CN112042034A - 包含无机电解液的锂二次电池 - Google Patents
包含无机电解液的锂二次电池 Download PDFInfo
- Publication number
- CN112042034A CN112042034A CN201980027788.6A CN201980027788A CN112042034A CN 112042034 A CN112042034 A CN 112042034A CN 201980027788 A CN201980027788 A CN 201980027788A CN 112042034 A CN112042034 A CN 112042034A
- Authority
- CN
- China
- Prior art keywords
- secondary battery
- lithium secondary
- tio
- titanium oxide
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000003792 electrolyte Substances 0.000 title claims abstract description 33
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 68
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 54
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 229910021382 natural graphite Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims description 4
- 229910013350 LiBCl4 Inorganic materials 0.000 claims description 3
- 229910010937 LiGaCl4 Inorganic materials 0.000 claims description 3
- 229910010884 LiInCl4 Inorganic materials 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims 1
- 238000006276 transfer reaction Methods 0.000 abstract description 4
- 239000004020 conductor Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 239000006256 anode slurry Substances 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000010220 ion permeability Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910016127 LiNi1-x-y-zCoxM1yM2zO2 Inorganic materials 0.000 description 1
- 229910014359 LiNi1−x−y−zCoxM1yM2zO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000007760 metering rod coating Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/366—Composites as layered products
