CN107820642A - 锂‑硫电池组用玻璃‑陶瓷电解质 - Google Patents
锂‑硫电池组用玻璃‑陶瓷电解质 Download PDFInfo
- Publication number
- CN107820642A CN107820642A CN201680028992.6A CN201680028992A CN107820642A CN 107820642 A CN107820642 A CN 107820642A CN 201680028992 A CN201680028992 A CN 201680028992A CN 107820642 A CN107820642 A CN 107820642A
- Authority
- CN
- China
- Prior art keywords
- lithium
- component
- electrochemical cells
- sulfur electrochemical
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 15
- 229910021525 ceramic electrolyte Inorganic materials 0.000 title description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000005864 Sulphur Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 238000005192 partition Methods 0.000 claims abstract description 6
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 4
- 239000001989 lithium alloy Substances 0.000 claims abstract description 4
- 239000006182 cathode active material Substances 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000000919 ceramic Substances 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- 229910016850 F2n+1SO2 Inorganic materials 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000005373 porous glass Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920006254 polymer film Polymers 0.000 claims description 3
- 229910007549 Li2SiF6 Inorganic materials 0.000 claims description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Chemical group 0.000 claims description 2
- 239000011574 phosphorus Chemical group 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 239000010703 silicon Chemical group 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052713 technetium Inorganic materials 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910013375 LiC Inorganic materials 0.000 claims 1
- 229910013426 LiN(SO2F)2 Inorganic materials 0.000 claims 1
- 238000001465 metallisation Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 23
- 150000008117 polysulfides Polymers 0.000 description 23
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 21
- 239000005077 polysulfide Substances 0.000 description 18
- 229920001021 polysulfide Polymers 0.000 description 18
- -1 ketal Chemical class 0.000 description 17
