CN117525574B - Organic-inorganic co-modified PEO solid electrolyte and preparation method thereof - Google Patents
Organic-inorganic co-modified PEO solid electrolyte and preparation method thereof Download PDFInfo
- Publication number
- CN117525574B CN117525574B CN202410006667.6A CN202410006667A CN117525574B CN 117525574 B CN117525574 B CN 117525574B CN 202410006667 A CN202410006667 A CN 202410006667A CN 117525574 B CN117525574 B CN 117525574B
- Authority
- CN
- China
- Prior art keywords
- pvdf
- pmma
- peo
- lithium
- solid 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
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 142
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 81
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 81
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 79
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 71
- 239000002105 nanoparticle Substances 0.000 claims abstract description 61
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 150000003254 radicals Chemical class 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 229920000620 organic polymer Polymers 0.000 claims abstract description 11
- 239000011256 inorganic filler Substances 0.000 claims abstract description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 48
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
- 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 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- -1 na 2 S 2 O 8 Chemical compound 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical group [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001409 amidines Chemical class 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 101150058243 Lipf gene Proteins 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 229910013872 LiPF Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910015013 LiAsF Inorganic materials 0.000 claims description 2
- 229910013075 LiBF Inorganic materials 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 claims description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 24
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 29
- 239000012528 membrane Substances 0.000 description 14
- 239000002077 nanosphere Substances 0.000 description 14
- 239000005518 polymer electrolyte Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000945 filler Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XSBJUSIOTXTIPN-UHFFFAOYSA-N aluminum platinum Chemical compound [Al].[Pt] XSBJUSIOTXTIPN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to a battery chemical material, in particular to a modified PEO solid electrolyte and a preparation method thereof, wherein the PEO solid electrolyte consists of a PEO matrix, lithium salt, an organic polymer modifier and an inorganic filler modifier; the inorganic filler modifier is hollow mesoporous silica nano particles; the organic polymer modifier PMMA@PVDF-HFP copolymer is a copolymer obtained by copolymerizing PMMA (polyethyl methacrylate) and PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene) through a free radical initiator. The invention can greatly improve the oxidation window of the traditional PEO solid electrolyte to ensure that the PEO solid electrolyte has high-voltage electrode adaptability, improves the mechanical strength and the thermal stability, reduces the puncture risk of lithium dendrites, provides more lithium ion transmission paths, improves the system viscosity, reduces the stripping risk of pole pieces, reduces the interface impedance, and improves the transfer rate and the cycle performance of lithium ions.
Description
Technical Field
The invention relates to a battery chemical material, in particular to a modified PEO solid electrolyte and a preparation method thereof.
Background
With the popularization and application of electric automobiles, electronic products and smart grids, the development of high-energy, rechargeable, safe batteries is a trend. Conventional Lithium Ion Batteries (LIBs) are currently the most popular and most capable energy storage devices. However, liquid organic electrolytes of LIBs present problems of environmental inefficiency, often corrosiveness, flammability, and thermal instability, which can present a safety risk. The solid-state battery adopts the solid electrolyte to replace the liquid electrolyte, so that the use safety of the battery can be improved, and the battery structure can be simplified. The solid polymer electrolyte has good application prospect in solid electrochemical energy storage devices such as rechargeable batteries, fuel cells, super capacitors and the like, has the advantages of good elasticity and plasticity, mechanical stability, thermal stability, simple processing technology, no solvent, stable electrochemical properties and the like, and is favorable for preparing devices with ideal size or shape, which have close electrode/electrolyte contact, long charging period and wide operating temperature range. In addition, the solid polymer electrolyte can relieve short circuit caused by lithium dendrite, is beneficial to avoiding the influence caused by internal short circuit and leakage problems, and reduces the probability of chemical reaction between the electrolyte and the electrode and the container; and because of the advantages of flexible polymer electrolyte geometry, wide operable temperature range, high energy density and the like, the polymer electrolyte has great potential for designing and manufacturing special application occasions (such as flexible batteries and wearable electronic equipment) and durable and safe solid-state lithium batteries.
Solid electrolytes are a class of electrolytes formed by incorporating lithium salts such as LiTFSI into conventional polymer electrolytes. The polymer-based electrolyte can compensate for the volume change of the electrode during charge and discharge by elastic and plastic deformation. The PEO matrix electrolyte is a typical polymer solid electrolyte. The working mechanism of PEO electrolyte is mainly: lithium ions realize lithium ion migration through the continuous complexing-decomplexing process with ether oxygen bonds in the PEO long chain by the segmental motion of PEO. The ability of the PEO segments to move largely determines the ionic conductivity of the PEO-based solid state electrolyte. However, pure PEO is easy to crystallize at room temperature, the solubility of lithium salt in amorphous phase is low, the carrier concentration is low, the migration number of lithium ions is small, and the room-temperature ion conductivity of PEO-based electrolyte is only 10 -7 S·cm -1 The battery cannot be operated normally. To solve this problem, related researchers have proposed incorporating inorganic fillers into the PEO matrix material of polymer electrolytes, whereby inhibition can be achievedCrystallization of the polymer substrate and interaction of the recombinant polymer and lithium ions, so that the ion conduction performance, interface performance and mechanical strength of the electrolyte are effectively improved.
For example, CN 113851709B discloses a ceramic inorganic filler-PEO-LiTFSI solid electrolyte, but the electrolyte still has the following problems: (1) Poor viscosity and easy falling off with the pole piece in the long-time cyclic test process. (2) The compatibility problem between the introduced inorganic filler and the polymer matrix needs to be improved, and the inorganic filler is easy to agglomerate in the polymer matrix, so that the performance of the electrolyte is influenced. (3) Although this proposal mentions that the inorganic ceramic-based material is selected as silica, solid nanospheres are generally used, and most of them are used and studied as negative electrode materials. When the solid nano silica spheres are dispersed in the PEO matrix, lithium ions are mainly diffused through gaps among the silica, and although the mechanical property can be greatly improved, the capability of resisting lithium dendrite penetration is outstanding, but the lithium ion transmission is not facilitated. (4) PEO-based solid electrolyte has a low electrochemical window, is difficult to adapt to a high-voltage electrode, and has poor cycle performance at high voltage.
Disclosure of Invention
First, the technical problem to be solved
In view of the above-mentioned shortcomings and disadvantages of the prior art, the present invention provides an organic-inorganic co-modified PEO solid electrolyte and a preparation method thereof, and simultaneously, organic polymers and inorganic particles are adopted to modify the PEO electrolyte, so that an oxidation window is greatly improved to be adapted to a high-voltage electrode, mechanical strength and thermal stability are improved, and lithium dendrite puncture risk is reduced, more lithium ion transmission paths are provided, system viscosity is improved, pole piece stripping risk is reduced, interface impedance is reduced, and lithium ion transport rate and cycle performance are improved.