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
-
- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H01M50/431—Inorganic material
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- H01M2300/002—Inorganic electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
- H01M50/437—Glass
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- 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
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
本发明提供一种锂二次电池,其包含正极、负极、置于所述正极与所述负极之间的隔膜和二氧化硫类无机电解液,其中所述负极包含涂有钛氧化物(TiOx,0<x<2)的碳材料作为负极活性材料。根据本发明,所述钛氧化物改善所述碳材料负极对所述无机电解液的润湿性和表面上的电荷转移反应并且将所述碳材料/无机电解液的界面电阻减到最低限度,由此可以改善高倍率充电/放电特性。
Description
技术领域
本公开涉及一种具有改善的高倍率特性的包含无机电解液的锂二次电池。
本申请要求于2018年7月12日向韩国知识产权局提交的韩国专利申请第10-2018-0081308号的权益,该韩国专利申请的公开内容以引用的方式整体并入本文中。
背景技术
随着技术的发展和对移动装置的需求的增加,对具有小尺寸和高容量的可再充电二次电池的需求正急剧增加。在二次电池中,具有高能量密度和电压的锂二次电池被商业化并且被广泛使用。
锂二次电池一般通过放置具有不同电位的两个电极且将隔膜置于这两个电极之间以防止它们之间的电短路并且注入用于将锂离子转移到这两个电极的电解质来制造。大多数的锂二次电池使用含有溶解在有机溶剂中的锂盐的液体电解质。
近来,在诸如高温和过度充电的极端情况下,锂二次电池的诸如起火和爆炸的安全问题驱动了对设计不含可燃和易燃有机溶剂的电池的需求,并且为了满足这一需求,正在进行许多有关不易燃的电解质如二氧化硫类无机电解液的研究。
二氧化硫类无机电解液的离子电导率(约78mS/cm至约80mS/cm)为有机电解液的约7倍,并且因此它们在高倍率特性方面将具有优势。
然而,二氧化硫类无机电解液在通常用于锂二次电池中的疏水性碳材料负极上的润湿性不足,这会降低锂离子的扩散速率,并且在高倍率充电/放电期间锂离子在碳材料负极处的嵌入和脱嵌不佳,从而导致低的充电/放电效率,并且因此需要进行改善。
发明内容
技术问题
本公开是为了解决上述问题而被设计的,并且因此,本公开旨在提供一种将二氧化硫类无机电解液和碳类负极一起使用的具有改善的高倍率充电/放电特性的锂二次电池。
技术方案
根据本公开的一个方面,在第一实施方式中,提供一种锂二次电池,其包含正极、负极、置于所述正极与所述负极之间的隔膜和二氧化硫类无机电解液,其中所述负极包含涂有钛氧化物(TiOx,0<x<2)的碳材料作为负极活性材料。
根据本公开的第二实施方式,在第一实施方式中,提供所述锂二次电池,其中所述钛氧化物包含TiO、TiO0.5、TiO0.68、TiO1.3、TiO1.5、TiO1.7、TiO1.9或其中两种以上的混合物。
根据本公开的第三实施方式,在第一实施方式或第二实施方式中,提供所述锂二次电池,其中基于所述碳材料的量,涂有0.5重量%至20重量%、0.5重量%至10重量%或1重量%至5重量%的量的所述钛氧化物。