- 239000010408 film Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000011324 bead Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- 229940052303 ethers for general anesthesia Drugs 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 125000006091 1,3-dioxolane group Chemical class 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical class CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Chemical class CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910010951 LiH2 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910006270 Li—Li Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 210000004262 dental pulp cavity Anatomy 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229920002627 poly(phosphazenes) Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical class COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- UUAMLBIYJDPGFU-UHFFFAOYSA-N 1,3-dimethoxypropane Chemical class COCCCOC UUAMLBIYJDPGFU-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical class CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- 208000000058 Anaplasia Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010954 LiGe2(PO4)3 Inorganic materials 0.000 description 1
- 229910000857 LiTi2(PO4)3 Inorganic materials 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical class CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- LPEBZWCCILEKJA-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(COCCOCCO)O Chemical compound N=NC=NN.N=NC=NN.C(COCCOCCO)O LPEBZWCCILEKJA-UHFFFAOYSA-N 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000012459 muffins Nutrition 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000003625 skull Anatomy 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- 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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
-
- 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
-
- 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
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
- H01M50/437—Glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Ceramic Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Separators (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
本发明涉及一种锂‑硫电化学电池,包含作为组分的(A)包含锂金属或锂合金和与其导电连接的锂离子的电解质,作为组分的(B)包含无定形相的玻璃陶瓷膜,作为组分的(C)包含至少一种溶剂和至少一种锂盐的液体电解质,作为组分的(D)包含硫作为阴极活性物质的电极。本发明还涉及包含本文所定义的锂‑硫电化学电池的电池组。本发明进一步涉及本文所定义的玻璃陶瓷膜在(i)锂‑硫电化学电池或(ii)包含至少一个锂‑硫电化学电池的电池组中作为隔片的用途。
Description
本发明涉及一种锂-硫电化学电池,包含作为组分的(A)包含锂金属或锂合金和与其导电连接的锂离子的电解质,作为组分的(B)包含无定形相的玻璃陶瓷膜,作为组分的(C)包含至少一种溶剂和至少一种锂盐的液体电解质,作为组分的(D)包含硫作为阴极活性物质的电极。
本发明还涉及包含本文所定义的锂-硫电化学电池的电池组。本发明进一步涉及本文所定义的玻璃陶瓷膜在(i)锂-硫电化学电池或(ii)包含至少一个锂-硫电化学电池的电池组中作为隔片的用途。
据信可再充电锂-硫(Li/S)电池组对于长车程(>300km)纯电动车(PEV)和插电式电动车(PHEV)是非常有前景的替代能源,因为基于插层材料的当前锂离子电池组(LIB)仅可潜在提供至多200Wh kg-1的能量密度。该类新型电池组系统提高高得多的能量密度并且相对廉价。假定硫(S8)完全电化学转化为硫化锂(Li2S),理论能量密度值可以达到2500Whkg-1,实际值为500-600Wh kg-1。因此,对于移动和便携式应用,尤其是高能应用已经研究Li/S电池组。
作为阳极材料的锂由于其负电化学电势和与其它材料组合时其宽电化学窗口、其轻质以及因此在所有金属阳极材料中重量能量密度最高而提供几个优于其它材料的优点。锂-硫电池组中的阴极活性材料由硫构成。硫在阴极中的浓度可以在30-80重量%之间变化。由于流的电子绝缘性能,要求存在其他添加剂。作为导电添加剂使用碳(20-60重量%)且为了确保阴极层的机械完整性,使用额外的粘合剂(1-10重量%)。
目前容量快速衰减和硫利用率低是将Li/S用作可再充电系统的主要障碍。仅可使用作为理论容量的1672mAhg-1中的约50%或-800mAhg-1。原因是“多硫化物穿梭”机理。元素硫分子在第一放电过程中接受电子并逐渐由高阶转化成低阶多硫化物。具有少于3个硫原子的低阶多硫化物(Li2S3)在电解质中不可溶,因而妨碍接下来得到不溶性非电子导电的Li2S2的还原步骤。因此,在大于C/10的比值下观察到低放电效率。此外,在充电循环过程中多硫化物不转化为元素硫。代替在最后步骤中被氧化成硫,高阶多硫化物不断扩散到阳极,在这里它们以寄生反应被元素锂逐渐还原成低阶多硫化物。可溶性低阶多硫化物则扩散回到阴极,从而产生“多硫化物穿梭”。不溶性低阶多硫化物从电解质中沉淀并在阳极侧聚集。总之,该机理降低充电效率并在阳极和阴极上引起腐蚀。结果Li/S电池组具有的缺点是容量衰减和循环寿命不足。本领域Li/S电池组系统的典型状态可以达到50-80个循环的寿命。
因此,本发明的目的是要提供显示出改善的容量和循环寿命的锂-硫电化学电池。该目的由本文所述锂-硫电化学电池实现。
因此,本发明在第一方面涉及锂-硫电化学电池,包括:
作为组分的(A)包含锂金属或锂合金和与其导电连接的锂离子的电解质,
作为组分的(B)包含无定形相的纳米多孔玻璃陶瓷膜,
作为组分的(C)包含至少一种溶剂和至少一种锂盐的液体电解质,
作为组分的(D)包含硫作为阴极活性物质的电极。
惊人地发现包含无定形相的玻璃陶瓷膜提供多硫化物和锂树枝状结晶的良好阻断。不希望受任何理论束缚,据信在包含无定形相的玻璃陶瓷中,封闭了陶瓷晶体之间的孔。用于本发明用途的包含无定形相的纳米多孔玻璃陶瓷膜例如可以如DE 10 2011 013018 B和DE 10 2014 100 684所述制备。
相比之下,通过标准烧结制备的陶瓷具有残留孔隙率,这导致锂树枝状结晶的快速生长和随后的电池短路。该类陶瓷仅可作为非常厚的膜使用,这将强烈增加电池极化。或者,必须在额外的步骤封闭孔,例如通过聚合物树脂灌注。相比之下,通过SCHOTT的有利熔体合成得到也可以作为非常薄,例如低至180μm的膜使用的具有固有高密度的陶瓷。
本文所用“纳米多孔”玻璃陶瓷膜由支撑规则多孔结构的规则骨架构成。孔的平均尺寸通常为100纳米或更小。
“无定形相”是缺少结晶相的长程有序特征的非晶相。
根据本发明优选在本文所述的锂-硫电化学电池中,该无定形相占组分(B)的5-40体积%,更优选5-30体积%,最优选10-25体积%。
根据本发明还优选在本文所述的锂-硫电化学电池中,组分(B)具有40体积%或更小,更优选30体积%或更小,甚至更优选20体积%或更小,最优选5体积%或更小的平均孔隙率,和/或组分(B)具有至少1体积%的孔隙率。
平均孔隙率例如可以使用压汞仪测量。简单地讲,平均孔隙率可以通过测量迫使液体(例如汞)进入孔中(例如抵抗液体和孔之间的表面张力的反向力)所要求的外部压力而测定。本领域熟练技术人员能够基于选取的颗粒选择合适范围的外部压力。
如前所述,通过SCHOTT的有利熔体合成得到也可以作为非常薄的膜使用的具有固有高密度的陶瓷。
因此,根据本发明优选在本文所述的锂-硫电化学电池中,组分(B)具有500μm或更小,更优选400μm或更小,甚至更优选200μm或更小,进一步甚至更优选100μm或更小,最优选50μm或更小的平均厚度。
根据本发明优选在本文所述的锂-硫电化学电池中,组分(B)满足下列标准中的一个或多个:
-它包含一种或多种选自Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Y,Zr,Nb,Mo,Tc,Ru,Rh,Pd,Ag,Cd,La,Hf,Ta,W,Re,Os,Ir,Pt,Au,Hg,Al,Ga,In,Tl,Si,Ge,Sn,Pb的金属;
-其表面在与组分(C)接触时带正电或带负电;
-它在与组分(C)接触时能够释放阳离子,该阳离子在组分(B)的表面处被组分(C)的溶剂溶剂化;
-它能够经由氧原子与锂离子配位。
在本文所述的锂-硫电化学电池中,该电解质可以包含一种或多种离子性电解质盐以提供离子传导性和一种或多种液体电解质溶剂、凝胶聚合物材料或聚合物材料。优选的非水电解质包括包含一种或多种选自液体电解质、凝胶聚合物电解质和固体聚合物电解质的材料的有机电解质。
非水液体电解质溶剂包括但不限于非水有机溶剂,后者优选选自N-甲基乙酰胺、乙腈、缩醛、缩酮、酯类、碳酸酯类、砜类、亚硫酸酯类、环丁砜类、脂族醚类、无环醚类、环状醚类、甘醇二甲醚类、聚醚、磷酸酯类、硅氧烷类、二氧戊环类、N-烷基吡咯烷酮类、前述物质的取代形式及其共混物。优选的无环醚类选自乙醚、二丙基醚、二丁基醚、二甲氧基甲烷、三甲氧基甲烷、二甲氧基乙烷、二乙氧基乙烷、1,2-二甲氧基丙烷和1,3-二甲氧基丙烷。优选的环状醚类选自四氢呋喃、四氢吡喃、2-甲基四氢呋喃、1,4-二烷、1,3-二氧戊环和三烷。优选的聚醚选自二甘醇二甲基醚(二甘醇二甲醚)、三甘醇二甲基醚(三甘醇二甲醚)、四甘醇二甲基醚(四甘醇二甲醚)、高级甘醇二甲醚类、乙二醇二乙烯基醚、二甘醇二乙烯基醚、三甘醇二乙烯基醚、二丙二醇二甲基醚和丁二醇醚类。优选的砜类选自环丁砜、3-甲基环丁砜和3-环丁烯砜。前述物质的氟代衍生物也可以用作液体电解质溶剂。还可以使用本文所述溶剂的混合物。
优选的溶剂混合物选自1,3-二氧戊环和二甲氧基乙烷、1,3-二氧戊环和二甘醇二甲基醚、1,3-二氧戊环和三甘醇二甲基醚以及1,3-二氧戊环和环丁砜。混合物中这两种溶剂的重量比优选在约5:95-95:5内变化。
优选的凝胶聚合物电解质选自聚氧乙烯、聚氧丙烯、聚丙烯腈、聚硅氧烷、聚酰亚胺、聚磷腈、聚醚、磺化聚酰亚胺、全氟化膜(NAFION树脂)、聚二乙烯基聚乙二醇、聚乙二醇二丙烯酸酯、聚乙二醇二甲基丙烯酸酯、前述物质的衍生物、前述物质的共聚物、前述物质的交联和网络结构以及前述物质的共混物。
优选的固体聚合物电解质选自聚醚、聚氧乙烯、聚氧丙烯、聚酰亚胺、聚磷腈、聚丙烯腈、聚硅氧烷、前述物质的衍生物、前述物质的共聚物、前述物质的交联和网络结构以及前述物质的共混物。
根据本发明优选在本文所述的锂-硫电化学电池中,组分(C)的至少一种锂盐选自LiNO3,LiPF6,LiBF4,LiClO4,LiAsF6,Li2SiF6,LiSbF6,LiAlCl4,二草酸硼酸锂,LiCF3SO3,LiN(SO2F)2,LiC(CnF2n+1SO2)3,,其中n为1-20的整数,以及(CnF2n+1SO2)mXLi,其中n为1-20的整数,m在X选自氧或硫时为1,m在X选自氮或磷时为2,并且m在X选自碳或硅时为3。
根据本发明还优选在本文所述的锂-硫电化学电池中,组分(D)包含元素硫作为电活性物质。
本文所用“电活性含硫材料”涉及以任何形式包含元素硫的阴极活性材料,其中电化学活性涉及硫-硫共价键的断裂或形成。优选的电活性含硫材料选自元素硫以及包含硫原子和碳原子的有机材料,后者可以是或者可以不是聚合物。有机材料包括进一步包含杂原子的那些、导电聚合物链段、复合体和导电聚合物。
优选该含硫材料以其还原形式包含选自共价Sm结构部分、离子Sm结构部分和离子Sm2-结构部分的多硫化物结构部分Sm,其中m为等于或大于3的整数。优选该含硫聚合物的多硫化物结构部分Sm的m为等于或大于6的整数。更优选该含硫聚合物的多硫化物结构部分Sm的m为等于或大于8的整数。在本发明的优选方面,该含硫材料为含硫聚合物。在本发明的另一优选方面,该含硫聚合物具有聚合物骨架链且多硫化物结构部分Sm通过其末端硫原子之一或二者作为侧基共价键合于聚合物骨架链。在本发明的再一优选方面,该含硫聚合物具有聚合物骨架链且多硫化物结构部分Sm通过多硫化物结构部分的末端硫原子的共价键合掺入聚合物骨架链中。
优选该电活性含硫材料包含大于50重量%的硫。更优选该电活性含硫材料包含大于75重量%的硫。最优选该电活性含硫材料包含大于90重量%的硫。
可以用于实施本发明的该电活性含硫材料的性质正如本领域已知那样可以宽泛变化。在本发明的优选方面,该电活性含硫材料包含元素硫。在本发明的另一优选方面,该电活性含硫材料包含元素硫和含硫聚合物的混合物。
根据本发明优选本文所述的锂-硫电化学电池进一步包括作为组分的(E)接触组分(A)的集电器。
用于集电器的材料优选选自金属(例如铜、镍、铝、钝化金属和其他合适的金属);金属化聚合物;导电聚合物;包括分散于其中的导电颗粒的聚合物;以及其他合适材料。在本发明的优选方面,使用物理气相沉积、化学汽相淀积、电化学沉积、溅射、刮涂、闪蒸或者任何其他适合选取材料的沉积技术将集电器沉积于电极层上。或者,集电器可以分开形成并与电极结构结合。
根据本发明优选本文所述的锂-硫电化学电池进一步包括作为组分的(F)接触组分(A)或接触组分(E)的载体基板。