(II) technical scheme
In a first aspect, the present invention is directed to an organic-inorganic co-modified PEO solid state electrolyte comprised of a PEO matrix, a lithium salt, an organic polymer modifier, and an inorganic filler modifier; the inorganic filler modifier is hollow mesoporous silica nano particles; the organic polymer modifier PMMA@PVDF-HFP copolymer is a copolymer obtained by copolymerizing PMMA (polyethyl methacrylate) and PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene) through a free radical initiator.
According to a preferred embodiment of the present invention, the radical initiator is azobisisobutyronitrile, azobisisobutyronitrile amidine hydrochloride, dibenzoyl peroxide, na 2 S 2 O 8 、K 2 S 2 O 8 、(NH 4 ) 2 S 2 O 8 At least one of (a) and (b); and (3) carrying out chain segment reaction on PMMA and PVDF-HFP under the action of a free radical initiator to obtain the PMMA@PVDF-HFP copolymer.
According to a preferred embodiment of the invention, the lithium salt is lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium trifluoromethylsulfonate (LiCF) 3 SO 3 ) At least one of lithium bisoxalato borate (LiBOB), lithium difluorooxalato borate (liodbb), and lithium chloride (LiCl).
According to a preferred embodiment of the invention, the mass ratio of organic polymer modifier to PEO matrix is 3-10:10.
According to a preferred embodiment of the present invention, the mass fraction of hollow mesoporous silica nanoparticles in the solid electrolyte is 1-35%, and the mass fraction of lithium salt in the solid electrolyte is 15-35%.
In a second aspect, the invention provides a method for preparing an organic-inorganic co-modified PEO solid electrolyte, comprising the steps of:
s1, preparing hollow mesoporous silica nanoparticles;
s2, carrying out copolymerization reaction on PMMA and PVDF-HFP to obtain a PMMA@PVDF-HFP copolymer;
s3, dissolving PEO and PMMA@PVDF-HFP copolymer in an organic solvent according to a proportion, and homogenizing to obtain a polymer solution;
s4, dispersing lithium salt and hollow mesoporous silica nano particles in the polymer solution, uniformly dispersing, casting to form a film, and volatilizing the solvent to obtain the organic-inorganic co-modified PEO solid electrolyte.
According to a preferred embodiment of the present invention, the method for preparing hollow mesoporous silica nanoparticles in step S1 is as follows:
step 1: dispersing nano ferroferric oxide particles into a solvent, wherein the dispersion mass concentration is 0.1-10%, and the ultrasonic dispersion is uniform;
step 2: under the standing condition, adding a soluble silicon source into the dispersion liquid in the step 1 to obtain a reaction liquid, wherein the mass ratio of the ferroferric oxide to the soluble silicon source is 10:1-1:10, adding ammonia water accounting for 1-5wt% of the mass of the reaction liquid under stirring, and stirring for 1-5h;
step 3: adding a cationic surfactant at 30-120 ℃ for reaction for 0.5-12h, magnetically collecting a product, dispersing in alkali liquor, stirring at 20-80 ℃, magnetically collecting the product again, washing with absolute ethyl alcohol, and calcining at 300-500 ℃ or refluxing with acetone (to remove the surfactant), thus obtaining the silicon dioxide coated ferroferric oxide nano particles;
step 4: and (3) carrying out acid etching on the silicon dioxide coated ferroferric oxide nano particles to remove the ferroferric oxide, washing and drying to obtain the hollow mesoporous silicon dioxide nano particles. The hollow mesoporous silica nanoparticle has good dispersibility.
Preferably, the particle size of the nano ferroferric oxide particles in the step 1 is 50-200nm.
Preferably, the solvent in step 1 is at least one of methanol, ethanol, tetrahydrofuran, toluene, xylene and dichloromethane.
Preferably, the soluble silicon source in step 2 is ethyl orthosilicate, methyl orthosilicate, trimethylethoxysilane or sodium silicate; the concentration of the ammonia water is industrial ammonia water and is an aqueous solution containing 35% -28% of ammonia.
In the step 2, in the presence of ammonia water, catalyzing a silicon source to perform hydrolytic polycondensation reaction, and under the action of a cationic surfactant, self-assembling the obtained product on the surface of ferroferric oxide nano particles to form a shell structure, so as to obtain silicon dioxide nano particles with shell structures, and then etching in alkali liquor to obtain the silicon dioxide nano particles with mesoporous shell structures.
Preferably, in step 3, the cationic surfactant is at least one of dodecyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium bromide, octadecyl dimethyl benzyl ammonium chloride. Preferably, the alkali liquor in the step 3 is sodium hydroxide solution with the concentration of 0.1mol/L to 0.8mol/L, and the alkali liquor is stirred for 0.1 to 12 hours.
Preferably, when the acid etching treatment in the step 4 is used for removing the ferroferric oxide, the acid is concentrated hydrochloric acid, concentrated sulfuric acid or concentrated nitric acid, the ferroferric oxide is removed by a soaking method, and the soaking treatment time is 0.1-12h, and is particularly related to the reaction temperature; wherein the acid is in excess relative to the ferroferric oxide.
According to a preferred embodiment of the present invention, in step S2, the PMMA@PVDF-HFP copolymer is prepared by using azobisisobutyronitrile as the free radical initiator to initiate the free radical segment reaction of PVDF-HFP and PMMA to form the copolymer.
According to a preferred embodiment of the present invention, in step S2, the PMMA@PVDF-HFP copolymer is prepared as follows: PVDF-HFP is added into acetone/dimethyl sulfoxide, bubbling and stirring are carried out for 0.5-3h at 60-80 ℃ under the nitrogen atmosphere, polymethyl methacrylate PMMA (PMMA: PVDF-HFP mass ratio is 5:2-5) is added, free radical initiator is added, and stirring and reacting are continued for 6-18h, thus obtaining PMMA@PVDF-HFP copolymer solution. The free radical initiator is azobisisobutyronitrile, azobisisobutyronitrile amidine hydrochloride, dibenzoyl peroxide or Na 2 S 2 O 8 、K 2 S 2 O 8 、(NH 4 ) 2 S 2 O 8 At least one of them.