根据本公开的第四实施方式,在第一实施方式至第三实施方式中的任一者中,提供所述锂二次电池,其中所述碳材料包含天然石墨、人造石墨、无定形硬碳、低结晶性软碳、炭黑、乙炔黑、科琴黑(ketjen black)、Super P、石墨烯、纤维状碳或其中两种以上的混合物。
根据本公开的第五实施方式,在第一实施方式至第四实施方式中的任一者中,提供所述锂二次电池,其中所述二氧化硫类无机电解液包含二氧化硫(SO2)和锂盐。
根据本公开的第六实施方式,在第一实施方式至第五实施方式中的任一者中,提供所述锂二次电池,其中所述涂有钛氧化物(TiOx,0<x<2)的碳材料是通过将钛氧化物前体分散在溶剂中以制备溶胶溶液,使所述溶胶溶液与碳材料之间发生反应以引起溶胶-凝胶反应,然后进行热处理而获得的。
根据本公开的第七实施方式,在第一实施方式至第六实施方式中的任一者中,提供所述锂二次电池,其中所述钛氧化物前体为钛酸四丁酯、钛酸四异丙酯、四氯化钛、钛酸四乙酯或其中两种以上的混合物。
根据本公开的第八实施方式,在第一实施方式至第七实施方式中的任一者中,提供所述锂二次电池,其中所述锂盐包含LiAlCl4、LiGaCl4、LiBF4、LiBCl4、LiInCl4或其中两种以上的混合物。
根据本公开的第九实施方式,在第一实施方式至第八实施方式中的任一者中,提供所述锂二次电池,其中基于所述二氧化硫类无机电解液中的所述锂盐1mol,所述二氧化硫(SO2)以1mol至6mol的量存在。
根据本公开的第十实施方式,在第一实施方式至第九实施方式中的任一者中,提供所述锂二次电池,其中所述隔膜由玻璃纤维制成。
有益效果
由于有助于改善碳材料负极对无机电解液的润湿性和表面上的电荷转移反应并且将碳材料/无机电解液的界面电阻减到最低限度的钛氧化物的存在,因此包含二氧化硫类无机电解液和包含涂有钛氧化物的碳材料的负极的本公开的锂二次电池具有改善的高倍率充电/放电特性。
具体实施方式
在下文中,本说明书和所附权利要求书中所用的术语或词语不应当被解释为限于一般含义和字典含义,而是应基于允许本发明人适当地定义术语以进行最佳解释的原则,基于符合本公开的技术构思的含义和概念来解释。
本公开的一个实施方式涉及一种锂二次电池,其包含正极、负极、置于所述正极与所述负极之间的隔膜和二氧化硫类无机电解液。
用于本公开的锂二次电池中的二氧化硫类无机电解液包含二氧化硫和锂盐,并且所述锂盐可以为LiAlCl4、LiGaCl4、LiBF4、LiBCl4、LiInCl4或其中两种以上的混合物。所述锂盐以固态存在,并且在注入SO2气体时,变为液态。在本公开的一个具体实施方式中,可以通过打开和关闭阀门通过连接在气密容器之间的特氟隆软管来注入SO2气体,并且所述注入可以在约1.2巴的压力下进行。例如,所述二氧化硫类无机电解液可以通过将SO2气体注入到LiAlCl4(或AlCl3和LiCl的混合物)中而获得。在本公开的一个具体实施方式中,基于1mol的锂盐,SO2可以以1mol至6mol,特别是1mol至3mol的量存在。
由于二氧化硫类无机电解液具有不易燃性,因此当二次电池暴露于高温或过度充电环境时,所述二氧化硫类无机电解液可以避免起火和爆炸的风险,并且因此比易燃的有机电解液更安全。然而,二氧化硫类无机电解液在通常用于锂二次电池中的疏水性碳材料负极上的润湿性不足,这会降低锂离子的扩散速率,并且在高倍率充电/放电期间锂离子在碳材料负极处的嵌入和脱嵌不佳,从而导致低的充电/放电效率。
因此,本公开的锂二次电池的特征在于包含具有安全优势的二氧化硫类无机电解液和使用涂有钛氧化物(TiOx,0<x<2)的碳材料作为负极活性材料的负极。
具体地,所述涂有钛氧化物(TiOx,0<x<2)的碳材料可以通过如下获得:将钛氧化物前体分散在溶剂中以制备TiOx溶胶溶液,使所述溶胶溶液与碳材料之间发生反应以引起溶胶-凝胶反应,然后在热水浴中在约70℃下搅拌反应溶液的同时通过蒸发来去除溶剂,然后在氮气(N2)气氛下在400℃至500℃下对所产生的粉末进行热处理。
在这种情况下,所述溶剂可以包含乙醇、水、四氢呋喃或其中两种以上的混合物。此外,所述钛氧化物前体可以包含钛酸四丁酯、钛酸四异丙酯、四氯化钛、钛酸四乙酯或其中两种以上的混合物。
通过这一系列工序,获得了在碳材料的表面上具有钛氧化物(TiOx,0<x<2)涂层的粉末,并且其可以用作负极活性材料。
所述碳材料可以包含天然石墨、人造石墨、无定形硬碳、低结晶性软碳、炭黑、乙炔黑、科琴黑、Super P、石墨烯、纤维状碳或其中两种以上的混合物。
所述钛氧化物(TiOx,0<x<2)例如可以为TiO、TiO0.5、TiO0.68、TiO1.3、TiO1.5、TiO1.7、TiO1.9或其中两种以上的混合物。所述钛氧化物(TiOx,0<x<2)由于其亲溶剂性而对电解液具有良好的润湿性。此外,与作为具有3.2eV的带隙能量的绝缘体并且具有低电导率的二氧化钛(TiO2)相比,所述钛氧化物(TiOx,0<x<2)由于具有低的带隙能量而具有良好的电导率。
因此,当在碳材料电极中包含上述钛氧化物时,所述钛氧化物由于其亲溶剂性并且由于其低带隙能量因而可以改善碳材料电极对电解液的润湿性,改善电极表面上的电荷转移反应,从而改善锂离子的扩散速率并且实现锂二次电池的高倍率充电/放电。
所述钛氧化物可以呈粒子形式,并且钛氧化物与碳材料的粒径比可以为1:1000至1:6000,特别是1:2000至1:3000。例如,当碳材料为呈具有10μm至50μm,特别是15μm至30μm的平均粒径的二次粒子形式的球形天然石墨时,上述钛氧化物可以具有1nm至30nm,特别是5nm至15nm的平均粒径。在这种情况下,可以通过激光衍射粒度分布测量方法来测量平均粒径。
基于碳材料的总量,钛氧化物的涂布量可以为0.5重量%至20重量%,特别是0.5重量%至10重量%,并且特别是1重量%,并且当满足所述涂布量的范围时,可以实现每单位重量的活性材料(即碳材料)的足够的容量。也就是说,由于钛氧化物不是活性材料而是用于提供润湿性效果的涂层剂,因此满足上述范围以显示出活性材料的容量是有利的。
在本公开的一个实施方式中,可以通过将负极浆料涂布在集电器的至少一个表面上,随后进行干燥和压制来制造负极,其中所述负极浆料是通过将作为负极活性材料的如上文所述的涂有钛氧化物的碳材料和粘结剂在溶剂中一起混合而制备的。在这种情况下,干燥可以在100℃至150℃的温度下进行1小时至24小时。此外,当制备负极浆料时可以添加导电材料。
除了碳材料之外,如果需要的话,负极可以还包含例如Si类材料,如Si、SiO、SiO2;Sn类材料,如Sn、SnO、SnO2;或其中两种以上的混合物作为负极活性材料。基于负极浆料的总重量,包含碳材料的负极活性材料可以以80重量%至99重量%的量存在。
粘结剂是有助于活性材料与导电材料之间或活性材料、导电材料和集电器之间的粘结的物质,并且通常地,基于负极浆料组合物的总重量,粘结剂以0.1重量%至20重量%的量存在。粘结剂的实例包含聚偏二氟乙烯-六氟丙烯共聚物(PVDF-HEP共聚物)、聚偏二氟乙烯(PVDF)、聚丙烯腈、聚甲基丙烯酸甲酯、聚乙烯醇、羧甲基纤维素(CMC)、淀粉、羟丙基纤维素、再生纤维素、聚乙烯吡咯烷酮、四氟乙烯、聚乙烯、聚丙烯、聚丙烯酸酯和苯乙烯-丁二烯橡胶(SBR)。羧甲基纤维素(CMC)可以用作增稠剂以调节浆料的粘度。
导电材料不限于特定类型,只要其在相应的电池中不会引起化学变化并且具有导电性即可,并且导电材料的实例包含炭黑类,例如炭黑、乙炔黑、科琴黑、槽法炭黑、炉黑、灯黑、热裂法炭黑;导电纤维,例如碳纤维或金属纤维;氟化碳;金属粉末如铝粉末或镍粉末;导电晶须,例如锌氧化物、钛酸钾;导电金属氧化物,例如钛氧化物;和聚亚苯基衍生物。基于负极浆料组合物的总重量,导电材料可以以0.1重量%至20重量%的量存在。
所述溶剂可以包含水或有机溶剂,例如N-甲基-2-吡咯烷酮(NMP),并且当负极浆料包含负极活性材料以及任选的粘结剂和导电材料时,溶剂可以以合适的量存在以获得所期望的粘度。例如,溶剂可以以使得负极浆料中固体成分的浓度为50重量%至95重量%,并且优选70重量%至90重量%的量存在。
集电器不限于特定的类型,只要其在电池中不会引起化学变化并且具有导电性即可,并且例如包含铜、不锈钢、铝、镍、钛、烧结碳、用碳、镍、钛或银进行了表面处理的铜或不锈钢、和铝镉合金。集电器的厚度不受特别限制,但是如通常所应用的可以具有3μm至500μm的厚度。
此外,负极浆料的涂布方法不限于特定的类型,并且包含本领域中通常使用的任何涂布方法。例如,可以使用利用缝形模头的涂布方法,并且此外,可以使用迈耶棒(Meyerbar)涂布法、凹版印刷涂布法、浸涂法、喷涂法等。
在本公开的锂二次电池中,正极可以通过将正极活性材料、导电材料、粘结剂和溶剂混合以制备浆料,将所述浆料涂布到集电器的至少一个表面上,干燥并且压制来制造。
正极活性材料可以包含Li、LiCoO2、LiNiO2、LiMn2O4、LiCoPO4、LiFePO4、LiNi1-x-y- zCoxM1yM2zO2(M1和M2独立地为Al、Ni、Co、Fe、Mn、V、Cr、Ti、W、Ta、Mg、Mo或它们中的两种以上,并且x、y和z独立地为氧化物组成中元素的原子分数,其中0≤x<0.5,0≤y<0.5,0≤z<0.5,0≤x+y+z<1)或它们中的两种以上的活性材料粒子。
在这种情况下,导电材料、粘结剂、溶剂和集电器与关于负极所述的相同。
在本公开的锂二次电池中,隔膜被置于正极与负极之间,并且使用具有高离子渗透性和机械强度的绝缘薄膜。隔膜的孔径一般是0.01μm至10μm,并且厚度一般是5μm至300μm。
隔膜可以包含由聚烯烃类聚合物,如乙烯均聚物、丙烯均聚物、乙烯/丁烯共聚物、乙烯/己烯共聚物和乙烯/甲基丙烯酸酯共聚物制成的多孔聚合物膜、具有高离子渗透性和机械强度的绝缘薄膜和一般的多孔无纺布,例如由玻璃纤维或聚对苯二甲酸乙二醇酯纤维制成的无纺布。特别是,玻璃纤维隔膜对二氧化硫类无机电解液显示出良好的润湿性,降低电池的内阻并且具有容量和寿命保持优势。
本公开的二次电池可以用于用作小型装置的电源的电池单元,并且优选的是,也可以用于包含多个电池单元的中型和大型电池模块的单元电池。中型和大型装置的优选实例包含电动车辆、混合动力电动车辆、插电式混合动力电动车辆和储能系统。
公开的实施方式
尽管在上文中已经关于有限数量的实施方式和附图描述了本公开,但是本公开不限于此,并且对于本公开所属的技术领域的普通技术人员来说显而易见的是,可以在技术特征以及所附权利要求和其等同范围内对其进行许多修改和变化。
实施例1:
将10ml的钛酸四丁酯和10ml的钛酸四异丙酯分散在100ml的乙醇中并且在室温下搅拌30分钟以制备含有TiO、TiO0.5、TiO0.68、TiO1.3、TiO1.5、TiO1.7和TiO1.9的混合物的TiOx(0<x<2)溶胶溶液。将呈具有20μm的平均粒径的二次粒子形式的天然石墨添加到所述溶胶溶液中以引起溶胶-凝胶反应1小时至2小时。将预定量的反应溶液在热水浴中在约70℃下搅拌以蒸发溶剂,并且在氮气气氛下在500℃下对所产生的粉末进行热处理。所得物是具有黑色钛氧化物TiOx(0<x<2)的表面涂层的天然石墨粉末,所述黑色钛氧化物TiOx具有10nm的平均粒径且其含量基于天然石墨的量为1%。
将含有以96:2:2的重量比分散在去离子水中的作为负极活性材料的涂有钛氧化物(TiOx,0<x<2)的碳材料、更特别地是如上文所述而获得的涂有黑色钛氧化物(TiOx,0<x<2)的天然石墨以及作为粘结剂的苯乙烯-丁二烯橡胶(SBR)和羧甲基纤维素(CMC)的负极浆料涂布在11μm厚的铜箔的一个表面上并且在130℃下干燥1小时并且压制以制造负极。
对于隔膜,使用玻璃纤维隔膜,例如ADVANTEC GC-50玻璃纤维隔膜(重量48g/m2,厚度190μm,标称孔径0.5μm)。
获得包含负极和作为对电极的锂金属箔以及置于它们之间的玻璃纤维隔膜的电极组件并且将其收容在电池壳中。随后,将SO2气体在约1.2巴下注入到气密容器中的AlCl3和LiCl的混合物中,从而产生二氧化硫类无机电解质LiAlCl4-3SO2,并且将所获得的无机电解液注入到电池壳中,以制造锂二次电池(2032硬币电池)。
实施例2:
除了在制造负极时,将在表面上涂有5%黑色钛氧化物(TiOx,0<x<2)的天然石墨用于负极活性材料以外,通过与实施例1相同的工序制造锂二次电池。
比较例1:
除了在制造负极时,将未涂有黑色钛氧化物(TiOx,0<x<2)的天然石墨用于负极活性材料以外,通过与实施例1相同的工序制造锂二次电池。
实验例1:充电/放电试验
将如上所述制造的锂二次电池进行充电/放电。在这种情况下,以1C倍率的电流密度进行充电至0.005V的电压,以相同的电流密度进行放电至2V的电压,并且将充电/放电进行100次循环。
此外,在进行充电/放电的同时,在室温下在大气条件下测量二次电池的界面电阻。具体地,通过向电池单元施加不同频率的小交流电(AC)信号来测量阻抗并且分离二次电池的电阻的电化学阻抗谱法(EIS)来测量界面电阻。
结果示于表1中。
[表1]
从表1中可以看出,使用二氧化硫类无机电解液和涂有钛氧化物的天然石墨的实施例1和实施例2的二次电池所显示出的1C放电容量是使用未经涂布的天然石墨的比较例1的约2倍,并且因此具有改善的高倍率特性,并且在降低界面电阻方面,它们的结果是良好的。据推测,这些结果归因于天然石墨上的钛氧化物涂层,所述钛氧化物涂层有助于改善无机电解液的润湿性和电极表面上的电荷转移反应。
另一方面,认为比较例1的容量保持率增加至高达125.4%的原因是因为由于未经涂布的天然石墨对无机电解液的润湿性低而随着循环次数增加而显示出天然石墨的容量。因此,预测比较例1的二次电池将具有低的初始效率。
与此相对,实施例1和实施例2的二次电池显示出稳定的容量保持率。
Claims (11)
1.一种锂二次电池,其包含:
正极、负极、置于所述正极与所述负极之间的隔膜和二氧化硫类无机电解液,
其中所述负极包含涂有钛氧化物(TiOx,0<x<2)的碳材料作为负极活性材料。
2.根据权利要求1所述的锂二次电池,其中所述钛氧化物为TiO、TiO0.5、TiO0.68、TiO1.3、TiO1.5、TiO1.7、TiO1.9或其中两种以上的混合物。
3.根据权利要求1所述的锂二次电池,其中基于所述碳材料的量,涂有0.5重量%至20重量%的量的所述钛氧化物。
4.根据权利要求3所述的锂二次电池,其中基于所述碳材料的量,涂有0.5重量%至10重量%的量的所述钛氧化物。
5.根据权利要求1所述的锂二次电池,其中所述碳材料包含天然石墨、人造石墨、无定形硬碳、低结晶性软碳、炭黑、乙炔黑、科琴黑、Super P、石墨烯、纤维状碳或其中两种以上的混合物。
6.根据权利要求1所述的锂二次电池,其中所述涂有钛氧化物(TiOx,0<x<2)的碳材料是通过将钛氧化物前体分散在溶剂中以制备溶胶溶液,使所述溶胶溶液与碳材料之间发生反应以引起溶胶-凝胶反应,然后进行热处理而获得的。
7.根据权利要求1所述的锂二次电池,其中所述钛氧化物前体为钛酸四丁酯、钛酸四异丙酯、四氯化钛、钛酸四乙酯或其中两种以上的混合物。
8.根据权利要求1所述的锂二次电池,其中所述二氧化硫类无机电解液包含二氧化硫(SO2)和锂盐。
9.根据权利要求8所述的锂二次电池,其中所述锂盐包含LiAlCl4、LiGaCl4、LiBF4、LiBCl4、LiInCl4或其中两种以上的混合物。
10.根据权利要求8所述的锂二次电池,其中基于所述二氧化硫类无机电解液中的所述锂盐1mol,所述二氧化硫(SO2)以1mol至6mol的量存在。
11.根据权利要求1所述的锂二次电池,其中所述隔膜由玻璃纤维制成。
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