method for making the same, and lithium metal battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |