CN109309246A - 电解液及电化学储能装置 - Google Patents
电解液及电化学储能装置 Download PDFInfo
- Publication number
- CN109309246A CN109309246A CN201710624392.2A CN201710624392A CN109309246A CN 109309246 A CN109309246 A CN 109309246A CN 201710624392 A CN201710624392 A CN 201710624392A CN 109309246 A CN109309246 A CN 109309246A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- unsubstituted
- substituted
- nitrile
- quaternary ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 75
- 238000012983 electrochemical energy storage Methods 0.000 title claims abstract description 23
- -1 sulfonate cyclic quaternary ammonium salt Chemical class 0.000 claims abstract description 87
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 125000001118 alkylidene group Chemical group 0.000 claims description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 13
- 125000005700 haloalkyleneoxy group Chemical group 0.000 claims description 11
- 125000004450 alkenylene group Chemical group 0.000 claims description 10
- BCGCCTGNWPKXJL-UHFFFAOYSA-N 3-(2-cyanoethoxy)propanenitrile Chemical compound N#CCCOCCC#N BCGCCTGNWPKXJL-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000005518 polymer electrolyte Substances 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 150000001768 cations Chemical group 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011244 liquid electrolyte Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- OEICGMPRFOJHKO-UHFFFAOYSA-N 2-(ethoxymethylidene)propanedinitrile Chemical compound CCOC=C(C#N)C#N OEICGMPRFOJHKO-UHFFFAOYSA-N 0.000 claims description 2
- WEOKHGKSYLOTPP-UHFFFAOYSA-N 2-methylbutanedinitrile Chemical compound N#CC(C)CC#N WEOKHGKSYLOTPP-UHFFFAOYSA-N 0.000 claims description 2
- NGCJVMZXRCLPRQ-UHFFFAOYSA-N 2-methylidenepentanedinitrile Chemical compound N#CC(=C)CCC#N NGCJVMZXRCLPRQ-UHFFFAOYSA-N 0.000 claims description 2
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 2
- PPHVNJZVJZMSRM-UHFFFAOYSA-N 3-[3-(2-cyanoethoxy)propoxy]propanenitrile Chemical compound N#CCCOCCCOCCC#N PPHVNJZVJZMSRM-UHFFFAOYSA-N 0.000 claims description 2
- RCRNVWKZQROUJM-UHFFFAOYSA-N 3-[4-(2-cyanoethoxy)butoxy]propanenitrile Chemical compound N#CCCOCCCCOCCC#N RCRNVWKZQROUJM-UHFFFAOYSA-N 0.000 claims description 2
- YPNMWIVQXFZROZ-UHFFFAOYSA-N 3-[5-(2-cyanoethoxy)pentoxy]propanenitrile Chemical compound N#CCCOCCCCCOCCC#N YPNMWIVQXFZROZ-UHFFFAOYSA-N 0.000 claims description 2
- SZJIJFGCCHVXPQ-UHFFFAOYSA-N 5-(4-cyanobutoxy)pentanenitrile Chemical compound N#CCCCCOCCCCC#N SZJIJFGCCHVXPQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017048 AsF6 Inorganic materials 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229910005143 FSO2 Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004419 alkynylene group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 2
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- ZVQXQPNJHRNGID-UHFFFAOYSA-N tetramethylsuccinonitrile Chemical compound N#CC(C)(C)C(C)(C)C#N ZVQXQPNJHRNGID-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 239000001273 butane Substances 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 claims 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 21
- 238000006722 reduction reaction Methods 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 229920005554 polynitrile Polymers 0.000 abstract 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000002161 passivation Methods 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 description 53
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 52
- 125000004122 cyclic group Chemical group 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 230000006872 improvement Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000002955 isolation Methods 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000008961 swelling Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical group 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000011356 non-aqueous organic solvent Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- WKFDWSVVMAKCDI-UHFFFAOYSA-N C(C=1C(C(=O)OCC)=CC=CC1)(=O)OCC.[C] Chemical compound C(C=1C(C(=O)OCC)=CC=CC1)(=O)OCC.[C] WKFDWSVVMAKCDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910013275 LiMPO Inorganic materials 0.000 description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical class CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- PNLVGFSEHLOUTK-UHFFFAOYSA-N 2-(bromomethyl)pentanedinitrile Chemical compound BrCC(C#N)CCC#N PNLVGFSEHLOUTK-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- HSWAMGUUBGUSOF-UHFFFAOYSA-N C1(OCCCCCC(CO1)F)=O Chemical compound C1(OCCCCCC(CO1)F)=O HSWAMGUUBGUSOF-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910007857 Li-Al Inorganic materials 0.000 description 1
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
- 229910008410 Li-Sn-O Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 1
- 229910008447 Li—Al Inorganic materials 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- 229910006763 Li—Sn—O Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910010248 TiO2—Li4Ti5O12 Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910021435 silicon-carbon complex Inorganic materials 0.000 description 1
- 239000011867 silicon-carbon complex material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
本申请提供一种电解液及电化学储能装置。所述电解液包括电解质盐以及添加剂。所述添加剂包括磺酸酯环状季铵盐以及多腈化合物。所述磺酸酯环状季铵盐和多腈化合物可以在正、负极表面形成一层致密均匀且具有较高离子传导性的钝化膜,可以避免电解液与正、负极之间发生持续的氧化和还原反应,同时使电化学储能装置具有良好的高温循环性能和高温存储性能。
Description
技术领域
本申请涉及储能装置领域,尤其涉及一种电解液及电化学储能装置。
背景技术
随着化石能源的日益枯竭及环境污染的压力越来越大,汽车行业迫切需要一种新型能源为其提供驱动,锂离子电池由于具有能量密度高、无记忆效应、工作电压高等特点脱颖而出,使其当前成为新能源汽车动力电源的首选方案。然而随着电子产品市场需求的扩大及动力、储能设备的发展,人们对锂离子电池的要求不断提高,开发具有高能量密度且满足快速充放电的锂离子电池成为当务之急。目前,有效的方法是提高电极活性材料的电压、压实密度以及选择合适的电解液。
目前,在锂离子电池中广泛应用的电解液包括以六氟磷酸锂为电解质盐和以环状碳酸酯以及链状碳酸酯的混合物为有机溶剂的电解液,然而上述电解液存在诸多不足,特别的是在高电压下,锂离子电池的高温存储性能较差,其中,电解液作为锂离子电池的重要组成部分,其对锂离子电池的电化学性能有着重大的影响,通过改善电解液的组成能够一定程度上改善锂离子电池的高温存储性能和高温循环性能。
发明内容
鉴于背景技术中存在的问题,本申请的目的在于提供一种电解液及电化学储能装置,所述电解液的添加剂包括磺酸酯环状季铵盐以及多腈化合物,所述磺酸酯环状季铵盐和多腈化合物可以在正、负极表面形成一层致密均匀且具有较高离子传导性的钝化膜,可以避免电解液与正、负极之间发生持续的氧化和还原反应,同时使电化学储能装置具有良好的高温循环性能和高温存储性能。
为了达到上述目的,在本申请的一方面,本申请提供了一种电解液,其包括电解质盐以及添加剂。所述添加剂包括磺酸酯环状季铵盐以及多腈化合物。
在本申请的另一方面,本申请提供了一种电化学储能装置,其包括本申请一方面电解液。
相对于现有技术,本申请的有益效果为:
本申请的电解液的添加剂包括磺酸酯环状季铵盐以及多腈化合物,所述磺酸酯环状季铵盐和多腈化合物可以在正、负极表面形成一层致密均匀且具有较高离子传导性的钝化膜,可以避免电解液与正、负极之间发生持续的氧化和还原反应,同时使电化学储能装置具有良好的高温循环性能和高温存储性能。
具体实施方式
下面详细说明根据本申请的电解液及电化学储能装置。
首先说明根据本申请第一方面的电解液。
根据本申请第一方面的电解液包括电解质盐以及添加剂。所述添加剂包括磺酸酯环状季铵盐以及多腈化合物。
在根据本申请第一方面所述的电解液中,所述磺酸酯环状季铵盐选自式1所示的化合物中的一种或几种;在式1中,R11选自-CN、取代或未取代的C1~12烷基、取代或未取代的C2~12的烯基、取代或未取代的C2~12的炔基、取代或未取代的C1~12的烷氧基、取代或未取代的C1~12的酰氧基中的一种;R12选自取代或未取代的C1~12的亚烷基、取代或未取代的C2~12的亚烯基、取代或未取代的C2~12的亚炔基、取代或未取代的C1~12的亚烷酰基中的一种;R13选自取代或未取代的C1~12的烷基、取代或未取代的C2~12的烯基、取代或未取代的C2~12的炔基、取代或未取代的C1~12的烷氧基、取代或未取代的C1~12的酰氧基、取代或未取代的C6~22的芳基、取代或未取代的C5~22的芳杂基中的一种;R14选自取代或未取代的C1~3的亚烷基;取代基选自-CN、卤素原子中的一种或几种。
在式1中,表示阴离子,选自F-、NO3 -、SO4 2-、PF6 -、PF4 -、AsF6 -、(FSO2)2N-、 中的一种。
在根据本申请第一方面所述的电解液中,所述多腈化合物选自二腈化合物、三腈化合物以及四腈化合物中的一种或几种。具体地,所述二腈化合物可选自式2所示的化合物中的一种或几种,在式2中,R21选自C1~20的亚烷基或卤代亚烷基、C1~20的亚烷氧基或卤代亚烷氧基、C2~20的亚烯基或卤代亚烯基、C2~20的亚烯氧基或卤代亚烯氧基中的一种;所述三腈化合物可选自式3所示的化合物中的一种或几种,在式3中,R31、R32、R33各自独立地选自C0~20的亚烷基或卤代亚烷基、C1~20的亚烷氧基或卤代亚烷氧基、C2~20的亚烯基或卤代亚烯基、C2~20的亚烯氧基或卤代亚烯氧基中的一种;所述四腈化合物可选自式4所示的化合物中的一种或几种,在式4中,R41、R42、R43、R44各自独立地选自C0~20的亚烷基或卤代亚烷基、C1~20的亚烷氧基或卤代亚烷氧基、C2~20的亚烯基或卤代亚烯基、C2~20的亚烯氧基或卤代亚烯氧基中的一种。其中,卤素原子可选自F、Cl、Br、I中的一种或几种。
在根据本申请第一方面所述的电解液中,所述电解液为液体电解液、固态聚合物电解液或凝胶聚合物电解液。由于液态电解液与固态聚合物电解液、凝胶聚合物电解液的作用机理相似,因此在本申请中仅以液态电解液举例进行说明。
在根据本申请第一方面所述的电解液中,所述多腈化合物可以与正极活性材料中的金属离子发生络合反应,并在正极表面形成一层致密且均匀的钝化膜,从而能够有效地抑制正极片中金属的溶出,同时还可以减小高温时电解液在正极界面处的副反应,改善电化学储能装置的高温存储性能和高温循环性能,但是由于腈基具有较强的吸电子特性,其容易在负极得到电子而发生还原反应,其还原产物不稳定会沉积于负极上,从而影响电化学储能装置的高温存储性能和高温循环性能;而磺酸酯环状季铵盐由于其阳离子基团具有特殊的结构(即所述磺酸酯环状季铵盐的阳离子基团部分由带单位正电荷的环状季铵头部和功能性的磺酸酯尾部通过中间的有机碳链连接而成),在还原电位为1.5V时,其带单位正电荷的环状季铵头部能够带动整个阳离子基团主动靠近负极而被优先还原分解断裂,并释放出功能性的磺酸酯尾部,其可以在负极表面建立一层由烷基磺酸金属盐(RSO3X)等物质组成的钝化膜,由于烷基磺酸金属盐具有较高的本征离子传导率,且具有很高的热稳定性,故由此在负极表面形成的钝化膜具有内部结构致密且均匀、阻抗低、高温性能优异等特点,可抑制多腈化合物在负极的还原反应,从而改善电化学储能装置的高温循环性能和高温存储性能。
在根据本申请第一方面所述的电解液中,在式1中,优选地,R11选自取代或未取代的C1~6的烷基或卤代烷基中的一种,R12选自取代或未取代的C1~12的亚烷基中的一种,R13选自取代或未取代的C1~6的烷基或卤代烷基中的一种,R14选自取代或未取代的C1~2的亚烷基中的一种。
在根据本申请第一方面所述的电解液中,所述磺酸酯环状季铵盐的阳离子基团选自
中的一种。
在根据本申请第一方面所述的电解液中,所述磺酸酯环状季铵盐选自下述化合物中的一种或几种;但本申请不限于此;
在根据本申请第一方面所述的电解液中,在式2中,优选地,R21选自C1~10的亚烷基或卤代亚烷基、C0~10的亚烷氧基或卤代亚烷氧基、C2~10的亚烯基或卤代亚烯基、C2~10的亚烯氧基或卤代亚烯氧基中的一种。其中,卤素原子可选自F、Cl、Br中的一种或几种,亚烷氧基、卤代亚烷氧基、亚烯氧基、卤代亚烯氧基中的氧原子数可为1个、2个或多个。
在根据本发明第一方面所述的电解液中,具体地,所述二腈化合物可选自丙二腈、丁二腈、2-甲基丁二腈、四甲基丁二腈、戊二腈、2-甲基戊二腈、己二腈、富马二腈、2-亚甲基戊二腈、3,5-二氧杂-庚二腈、乙二醇二(2-氰基乙基)醚、二乙二醇二(2-氰基乙基)醚、三乙二醇二(2-氰基乙基)醚、四乙二醇二(2-氰基乙基)醚、1,2-二(2-氰乙氧基)乙烷、1,3-二(2-氰基乙氧基)丙烷、1,4-二(2-氰基乙氧基)丁烷、1,5-二(2-氰基乙氧基)戊烷、乙二醇二(4-氰基丁基)醚、1,6-二氰基己烷、1,2-二溴-2,4-二氰基丁烷、乙氧基亚甲基丙二腈中的一种或几种。
在根据本发明第一方面所述的电解液中,在式3中,优选地,R31、R32、R33各自独立地选自C0~10的亚烷基或卤代亚烷基、C1~10的亚烷氧基或卤代亚烷氧基、C2~10的亚烯基或卤代亚烯基、C2~10的亚烯氧基或卤代亚烯氧基中的一种。其中,卤素原子可选自F、Cl、Br中的一种或几种,亚烷氧基、卤代亚烷氧基、亚烯氧基、卤代亚烯氧基中的氧原子数可以为1个、2个或多个。
在根据本申请第一方面所述的电解液中,具体地,所述三腈化合物可选自甲烷三甲腈、乙烯-1,1,2-三甲腈、1,3,6-己烷三腈、1,2,3-丙三甲腈、1,3,5-戊三甲腈中的一种或几种。
在根据本申请第一方面所述的电解液中,在式4中,优选地,R41、R42、R43、R44各自独立地选自C0~10的亚烷基或卤代亚烷基、C1~10的亚烷氧基或卤代亚烷氧基、C2~10的亚烯基或卤代亚烯基、C2~10的亚烯氧基或卤代亚烯氧基中的一种。其中,卤素原子可选自F、Cl、Br中的一种或几种,亚烷氧基、卤代亚烷氧基、亚烯氧基、卤代亚烯氧基中的氧原子数可以为1个、2个或多个。
在根据本申请第一方面所述的电解液中,具体地,所述四腈化合物可选自四氰基乙烯、1,2,2,3-丙烷四甲腈、甲烷四甲腈、1,1,3,3-丙烷四甲腈、1,1,2,2-乙烷四甲腈中的一种或几种。
在根据本申请第一方面所述的电解液中,所述磺酸酯环状季铵盐的含量为所述电解液总质量的0.05%~10%,所述多腈化合物的含量为所述电解液总质量的0.05%~7%,在本申请的电解液中,所述磺酸酯环状季铵盐和多腈化合物配合使用可以改善电化学储能装置的高温循环性能和高温存储性能,可以理解的是,所述磺酸酯环状季铵盐和多腈化合物的用量变化必然直接影响电解液的性能,从而影响电化学储能装置电化学性能的改善。例如,若磺酸酯环状季铵盐和/或多腈化合物的含量过少,则形成的SEI膜过薄,不足以阻止电解液在正、负极表面发生持续的氧化反应和还原反应,因此对电化学储能装置的电化学性能的改善也不明显,尤其是对高温存储产气性能的改善不明显。若磺酸酯环状季铵盐和/或多腈化合物的含量过多,一定程度上会使正、负极的界面阻抗增加,亦不利于对电化学储能装置电化学性能的改善。但是,对于一些要求相对较低或者较次的使用需求中,电解液中同时加入磺酸酯环状季铵盐和多腈化合物即可以在一定程度上改善电化学储能装置的高温循环性能和高温存储性能。优选地,所述磺酸酯环状季铵盐的含量为所述电解液总质量的0.1%~5%,所述多腈化合物的含量为所述电解液总质量的0.1%~4%。
在根据本申请第一方面所述的电解液中,所述电解液还包括有机溶剂,所述有机溶剂的种类并没有具体的限制,可根据实际需求进行选择。优选地,使用非水有机溶剂。所述非水有机溶剂可包括任意种类的碳酸酯和/或羧酸酯。所述碳酸酯可为环状碳酸酯以及链状碳酸酯的混合物。所述非水有机溶剂还可包括碳酸酯的卤代化合物。具体地,所述有机溶剂可选自碳酸亚乙酯、碳酸亚丙酯、碳酸亚丁酯、碳酸亚戊酯、氟代碳酸亚乙酯、碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸甲乙酯、甲酸甲酯、甲酸乙酯、乙酸乙酯、丙酸丙酯、丙酸乙酯、γ-丁内酯、四氢呋喃中的一种或几种。
在根据本申请第一方面所述的电解液中,所述电解质盐的浓度没有具体的限制,可根据实际需求进行选择。具体地,所述电解质盐的含量为所述电解液的总质量的6%~25%,优选地,所述电解质盐的含量为所述电解液的总质量的6%~20%,进一步优选地,所述电解质盐的含量为所述电解液的总质量的10%~15%。
其次说明根据本申请第二方面的电化学储能装置。
根据本申请第二方面所述的电化学储能装置包括根据本申请第一方面所述的电解液。
在根据本申请第二方面所述的电化学储能装置中,所述电化学储能装置还包括正极片、负极片、隔离膜以及包装壳等。
在根据本申请第二方面所述的电化学储能装置中,需要说明的是,所述电化学储能装置可为锂离子电池、钠离子电池、锌离子电池、金属锂电池、全固态锂电池、全固态钠电池或超级电容器。在本申请的实施例中,仅示出电化学储能装置为锂离子电池的实施例,但本申请不限于此。
在锂离子电池中,正极片包括正极集流体和设置于正极集流体上的正极膜片。所述正极集流体为铝箔。所述正极膜片包括正极活性材料,所述正极膜片还可包括导电剂、粘结剂。正极活性材料可选自钴酸锂(LiCoO2)、镍酸锂(LiNiO2)、尖晶石型的锰酸锂(LiMn2O4)、橄榄石型的LiMPO4、三元材料LiaNixAyB(1-x-y)O2中的一种或几种。其中,在橄榄石型的LiMPO4中,M选自Co、Ni、Fe、Mn、V中的一种或几种;在三元材料LiaNixAyB(1-x-y)O2中,A、B各自独立地选自Co、Al、Mn中的一种,且A和B不相同,0.95≤a≤1.2,0<x<1,0<y<1,且x+y<1。导电剂和粘结剂的种类没具体的限制,可根据实际需求进行选择。
在锂离子电池中,负极片包括负极集流体和设置于负极集流体上的负极膜片。所述负极集流体为铜箔。所述负极膜片包括负极活性材料,所述负极膜片还可包括导电剂、粘结剂。负极活性材料可以选自在电压<2V(vs.Li/Li+)时可以嵌入锂的材料,具体地,所述负极活性材料可选自天然石墨、人造石墨、中间相微碳球(简称为MCMB)、硬碳、软碳、硅、硅-碳复合物、Li-Sn合金、Li-Sn-O合金、Sn、SnO、SnO2、尖晶石结构的锂化TiO2-Li4Ti5O12、Li-Al合金中的一种或几种。导电剂和粘结剂的种类没具体的限制,可根据实际需求进行选择。所述负极片也可直接使用金属锂片。
在锂离子电池中,所述电解质盐为锂盐,所述锂盐的具体种类不受限制。优选地,所述锂盐至少包括LiPF6。所述锂盐还可以进一步包括LiBF4、LiFSI、LiTFSI、LiClO4、LiAsF6、LiBOB、LiDFOB、LiPO2F2、LiTFOP、LiN(SO2RF)2、LiN(SO2F)(SO2RF)中的一种或几种,其中,RF=CnF2n+1,表示饱和全氟烷基,n为1~10内的整数。
在锂离子电池中,所述隔离膜的种类没有具体限制,可根据实际需求进行选择,具体地,所述隔离膜可选自聚乙烯膜、聚丙烯膜、聚偏氟乙烯膜以及它们的多层复合膜。
下面结合实施例,进一步阐述本申请。应理解,这些实施例仅用于说明本申请而不用于限制本申请的范围。在实施例中仅示出电化学储能装置为锂离子电池的情况,但本申请不限于此。
在下述实施例中,所使用到的试剂、材料以及仪器如没有特殊的说明,均可商购获得,所用到的磺酸酯环状季铵盐可参照2016年8月10日公开的中国专利CN105845981A。
实施例1~13以及对比例1~7中的锂离子电池均按照下述方法进行制备:
(1)正极片的制备
将正极活性材料LiNi0.6Co0.2Mn0.2O2、导电剂乙炔黑、粘结剂聚偏二氟乙烯按质量比为LiNi0.6Co0.2Mn0.2O2:乙炔黑:聚偏二氟乙烯=98:1:1进行混合,加入溶剂N-甲基吡咯烷酮,在真空搅拌机作用下搅拌至体系成均一透明状,获得正极浆料;将正极浆料均匀涂覆于厚度为12μm的正极集流体铝箔上;将铝箔在室温晾干后转移至120℃烘箱干燥1h,然后经过冷压、分切得到正极片。
(2)负极片的制备
将负极活性材料人造石墨、增稠剂羧甲基纤维素钠(CMC)、粘结剂丁苯橡胶乳液按照质量比98:1:1进行混合,加入去离子水,在真空搅拌机作用下获得负极浆料;将负极浆料均匀涂覆在厚度为8μm的负极集流体铜箔上;将铜箔在室温晾干后转移至120℃烘箱干燥1h,然后经过冷压、分切得到负极片。
(3)电解液的制备
在含水量<10ppm的氩气气氛手套箱中,将碳酸亚乙酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照体积比为EC:EMC:DEC=1:1:1进行混合,接着将充分干燥的锂盐LiPF6溶解于混合有机溶剂中,之后加入磺酸酯环状季铵盐和多腈化合物,混合均匀后获得电解液。其中,LiPF6的含量为电解液的总质量的12.5%。电解液中所用到的磺酸酯环状季铵盐和多腈化合物的具体种类以及含量如表1所示。在表1中,磺酸酯环状季铵盐、多腈化合物含量为基于电解液的总质量计算得到的质量百分数。
(4)隔离膜的制备
选用16μm厚的聚丙烯隔离膜(型号为A273,由Celgard公司提供)。
(5)锂离子电池的制备
将正极片、隔离膜、负极片按顺序叠好,使隔离膜处于正、负极片之间起到隔离的作用,然后卷绕得到裸电芯;将裸电芯置于外包装壳中,将上述制备好的电解液注入到干燥后的裸电芯中,经过真空封装、静置、化成、整形等工序,获得锂离子电池。
表1实施例1~13和对比例1~7的参数
接下来说明锂离子电池的测试过程。
(1)锂离子电池的高温循环性能测试
在45℃下,将锂离子电池以1C恒流充电至电压为4.4V,进一步以4.4V恒压充电至电流为0.05C,然后以1C恒流放电至电压为3.0V,此为一个充放电循环过程,此次的放电容量为首次循环的放电容量。将锂离子电池按照上述方法进行300次循环充电/放电测试,检测得到第300次循环的放电容量。每组测试15支锂离子电池,取平均值。
锂离子电池45℃循环300次后的容量保持率(%)=(锂离子电池第300次循环的放电容量/锂离子电池首次循环的放电容量)×100%。
(2)锂离子电池的高温存储性能测试
在25℃下,将锂离子电池以0.5C恒流充电至电压为4.4V,然后以4.4V恒压充电至电流为0.05C,此时测试锂离子电池的厚度并记为h0;之后将锂离子二次电池放入60℃的恒温箱,存储30天后取出,测试此时锂离子电池的厚度并记为h1。每组测试15支锂离子电池,取平均值。
锂离子电池60℃存储30天后的厚度膨胀率(%)=[(h1-h0)/h0]×100%。
表2实施例1~13和对比例1~7的性能测试结果
从表2的相关数据分析可知,锂离子电池在磺酸酯环状季铵盐以及多腈化合物的共同作用下可具有较好的高温存储性能和高温循环性能。
在对比例1~3中分析可知,对比例1中没有加入磺酸酯环状季铵盐和多腈化合物,锂离子电池的高温循环容量保持率及高温存储厚度膨胀率均较低;对比例2中加入磺酸酯环状季铵盐,锂离子电池的高温循环容量保持率和高温存储厚度膨胀率均可以一定程度上得到改善,其中,锂离子电池的高温循环容量保持率的改善较为明显,而高温存储厚度膨胀率的改善则相对不明显,因此其总体上依旧不能满足锂离子电池的实际使用需求;对比例3中加入多腈化合物,锂离子电池的高温厚度膨胀率得到显著改善,但锂离子电池的高温循环容量保持率改善则相对不明显。
在实施例1~13和对比例4~7中分析可知,电解液中同时加入磺酸酯环状季铵盐以及多腈化合物,锂离子电池可以兼具有较好的高温存储性能和高温循环性能,同时可以理解的是,磺酸酯环状季铵盐以及多腈化合物用量的变化必然直接影响电解液的性能,从而影响对锂离子电池电化学性能的改善。
在对比例4中,磺酸酯环状季铵盐的含量不足,对锂离子电池的高温循环性能的改善作用较弱。在实施例1~5中,随着磺酸酯环状季铵盐含量的增加,锂离子电池的高温存储性厚度膨胀率可以得到显著的降低,同时锂离子电池的高温循环容量保持率也一定程度得到改善。当磺酸酯环状季铵盐的含量过高时,例如在对比例5中,会明显恶化锂离子电池的高温循环性能。
在对比例6中,多腈化合物的含量不足,对锂离子电池的高温存储性能的改善不明显。在实施例6~10中,随着多腈化合物含量的增加,在锂离子电池的高温循环容量保持率基本保持稳定的情况下,锂离子电池的高温厚度膨胀率得到显著改善。但是当多腈化合物的含量过高时,例如在对比例7中,会明显恶化锂离子电池的高温循环性能。
因此磺酸酯环状季铵盐和多腈化合物的含量过少或过多均不利于从总体上改善锂离子电池的电化学性能,但对于一些要求相对较低或者较次的使用需求中,其同样可以在一定程度上改善锂离子电池的电化学性能。
根据上述说明书的揭示,本申请所属领域的技术人员还可以对上述实施方式进行适当的变更和修改。因此,本申请并不局限于上面揭示和描述的具体实施方式,对本申请的一些修改和变更也应当落入本申请的权利要求的保护范围内。
Claims (10)
1.一种电解液,包括:
电解质盐;以及
添加剂;
其特征在于,
所述添加剂包括磺酸酯环状季铵盐以及多腈化合物。
2.根据权利要求1所述的电解液,其特征在于,所述磺酸酯环状季铵盐选自式1所示的化合物中的一种或几种;
在式1中,R11选自-CN、取代或未取代的C1~12烷基、取代或未取代的C2~12的烯基、取代或未取代的C2~12的炔基、取代或未取代的C1~12的烷氧基、取代或未取代的C1~12的酰氧基中的一种;
R12选自取代或未取代的C1~12的亚烷基、取代或未取代的C2~12的亚烯基、取代或未取代的C2~12的亚炔基、取代或未取代的C1~12的亚烷酰基中的一种;
R13选自取代或未取代的C1~12的烷基、取代或未取代的C2~12的烯基、取代或未取代的C2~12的炔基、取代或未取代的C1~12的烷氧基、取代或未取代的C1~12的酰氧基、取代或未取代的C6~22的芳基、取代或未取代的C5~22的芳杂基中的一种;
R14选自取代或未取代的C1~3的亚烷基;
取代基选自-CN、卤素原子中的一种或几种;
表示阴离子,选自F-、NO3 -、SO4 2-、PF6 -、PF4 -、AsF6 -、(FSO2)2N-、 中的一种。
3.根据权利要求2所述的电解液,其特征在于,所述磺酸酯环状季铵盐的阳离子基团选自
中的一种。
4.根据权利要求3所述的电解液,其特征在于,所述磺酸酯环状季铵盐选自下述化合物中的一种或几种:
5.根据权利要求1所述的电解液,其特征在于,所述多腈化合物选自二腈化合物、三腈化合物以及四腈化合物中的一种或几种。
6.根据权利要求5所述的电解液,其特征在于,
所述二腈化合物选自式2所示的化合物中的一种或几种;
NC-R21-CN 式2
在式2中,R21选自C1~20的亚烷基或卤代亚烷基、C1~20的亚烷氧基或卤代亚烷氧基、C2~20的亚烯基或卤代亚烯基、C2~20的亚烯氧基或卤代亚烯氧基中的一种;
所述三腈化合物选自式3所示的化合物中的一种或几种;
在式3中,R31、R32、R33各自独立地选自C0~20的亚烷基或卤代亚烷基、C1~20的亚烷氧基或卤代亚烷氧基、C2~20的亚烯基或卤代亚烯基、C2~20的亚烯氧基或卤代亚烯氧基中的一种;
所述四腈化合物选自式4所示的化合物中的一种或几种;
在式4中,R41、R42、R43、R44各自独立地选自C0~20的亚烷基或卤代亚烷基、C1~20的亚烷氧基或卤代亚烷氧基、C2~20的亚烯基或卤代亚烯基、C2~20的亚烯氧基或卤代亚烯氧基中的一种。
7.根据权利要求6所述的电解液,其特征在于,
所述二腈化合物选自丙二腈、丁二腈、2-甲基丁二腈、四甲基丁二腈、戊二腈、2-甲基戊二腈、己二腈、富马二腈、2-亚甲基戊二腈、3,5-二氧杂-庚二腈、乙二醇二(2-氰基乙基)醚、二乙二醇二(2-氰基乙基)醚、三乙二醇二(2-氰基乙基)醚、四乙二醇二(2-氰基乙基)醚、1,2-二(2-氰乙氧基)乙烷、1,3-二(2-氰基乙氧基)丙烷、1,4-二(2-氰基乙氧基)丁烷、1,5-二(2-氰基乙氧基)戊烷、乙二醇二(4-氰基丁基)醚、1,6-二氰基己烷、1,2-二溴-2,4-二氰基丁烷、乙氧基亚甲基丙二腈中的一种或几种;
所述三腈化合物选自甲烷三甲腈、乙烯-1,1,2-三甲腈、1,3,6-己烷三腈、1,2,3-丙三甲腈、1,3,5-戊三甲腈中的一种或几种;
所述四腈化合物选自四氰基乙烯、1,2,2,3-丙烷四甲腈、甲烷四甲腈、1,1,3,3-丙烷四甲腈、1,1,2,2-乙烷四甲腈中的一种或几种。
8.根据权利要求1所述的电解液,其特征在于,
所述磺酸酯环状季铵盐的含量为所述电解液总质量的0.05%~10%,优选地,所述磺酸酯环状季铵盐的含量为所述电解液总质量的0.1%~5%;
所述多腈化合物的含量为所述电解液总质量的0.05%~7%,优选地,所述多腈化合物的含量为所述电解液总质量的0.1%~4%。
9.根据权利要求1所述的电解液,其特征在于,所述电解液为液体电解液、固态聚合物电解液或凝胶聚合物电解液。
10.一种电化学储能装置,其特征在于,包括根据权利要求1-9中任一项所述的电解液。
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CN110797576A (zh) * | 2019-11-08 | 2020-02-14 | 广州天赐高新材料股份有限公司 | 一种高电压锂离子电池电解液及锂离子电池 |
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CN112927949A (zh) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | 一种水系混合电解液和其在锌离子混合超级电容器应用 |
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CN111129584B (zh) * | 2019-12-20 | 2022-03-11 | 杉杉新材料(衢州)有限公司 | 一种非水电解液及其锂离子电池 |
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