According to a preferred embodiment of the present invention, in step S3, PEO is dissolved in a solvent, and then mixed with the PMMA@PVDF-HFP copolymer solution prepared in S2 in a mass ratio of PEO to PMMA@PVDF-HFP copolymer of 10:3-10 (preferably 10:3-5), and homogenized to obtain a polymer solution. Preferably, the solvent is acetonitrile, acetone, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP).
According to the preferred embodiment of the invention, in the step S4, hollow mesoporous silica nano particles and lithium salt are added into the polymer solution, the polymer solution is continuously dispersed for 0.5 to 24 hours at the temperature of 20 to 90 ℃, casting film slurry is obtained after the uniform dispersion, the slurry is cast into a film, and the organic-inorganic co-modified PEO solid electrolyte is prepared after the solvent volatilizes.
According to a preferred embodiment of the present invention, in step S4, the hollow mesoporous silica nanoparticle accounts for 1-35% of the mass of the organic-inorganic co-modified PEO solid electrolyte, and the lithium salt accounts for 15-35% of the mass of the organic-inorganic co-modified PEO solid electrolyte.
Preferably, the method specifically comprises the following steps: and (3) coating the casting film slurry obtained in the step (S3) on the surface of an inert and flat substrate (such as a polytetrafluoroethylene plate) to obtain a polymer film, and drying in a drying oven for 5-12h in vacuum to obtain the organic-inorganic co-modified PEO solid electrolyte.
According to a preferred embodiment of the invention, the organic-inorganic co-modified PEO solid electrolyte has a thickness of 50-200 μm.
The free radical initiator, PEO, silicon source and the like used in the invention are all common reagents, and the preparation process is simple, low in cost, easy to control, good in repeatability and suitable for large-scale production. Simultaneously hollow mesoporous SiO 2 The nano particles can be uniformly dispersed in the PEO-based solid electrolyte, which is beneficial to improving the active surface area of the electrolyte.
(III) beneficial effects
The PEO/PMMA@PVDF-HFP/hollow mesoporous silica nanoparticle composite solid electrolyte is prepared by taking a PEO matrix as a solid electrolyte base polymer and simultaneously modifying the electrolyte by an organic polymer modifier PMMA@PVDF-HFP copolymer and an inorganic modifier hollow mesoporous silica nanoparticle, and has the following technical effects:
(1) The electrochemical window is improved, the problem that the electrochemical window of the solid electrolyte using PEO as a matrix is low in the traditional method is solved, the high-voltage electrode can be well adapted, and the cycle life is long.
(2) According to the invention, the hollow mesoporous silica nanoparticle inorganic filler is used for modifying the electrolyte, so that the thermal stability and electrochemical stability of the polymer solid electrolyte are improved, the application temperature range of the electrolyte is widened, the decay rate of the electrolyte performance is slowed down, the mechanical strength of the solid electrolyte is improved, and the puncture risk of lithium dendrites is reduced.
Compared with the silica nano solid sphere, the hollow mesoporous silica nano particle has better compatibility with the polymer, more importantly, a large number of pore structures of the hollow mesoporous silica nano particle provide more lithium ion transmission paths, shorten the transmission path and ensure that Li + The flux is uniform, the cycle life is prolonged, the rapid formation of lithium dendrites is prevented, and the ion conductivity of the electrolyte is improved and the electrolyte impedance is reduced due to the increase of the conduction path and the shortening of the conduction path.
The hollow mesoporous silica nano filler has better dispersibility, better compatibility with a polymer, and better dissociation capability on lithium salt, and greatly improves the mechanical property and the oxidation resistance of the solid electrolyte.
(3) In order to solve the problems that the solid electrolyte of a single PEO polymer is poor in viscosity and easy to fall off from a pole piece in the long-time cyclic test process, the invention improves the viscosity of the electrolyte, reduces the stripping risk of the pole piece and can form a stable SEI interface by adding the PMMA@PVDF-HFP copolymer and PEO synergistic effect, solves the problem that the interface impedance of an organic-inorganic solid electrolyte interface is large due to poor contact, and effectively reduces the internal resistance of a battery and improves the cyclic retention rate. By utilizing the strong polarity and higher dielectric constant of the PMMA@PVDF-HFP copolymer, the anode contact stability is improved, the addition of the amorphous polymer PMMA breaks the segment structure of PEO, the proportion of an amorphous region is increased (the proportion of a crystal region in a polymer electrolyte is reduced), and the limit of the crystal region on lithium ion diffusion is reduced. Modification of PEO-based electrolytes with PMMA@PVDF-HFP copolymers reduces the HOMO and LUMO energy levels of the solid state electrolytes, allowing Li to be + Has lower transport energy barrier and improves the transport rate of lithium ions. The lower the HOMO value of the solid electrolyte, the stronger the oxidation resistance; the lower the LUMO value, the higher the electrolyte stability, low HOMO and LUMO energy levelsThe polymer electrolyte can form a stable SEI interface with the high-voltage cathode electrode, so that the electrochemical stability of the solid electrolyte is improved.
In the experimental process, if PMMA is not contained in the organic polymer modifier, the PEO-based electrolyte is modified only by adding PVDF-HFP, and although the crystallinity of the polymer is reduced in a certain proportion, the ternary positive electrode material can not be well adapted, and the electrochemical window is difficult to lift. And by introducing PMMA, the oxidation window can be greatly improved, and the high-voltage electrode has good adaptability.
The polymer solid electrolyte provided by the invention exerts the synergistic effect of PMMA, PVDF-HFP and PEO, so that the tensile resistance of the film is greatly improved (can reach about 4.5 Mpa), the film has good mechanical strength, the composite electrolyte film contains a large number of carboxyl and fluorine functional groups which are respectively provided by PMMA and PVDF-HFP, the two functional groups can provide a path for lithium ion transmission, the ion conductivity is increased, and the film can be firmly attached to the surface of a pole piece and is not easy to peel.
(4) Preparation of mesoporous SiO in the prior art 2 The particles are difficult to collect, agglomeration easily occurs in the solvent, so that uneven dispersion or suspension and other phenomena are caused, interface contact performance is reduced, and interface impedance is increased.
For example, CN111232994B proposes to prepare hollow mesoporous silica nanoparticle by using polystyrene microsphere as template, the method has the advantages of fragile microsphere, harsh experimental condition, high collection difficulty, low yield, difficult removal of template, unstable nanoparticle parameter and low repeatability.
When the hollow mesoporous silica nanoparticle is prepared, the ferroferric oxide nanoparticle is used as a hard template, and self-assembly is realized on the surface of the template through the surfactant to form a shell structure, so that the collection difficulty is greatly reduced due to the magnetic response phenomenon of the ferroferric oxide, the template can be easily removed after subsequent acid etching, the shell structure of the hollow mesoporous silica is not damaged, and the prepared nano silica has the characteristics of good dispersibility and hollow and mesoporous shells. The mesoporous shell is directly communicated with the hollow, so that the diffusion path of lithium ions is shortened.
In the preparation process, a large number of hydroxyl groups are generated in the process of hydrolyzing the silicon source (ammonia water catalysis) to form shells, and the cationic surfactant is added to generate electrostatic action with the hydroxyl groups, so that the layer-by-layer SiO generated by the hydrolysis of the silicon source 2 Self-assembling attached to the outside of the template to form SiO 2 The shell, while the ferroferric oxide template does not react with hydroxyl groups, so that a large amount of-OH is reserved on the inner and outer surfaces of the silicon dioxide shell; after being made into solid electrolyte, siO 2 the-OH on the inner surface and the outer surface of the shell can interact with TFSI-and other anions of lithium salt, so that coordination diffusion of Li+ is reduced, the degree of freedom of the Li+ is increased, the concentration of the Li+ is increased, and the Li+ diffusion efficiency is improved.
The invention takes the ferroferric oxide nano-particles as the template, and can magnetically collect the hollow mesoporous SiO by magnetic stirring 2 Particles, hollow mesoporous SiO prepared by the method 2 The particles have good dispersity and improve SiO 2 The particles are in contact with the polymer electrolyte at a high interface, so that the solid electrolyte membrane has good uniformity, the cycle life of the battery is prolonged, and the preparation method is simple, low in cost and good in repeatability.
The hollow mesoporous silica nano filler has better dispersibility, better compatibility with a polymer, better dissociation capability on lithium salt, greatly improved mechanical property and oxidation resistance of the solid electrolyte, and simple preparation method and good repeatability.
Drawings
Fig. 1 is an SEM image of hollow mesoporous silica nanoparticles prepared in example 1.
Fig. 2 is a TEM image of hollow mesoporous silica nanoparticles prepared in example 2.
FIG. 3 is an infrared spectrum of the organic-inorganic co-modified PEO solid electrolyte prepared in example 3.
FIG. 4 is a graph of oxidative decomposition potential comparison of three different modified PEO solid electrolyte materials of example 3.
FIG. 5 is a long-cycling profile of LiTFSI/PEO/PMMA@PVDF-HFP/hollow mesoporous silica composite solid polymer electrolyte of example 3 at a current density of 0.1C.
FIG. 6 shows LPPMH solid electrolyte [ ]Hollow mesoporous SiO 2 Nanosphere modified) EIS electrochemical impedance test results.
FIG. 7 shows LPPMH solid electrolyte (hollow mesoporous SiO) 2 Nanosphere modified) impedance test results of EIS before and after polarization.
FIG. 8 is an LPPMS solid state electrolyte (solid SiO 2 Nanosphere modified) and LPPMH solid state electrolyte (hollow mesoporous SiO 2 Nanosphere modified).
Detailed Description
The invention will be better explained by the following detailed description of the embodiments with reference to the drawings.
Example 1
The preparation method of the hollow mesoporous silica nanoparticle is as follows:
(1) Dispersing nano ferroferric oxide particles into toluene, wherein the dispersion mass concentration is 6%, and the ultrasonic dispersion is uniform; the particle size of the ferroferric oxide particles is 100-150nm.
(2) Under the standing condition, adding tetraethoxysilane into the dispersion liquid to obtain a reaction liquid, enabling the mass ratio of the ferroferric oxide to the tetraethoxysilane to be 3:2, and then adding ammonia water accounting for 3wt% of the mass of the reaction liquid under the stirring condition, and stirring for 2h.
(3) Adding dodecyl trimethyl ammonium bromide at 50 ℃ for reaction for 2 hours, magnetically collecting a product, dispersing in 0.4M sodium hydroxide solution, stirring for 1 hour at 60 ℃, magnetically collecting the product again, washing with absolute ethyl alcohol, and calcining for 1.5 hours at 400 ℃ to obtain the silicon dioxide coated ferroferric oxide nano particles.
(4) And (3) throwing the silicon dioxide coated ferroferric oxide nano particles into concentrated hydrochloric acid for soaking reaction for 3 hours, taking out, repeatedly washing with water, and drying to obtain the hollow mesoporous silicon dioxide nano particles.
As shown in fig. 1, which is an SEM image of the hollow mesoporous silica nanoparticle prepared in example 1, it can be seen that the hollow mesoporous silica nanoparticle is a uniform sphere with high sphericity and fine pores on the surface.
Example 2
The preparation method of the hollow mesoporous silica nanoparticle is as follows:
(1) Dispersing nano ferroferric oxide particles into tetrahydrofuran, wherein the dispersion mass concentration is 4%, and the ultrasonic dispersion is uniform; the particle size of the ferroferric oxide particles is 80-120nm.
(2) Under the standing condition, adding methyl orthosilicate into the dispersion liquid to obtain a reaction liquid, enabling the mass ratio of the ferroferric oxide to the methyl orthosilicate to be 5:2, and then adding ammonia water accounting for 4wt% of the mass of the reaction liquid under the stirring condition to stir for 3h.
(3) Adding hexadecyl trimethyl ammonium chloride at 50 ℃ for reaction for 3 hours, magnetically collecting a product, dispersing in 0.5M sodium hydroxide solution, stirring for 1.5 hours at 40 ℃, magnetically collecting the product again, washing with absolute ethyl alcohol, and calcining for 4 hours at 400 ℃ to obtain the silicon dioxide coated ferroferric oxide nano particles.
(4) And (3) throwing the silicon dioxide coated ferroferric oxide nano particles into concentrated nitric acid for soaking reaction for 4 hours, taking out, repeatedly washing and cleaning, and drying to obtain the hollow mesoporous silicon dioxide nano particles.
As shown in fig. 2, a TEM image of the hollow mesoporous silica nanoparticle prepared in example 2 shows that the silica nanoparticle is a uniform sphere, the inside is hollow, the thickness of the silica shell layer is very uniform, and the surface is uneven (mesoporous formed by etching with alkali solution).
Example 3
The organic-inorganic co-modified PEO solid electrolyte is prepared in this example, and the preparation method is as follows:
(1) PVDF-HFP is added into acetone, bubbling and stirring are carried out for 2 hours at 60 ℃ under the nitrogen atmosphere, PMMA (PMMA: PVDF-HFP mass ratio is 5:4) and azodiisobutyronitrile are added, and stirring and reaction are continued for 10 hours, so that PMMA@PVDF-HFP copolymer solution is obtained.
(2) PEO is dissolved in acetonitrile, and then is mixed with the PMMA@PVDF-HFP copolymer solution according to the mass ratio of PEO to PMMA@PVDF-HFP copolymer (dry weight) of 10:3, and the polymer solution is obtained by homogenizing treatment.
(3) The hollow mesoporous silica nanoparticle prepared in example 1 and lithium bistrifluoromethylsulfonylimide (LiTFSI) were added to the polymer solution, stirred for 20 hours to obtain a uniform viscous solution, poured on a polytetrafluoroethylene plate, evaporated the solvent, and dried in a vacuum drying oven at 80℃to obtain a solid polymer electrolyte membrane with a thickness of 130. Mu.m. In the solid electrolyte membrane, the LiTFSI content is 24wt%, and the hollow mesoporous silica nanoparticle content is 12wt%. The electrochemical window of the prepared modified PEO solid electrolyte is 4.6V, and the ionic conductivity is 5.9X10 at 30 DEG C -6 S/cm。
The organic-inorganic co-modified PEO solid electrolyte is subjected to tensile test, and an electrolyte membrane is intact when the electrolyte membrane is elongated by 50%, so that the electrolyte membrane has good mechanical strength.
For the organic-inorganic co-modified PEO solid electrolyte (represented by LPPMH) and SiO-free 2 LiTFSI/PEO/PMMA@PVDF-HFP solid electrolyte (represented by LPPM) of nanospheres, solid SiO was introduced 2 The LiTFSI/PEO/PMMA@PVDF-HFP solid electrolyte (represented by LPPMS) of the nanospheres and the HMS of the hollow mesoporous silica nanospheres were subjected to infrared spectroscopic detection, and the detection results are shown in FIG. 3. As can be seen from FIG. 3, LPPMH is 2893cm -3 at-CH 2 The peak value of the functional group is obvious, which is caused by stretching vibration caused by PMMA@PVDF-HFP copolymerization, and the peak value is 3427cm -3 It was observed that HMS had a large number of-OH functional groups, but the peak-OH values in LPPMS and LPPMH were reduced because the strong polar functional group interactions reduced the peak-OH intensity.
As shown in FIG. 4, there are three oxidation-decomposition potential contrast plots of the modified PEO solid state electrolyte in three different ways, LPPM in the figure representing LiTFSI/PEO/PMMA@PVDF-HFP solid state electrolyte (SiO is not incorporated) 2 Nanofiller) having an oxidation potential of 4.36V, if solid SiO is incorporated on the basis 2 The oxidation potential of the LPPMS solid electrolyte prepared by the nanosphere filler is 4.63V, if solid SiO is used 2 The nanosphere filler is replaced by equivalent hollow mesoporous SiO 2 After the nanosphere filler, the LPPMH solid state electrolyte of this example was prepared with an oxidation potential raised to 4.84V. From this, it can be seen that hollow mesoporous SiO 2 Nanometer scaleThe ball filler can greatly improve the oxidation resistance of the solid electrolyte.
The organic-inorganic co-modified PEO solid electrolyte prepared in this example was used to fabricate NCM811 button cells. The positive plate is NMP added with 80% LiFePO 4 10% carbon black 10% PVDF, vigorously stirred for 45min, to give LFP slurry, uniformly coated on aluminum platinum, and dried overnight at 90 ℃. The negative electrode is graphite. The electrolyte was an organic-inorganic co-modified PEO solid state electrolyte prepared in this example.
The button cell was subjected to a long cycle test at a current density of 0.1C and a temperature of 60℃and the result showed that the cell using LPPMH was large in capacity retention as shown in FIG. 5, and after 250 cycles, the reversible capacity was 120.34mAh g -1 The capacity retention was 74.1% and the coulombic efficiency was 99.8%. The experimental result further shows that the LiTFSI/PEO/PMMA@PVDF-HFP/HMS system can form a stable interface layer, inhibit side reaction and ensure the long-cycle stability of the battery.
As shown in FIG. 6, hollow mesoporous SiO is introduced into LiTFSI/PEO/PMMA@PVDF-HFP solid electrolyte 2 The nanosphere filler is modified to obtain LPPMH solid electrolyte, and EIS electrochemical impedance test is carried out to test impedance change at 25 ℃,30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃ respectively. As can be seen from the graph, as the temperature increases, the impedance decreases rapidly, the lithium ion diffusion rate increases, and the ion conductivity increases; while the impedance curves are substantially coincident between 50-80 c. As shown in fig. 7, in the EIS test before and after poling (the poling time is 1000 s) the LPPMH solid electrolyte, the pre-poling impedance is 50Ω, the post-poling impedance is 18Ω, and the post-poling impedance is reduced by 4Ω, which indicates that the LPPMH has a strong lithium ion transporting capability.
Referring to fig. 8 a, which shows the polarization curve for LPPMS solid state electrolyte, the number of lithium ion transfers at an excitation voltage of 10mV was tested. The initial current was 0.295. Mu.A, the steady state current was 0.235. Mu.A, and the lithium ion transfer number of the LPPMS solid electrolyte was calculated to be 0.79. FIG. 8 b shows the polarization curve of the organic-inorganic co-modified PEO solid electrolyte (LPPMH) prepared in this example, and the number of lithium ion transfers at an excitation voltage of 10mV was tested. The initial current was 0.285. Mu.A, the steady state current was 0.235. Mu.A, and the lithium ion transfer number of the LPPMH solid electrolyte was calculated to be 0.81. Therefore, compared with the solid silica nanospheres modified PEO-based solid electrolyte, the hollow mesoporous silica nanospheres can be used for improving the transfer number of lithium ions.
Example 4
The organic-inorganic co-modified PEO solid electrolyte is prepared in this example, and the preparation method is as follows:
(1) PVDF-HFP is added into dimethyl sulfoxide, bubbling and stirring are carried out for 1h at 80 ℃ under the nitrogen atmosphere, polymethyl methacrylate PMMA (PMMA: PVDF-HFP mass ratio is 5:3) is added, dibenzoyl peroxide is added, and stirring and reaction are continued for 12h, thus obtaining PMMA@PVDF-HFP copolymer solution.
(2) PEO is dissolved in DMF and then mixed with the PMMA@PVDF-HFP copolymer solution according to the mass ratio of PEO to PMMA@PVDF-HFP copolymer (dry weight) of 5:3, and the mixture is homogenized to obtain a polymer solution.
(3) Hollow mesoporous silica nanoparticles prepared in example 1, lithium hexafluorophosphate (LiPF) was added to the polymer solution 6 ) Stirring for 12h to obtain uniform viscous solution, pouring a film on a polytetrafluoroethylene plate, evaporating the solvent, and drying in a vacuum drying oven at 70 ℃ to obtain a solid polymer electrolyte film with the thickness of 140 mu m. In the solid electrolyte membrane, liPF 6 The content of the hollow mesoporous silica nano particles is 20wt percent and the content of the hollow mesoporous silica nano particles is 16wt percent. The electrochemical window for testing the modified PEO solid electrolyte is larger than 4.5V, and the ionic conductivity at 30 ℃ is 4.5x10 -6 S/cm。
Example 5
The organic-inorganic co-modified PEO solid electrolyte is prepared in this example, and the preparation method is as follows:
(1) PVDF-HFP is added into acetone, bubbling and stirring are carried out for 2 hours at 80 ℃ under the nitrogen atmosphere, polymethyl methacrylate PMMA (PMMA: PVDF-HFP mass ratio is 5:5) is added, azodiisobutyronitrile amidine hydrochloride is added, and stirring and reaction are continued for 16 hours, so that PMMA@PVDF-HFP copolymer solution is obtained.
(2) PEO is dissolved in NMP, and then is mixed with the PMMA@PVDF-HFP copolymer solution according to the mass ratio of PEO to PMMA@PVDF-HFP copolymer (dry weight) of 1:1, and the mixture is homogenized to obtain polymer solution.
(3) Hollow mesoporous silica nanoparticles prepared in example 1, lithium perchlorate (LiClO) were added to the polymer solution 4 ) Stirring for 24 hr to obtain uniform viscous solution, casting film on polytetrafluoroethylene plate, evaporating solvent, and drying at 80deg.C in vacuum drying oven to obtain solid polymer electrolyte film with thickness of 160 μm. In the solid electrolyte membrane, liClO 4 The content of the hollow mesoporous silica nano particles is 13wt percent and the content of the hollow mesoporous silica nano particles is 10wt percent. The electrochemical window for testing the modified PEO solid electrolyte is larger than 4.5V, and the ionic conductivity at 30 ℃ is 3.1X10 -6 S/cm。
The LPPMH solid electrolyte prepared in examples 3-5 has relatively similar electrochemical properties.
Comparative example 1
The comparative example is LiTFSI/PEO/hollow mesoporous SiO 2 A solid electrolyte membrane free of PMMA@PVDF-HFP copolymer was prepared by removing the PMMA@PVDF-HFP copolymer from the substrate of example 3. Wherein, the LiTFSI content is 24wt%, and the hollow mesoporous silica nanoparticle content is 12wt%.
The solid electrolyte of this comparative example having only PEO polymer had lower polarity and viscosity than example 3, and had inferior adhesion to the pole piece than example 1.
The tensile strength of the electrolyte membrane in example 3 was 4.5MPa, and the tensile strength of the electrolyte membrane in this comparative example was 2.2MPa; therefore, the tensile resistance of the film can be greatly improved through the synergistic effect of the PEO, PVDF-HFP and PMMA.
Example 3 electrolyte Membrane having an ion conductivity of 5.9X10 at 30 ℃ -6 S/cm, and this comparative example is 3.2X10 - 7 S/cm. It follows that the PMMA@PVDF-HFP copolymer can increase ionic conductivity by utilizing a large number of carboxyl and fluorine functional groups contained in the copolymer.
The HOMO level of the electrolyte membrane in example 3 was-7.1 eV, and this comparative exampleIs-6.90 eV. From this, it can be seen that the embodiments of the present invention can reduce the HOMO level of the solid state electrolyte, reduce Li + And (5) transporting an energy barrier. Therefore, the antioxidant capacity of the electrolyte film can be obviously improved through the PEO and PMMA@PVDF-HFP polymer blend, and the adaptability to a high-voltage cathode is enhanced.
Comparative example 2
In this comparative example, liTFSI/PEO/PVDF-HFP/hollow mesoporous silica solid electrolyte was prepared by replacing PMMA@PVDF-HFP copolymer in example 3 with an equivalent amount of PVDF-HFP polymer, and the electrochemical window was tested to be 4.32V. Whereas the electrochemical window for the modified PEO solid electrolyte in example 3 was 4.6V. From this comparison, the introduction of PMMA can increase the oxidation window of the electrolyte, adapting the solid electrolyte membrane to the high voltage electrode.
Comparative example 3
In this comparative example, the PMMA@PVDF-HFP copolymer in example 3 was replaced with an equal amount of a physical mixture of PMMA and PVDF-HFP, a casting solution was prepared, the solvent was evaporated by casting on a polytetrafluoroethylene plate, and after drying in a vacuum drying oven at 80 ℃, GPE (gel electrolyte) characteristics were exhibited during film stripping, the casting solution was difficult to form a film, and the mechanical strength of the electrolyte film was weak, mainly due to the fact that PVDF-HFP had the characteristic of coordinating and absorbing with the solvent.
It follows that if PMMA, PVDF-HFP are directly incorporated into the PEO matrix as a mixture, the system film forming properties are poor and the mechanical strength is reduced. The copolymer with ultrahigh compatibility is obtained by copolymerizing PMMA and PVDF-HFP initiated by free radicals, and has physical and chemical properties of the PMMA and PVDF-HFP, so that the ductility and the fluidity of the film are greatly enhanced, and the mechanical strength of the film is enhanced. There is no report on the copolymerization of PMMA and PVDF-HFP followed by modification of PEO-based solid electrolytes.
In conclusion, the solid polymer electrolyte prepared by the invention has high ionic conductivity, mechanical strength, chemical stability, wider electrochemical stability window and good adhesion with an electrode, is suitable for the design and production of flexible batteries, and is beneficial to improving the safety performance of lithium ion batteries.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. An organic-inorganic co-modified PEO solid electrolyte is characterized by comprising a PEO matrix, lithium salt, an organic polymer modifier and an inorganic filler modifier; the inorganic filler modifier is hollow mesoporous silica nano particles; the organic polymer modifier PMMA@PVDF-HFP copolymer is a copolymer obtained by copolymerizing polyethyl methacrylate and polyvinylidene fluoride-hexafluoropropylene through a free radical initiator; the mass ratio of the organic polymer modifier to the PEO matrix is 3-10:10; the preparation method of the PMMA@PVDF-HFP copolymer comprises the following steps: PVDF-HFP is added into acetone/dimethyl sulfoxide, bubbling and stirring are carried out for 0.5-3h at 60-80 ℃ under the nitrogen atmosphere, polymethyl methacrylate PMMA is added, a free radical initiator is added, and stirring and reacting are continued for 6-18h, thus obtaining PMMA@PVDF-HFP copolymer.
2. The organic-inorganic co-modified PEO solid electrolyte of claim 1 wherein the free radical initiator is azobisisobutyronitrile, azobisisobutyronitrile amidine hydrochloride, dibenzoyl peroxide, na 2 S 2 O 8 、K 2 S 2 O 8 、(NH 4 ) 2 S 2 O 8 At least one of (a) and (b); and (3) carrying out chain segment reaction on PMMA and PVDF-HFP under the action of a free radical initiator to obtain the PMMA@PVDF-HFP copolymer.
3. The organic-inorganic co-modified PEO solid state electrolyte of claim 1 wherein the lithium salt is lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium trifluoromethylsulfonate (LiCF) 3 SO 3 ) At least one of lithium bisoxalato borate (LiBOB), lithium difluorooxalato borate (liodbb), and lithium chloride (LiCl).
4. The organic-inorganic co-modified PEO solid state electrolyte of claim 1 wherein the mass fraction of hollow mesoporous silica nanoparticles in the solid state electrolyte is 1-35% and the mass fraction of lithium salt in the solid state electrolyte is 15-35%.
5. A method for preparing organic-inorganic co-modified PEO solid electrolyte, which is characterized by comprising the following steps:
s1, preparing hollow mesoporous silica nanoparticles;
s2, carrying out copolymerization reaction on PMMA and PVDF-HFP to obtain a PMMA@PVDF-HFP copolymer;
s3, dissolving PEO and PMMA@PVDF-HFP copolymer in an organic solvent according to a proportion, and homogenizing to obtain a polymer solution;
s4, dispersing lithium salt and hollow mesoporous silica nano particles in the polymer solution, uniformly dispersing, casting to form a film, and volatilizing the solvent to obtain the organic-inorganic co-modified PEO solid electrolyte.
6. The method of preparing hollow mesoporous silica nanoparticles according to claim 5, wherein the method of preparing hollow mesoporous silica nanoparticles in step S1 is as follows:
step 1: dispersing nano ferroferric oxide particles into a solvent, wherein the dispersion mass concentration is 0.1-10%, and the ultrasonic dispersion is uniform; the particle size of the nano ferroferric oxide particles is 50-200nm; the solvent is at least one of methanol, ethanol, tetrahydrofuran, toluene, xylene and dichloromethane;
step 2: under the standing condition, adding a soluble silicon source into the dispersion liquid in the step 1 to obtain a reaction liquid, wherein the mass ratio of the ferroferric oxide to the soluble silicon source is 10:1-1:10, adding ammonia water accounting for 1-5wt% of the mass of the reaction liquid under stirring, and stirring for 1-5h; the soluble silicon source is ethyl orthosilicate, methyl orthosilicate, trimethylethoxysilane or sodium silicate;
step 3: adding a cationic surfactant at 30-120 ℃ for reaction for 0.5-12 hours, magnetically collecting a product, dispersing in alkali liquor, stirring at 20-80 ℃, magnetically collecting the product again, washing with absolute ethyl alcohol, and calcining at 300-500 ℃ or refluxing with acetone to obtain the silicon dioxide coated ferroferric oxide nano particles;
step 4: and (3) carrying out acid etching on the silicon dioxide coated ferroferric oxide nano particles to remove the ferroferric oxide, washing and drying to obtain the hollow mesoporous silicon dioxide nano particles, wherein the hollow mesoporous silicon dioxide nano particles have good dispersibility.
7. The method according to claim 6, wherein in the step S2, the PMMA@PVDF-HFP copolymer is prepared by the following steps: adding PVDF-HFP into acetone/dimethyl sulfoxide, bubbling and stirring at 60-80 ℃ for 0.5-3h under nitrogen atmosphere, adding polymethyl methacrylate PMMA, adding a free radical initiator, and continuing stirring and reacting for 6-18h to obtain PMMA@PVDF-HFP copolymer solution; the free radical initiator is azobisisobutyronitrile, azobisisobutyronitrile amidine hydrochloride, dibenzoyl peroxide or Na 2 S 2 O 8 、K 2 S 2 O 8 、(NH 4 ) 2 S 2 O 8 At least one of them.
8. The preparation method according to claim 6, wherein in the step S3, PEO is dissolved in a solvent, and then is mixed with the PMMA@PVDF-HFP copolymer solution prepared in the step S2 according to the mass ratio of PEO to PMMA@PVDF-HFP copolymer of 10:3-10, and the mixture is homogenized to obtain a polymer solution; the solvent is acetonitrile, acetone, N-Dimethylformamide (DMF) or N-methylpyrrolidone (NMP).
9. The preparation method according to claim 6, wherein in the step S4, hollow mesoporous silica nanoparticles and lithium salt are added into the polymer solution, and the polymer solution is continuously dispersed for 0.5 to 24 hours at the temperature of 20 to 90 ℃, so as to obtain casting film slurry after uniform dispersion, and the slurry is cast into a film, and after the solvent volatilizes, the organic-inorganic co-modified PEO solid electrolyte is prepared.
10. The method according to claim 6, wherein in step S4, the hollow mesoporous silica nanoparticle accounts for 1-35% of the mass of the organic-inorganic co-modified PEO solid electrolyte, and the lithium salt accounts for 15-35% of the mass of the organic-inorganic co-modified PEO solid electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410006667.6A CN117525574B (en) | 2024-01-03 | 2024-01-03 | Organic-inorganic co-modified PEO solid electrolyte and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410006667.6A CN117525574B (en) | 2024-01-03 | 2024-01-03 | Organic-inorganic co-modified PEO solid electrolyte and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117525574A CN117525574A (en) | 2024-02-06 |
| CN117525574B true CN117525574B (en) | 2024-03-22 |
Family
ID=89764840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410006667.6A Active CN117525574B (en) | 2024-01-03 | 2024-01-03 | Organic-inorganic co-modified PEO solid electrolyte and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117525574B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010010675A (en) * | 1999-07-22 | 2001-02-15 | 윤덕용 | Porous Polymeric Electrolytes Comprising Vinylidenefluoride and Polyacrylate Polymers and Process for Preparing the Same |
| CN102633265A (en) * | 2012-03-29 | 2012-08-15 | 中国科学院山西煤炭化学研究所 | Preparation method for controllable hollow mesoporous silicon dioxide nanospheres |
| CN104177738A (en) * | 2013-05-24 | 2014-12-03 | 苏州宝时得电动工具有限公司 | Polymer membrane, preparation method thereof, electrolyte possessing polymer membrane and cell |
| CN105529496A (en) * | 2015-10-23 | 2016-04-27 | 湘潭大学 | Gel polymer electrolyte membrane and preparation method thereof |
| CN106935906A (en) * | 2017-04-28 | 2017-07-07 | 张家港市国泰华荣化工新材料有限公司 | A kind of functional form polymer dielectric and its application in lithium ion battery |
| CN110048156A (en) * | 2019-05-06 | 2019-07-23 | 浙江大学 | A kind of solid electrolyte and its preparation method and application |
| WO2020034168A1 (en) * | 2018-08-16 | 2020-02-20 | 苏州大学张家港工业技术研究院 | Porous lithium ion battery separator film employing cross-linked polymer and linear polymer, preparation method and application thereof |
| CN111613760A (en) * | 2020-05-28 | 2020-09-01 | 珠海冠宇电池股份有限公司 | Battery separator, battery and preparation method of battery separator |
| CN115566264A (en) * | 2022-09-30 | 2023-01-03 | 辽宁登赛新能源有限公司 | Hollow nano-sphere-based composite solid electrolyte of lithium battery and preparation method thereof |
| CN115966759A (en) * | 2021-10-11 | 2023-04-14 | 南京航空航天大学 | Polyethylene oxide solid electrolyte and preparation method and application thereof |
-
2024
- 2024-01-03 CN CN202410006667.6A patent/CN117525574B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010010675A (en) * | 1999-07-22 | 2001-02-15 | 윤덕용 | Porous Polymeric Electrolytes Comprising Vinylidenefluoride and Polyacrylate Polymers and Process for Preparing the Same |
| CN102633265A (en) * | 2012-03-29 | 2012-08-15 | 中国科学院山西煤炭化学研究所 | Preparation method for controllable hollow mesoporous silicon dioxide nanospheres |
| CN104177738A (en) * | 2013-05-24 | 2014-12-03 | 苏州宝时得电动工具有限公司 | Polymer membrane, preparation method thereof, electrolyte possessing polymer membrane and cell |
| CN105529496A (en) * | 2015-10-23 | 2016-04-27 | 湘潭大学 | Gel polymer electrolyte membrane and preparation method thereof |
| CN106935906A (en) * | 2017-04-28 | 2017-07-07 | 张家港市国泰华荣化工新材料有限公司 | A kind of functional form polymer dielectric and its application in lithium ion battery |
| WO2020034168A1 (en) * | 2018-08-16 | 2020-02-20 | 苏州大学张家港工业技术研究院 | Porous lithium ion battery separator film employing cross-linked polymer and linear polymer, preparation method and application thereof |
| CN110048156A (en) * | 2019-05-06 | 2019-07-23 | 浙江大学 | A kind of solid electrolyte and its preparation method and application |
| CN111613760A (en) * | 2020-05-28 | 2020-09-01 | 珠海冠宇电池股份有限公司 | Battery separator, battery and preparation method of battery separator |
| CN115966759A (en) * | 2021-10-11 | 2023-04-14 | 南京航空航天大学 | Polyethylene oxide solid electrolyte and preparation method and application thereof |
| CN115566264A (en) * | 2022-09-30 | 2023-01-03 | 辽宁登赛新能源有限公司 | Hollow nano-sphere-based composite solid electrolyte of lithium battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Nano-SiO2@PMMA-doped composite polymer PVDF-HFP/PMMA/PEO electrolyte for lithium metal batteries;Li, Jian;《JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS》;20200229;第31卷(第3期);第2708-2719页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117525574A (en) | 2024-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101460282B1 (en) | Lithium electrode and lithium metal batteries fabricated by using the same | |
| CN102089240B (en) | Insert the porous carbon substrate of silicon and/or stannum | |
| US11362328B2 (en) | Composite-coated nano-tin negative electrode material and preparation method and use thereof | |
| CN112909234A (en) | Preparation method and application of lithium cathode or sodium cathode | |
| US11855275B2 (en) | Method of preparing cathode for secondary battery | |
| JP2012516531A (en) | Method for producing electrode composition | |
| WO2016161920A1 (en) | Composite separator and preparation method therefor, and lithium-ion battery | |
| CN111244438A (en) | Graphene/carbon-coated lithium titanate composite material and preparation method thereof | |
| US20190319262A1 (en) | Surface-stabilized selenium particles, alkali metal-selenium secondary battery containing same, and method of manufacturing | |
| CN110165152A (en) | Solid-state anode composite material, preparation method and application | |
| KR20220023753A (en) | Nanoparticles with a polythionate core | |
| JP2018073813A (en) | Formation of sulfur particles using organic acids in presence of polymer functionalized carbon | |
| CN111193022B (en) | Preparation and application of modified ammonium trifluorooxotitanate for lithium ion battery | |
| Kurc | Composite gel polymer electrolyte with modified silica for LiMn2O4 positive electrode in lithium-ion battery | |
| Liao et al. | Fabrication of SiOx-G/PAA-PANi/Graphene composite with special cross-doped conductive hydrogels as anode materials for lithium ion batteries | |
| CN109167036B (en) | TiN and conductive polymer composite modified lithium ion layered ternary positive electrode material and preparation method thereof | |
| CN110931727A (en) | Preparation method of conductive polymer-coated silicon-based negative electrode material | |
| KR101397417B1 (en) | Manufacturing method of metal nano particle-carbon complex, metal nano particle-carbon complex made by the same, and electrochemical device including the same | |
| CN110492175B (en) | Organic nano composite electrolyte membrane for all-solid-state alkali metal battery and preparation method thereof | |
| CN111342120B (en) | Polymer solid electrolyte, nano composite diaphragm and preparation method thereof, and lithium metal battery | |
| CN117525574B (en) | Organic-inorganic co-modified PEO solid electrolyte and preparation method thereof | |
| CN117059799A (en) | Graphite anode material and preparation method and application thereof | |
| CN110581273B (en) | Zinc-position sodium-copper co-doped synergetic nitrogen-sulfur doped carbon-coated modified zinc titanate negative electrode material and preparation method and application thereof | |
| CN115566264A (en) | Hollow nano-sphere-based composite solid electrolyte of lithium battery and preparation method thereof | |
| US20230095117A1 (en) | Cathode and cathode slurry for secondary 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 |