该载体基板可以由聚合物材料制成。例如,该载体基板可以包含聚酯,如聚对苯二甲酸乙二醇酯(PET)(例如光学级聚对苯二甲酸乙二醇酯),聚烯烃如聚丙烯和聚乙烯(可以任选金属化),尼龙,聚氯乙烯,聚乙烯醇。该载体基板还可以包含金属或陶瓷材料。
根据本发明优选在本文所述的锂-硫电化学电池中,该载体基板选自聚合物薄膜、金属化聚合物薄膜、陶瓷薄膜和金属薄膜。
在另一方面,本发明涉及一种包括至少一个本文所述的锂-硫电化学电池的电池组。
在另一方面,本发明涉及本文所定义的玻璃陶瓷膜在(i)锂-硫电化学电池或(ii)包括至少一个锂-硫电化学电池的电池组中作为隔片的用途。
本发明通过下列非限制性实施例进一步说明。
制备包含无定形相的纳米多孔玻璃陶瓷膜:
Li1.6Al0.5Ti0.95Ta0.5(PO3)4(LATTP)玻璃陶瓷如前面在US 2014/0057162中所述通过在石英坩埚中在1500-1650℃下在空气中感应熔融原料而制备。原料组成(重量%)如下:5.4%Al2O3(来源:Al(PO3)3),5.2%Li2O(来源:LiH2PO4),45.9%P2O5(包括LiH2PO4和Al(PO3)3),3.9%SiO2,23.2%Ta2O5和16.4%TiO2。将熔体浇铸与金属板上,形成厚度为3-8mm且直径为30-40mm的玻璃板。将一些玻璃倾于双辊装置上以产生用于粉末生产的玻璃带。将玻璃样品在530℃下刚好在玻璃化转变温度下退火并缓慢冷却至室温(速率20℃/h)。所得玻璃样品呈深紫色,在几个点处发生自发结晶。通过差热分析测定成核和结晶温度,相应地将样品在850-950℃下退火12小时并缓慢冷却至室温而形成用于我们的试验的玻璃陶瓷。主相是公称组成为Li1.6Al0.5Ti0.95Ta0.5(PO3)4的NASICON结构,与LiGe2(PO4)3和LiTi2(PO4)3同构。在XRD光谱中作为杂质相(<2重量%)观察到的SiO2(白硅石)可能在热处理步骤过程中形成。
为了制备Ta掺杂的Li7La3Zr2O12(LLZO)玻璃陶瓷,以下列比例(重量%)混合工业级原料:13.9%Li2O,53.6%La2O3,20.3%ZrO2和12.1%Ta2O5。因为该组合物是高度腐蚀性的,因此使用凝壳熔融技术。该技术使用水冷却的坩埚(凝壳炉),导致在坩埚和熔体之间形成固化熔体的阻挡层。将该批料使用煤气灯预热,然后使用高频感应加热熔融。在搅拌和均化该熔体之后,关闭感应加热,使该熔体缓慢冷却至室温。所得材料为白色至轻微黄色的且高度结晶,具有100%立方石榴石结晶相(通过XRD测定)。没有检测到杂质相。使用无水制备方法由结晶锭制备大块样品和粉末材料。
多硫化物穿梭:
将固态离子导体作为阳极和阴极之间的隔片整合到Li/S电池组设置中,避免短路但允许锂离子在充电和放电过程中输送。该膜本身厚180μm,由LATTP玻璃陶瓷制成。没有粘合剂或其他导电聚合物存在于所用膜内。
电池设置:
阳极:锂金属
液体电解质:具有1M LiTFSI的三甘醇二甲基醚
分隔:LATTP膜
阴极:硫-碳
没有其他添加剂如LiNO3用于该电解质中以阻断多硫化物穿梭。
结果:
该Li/S电池以由0.6mA/cm2到4mA/cm2变化的不同电流密度在1.8-2.8V的电压范围内循环。使用该设置并提高电流密度可以实现约150个循环(1个循环为充电和放电步骤)。固态离子传导膜抑制多硫化物穿梭,否则该电池将在1-2个循环后就不能用了。
多硫化物渗透:
还用U型管式扩散装置非现场测试膜对多硫化物的渗透性。
设置:
对于扩散测量,借助特氟隆密封件将陶瓷小球放置在具有连接的玻璃接头的两个玻璃管(内径17mm)之间。各管用夹子固定。将具有3个额外接头的玻璃盖安装在各管顶部。用氮气吹扫该设置。通过隔膜对一根管填充多硫化物溶液(0.05M Li2S6,在DOL/DME中),对另一根管填充DOL/DME。多硫化物在溶剂中的渗透用指定的UV探针光学跟踪(测量波长为380nm,ε=158m2/mol)。
结果:
图1示出了对于a)作为多孔膜的经典实例的聚烯烃隔片,b)500μm厚LATP膜和c)180μm LATP膜多硫化物浓度随时间的增加。清楚可见的是该陶瓷膜与该多孔材料相比对多硫化物的渗透低得多并且通过LATP的渗透与膜厚无关。
制备烧结陶瓷(对比例):
Li7La3Zr1.75Nb0.25O12陶瓷小球通过下列方法制备:
1.使用球磨以根据上式的正确化学计量混合LiOH、La2O3、ZrO2和Nb2O5。
2.将混合的粉末压制成小球并在1100℃下合成12小时。
3.将合成的小球研磨成粉饼在IPA中球磨24小时以减小尺寸。
4.然后将粉末干燥,压制成1英寸直径的小球并在1140℃下烧结12-24小时。
5.将烧结的小球从两侧抛光成1mm厚度。对它们进行组成、密度和Li-Li循环分析。压汞法(至多35,000psi)测量表明密度为理论密度的>99.9%。
Li-Li电池通过将直径稍微小于小球的锂箔(7/8”锂箔和1”小球)放置在各侧而构造。将该堆叠体放置在夹紧测试盒中,施加并在测试过程中维持10kg/cm2的压力。循环在0.01mA/cm2的比值下进行。在几个循环之后,观察到树枝状结晶形成(电压从至多±0.5V突然下降到1mV)。
Claims (15)
1.锂-硫电化学电池,包括:
作为组分的(A)包含锂金属或锂合金和与其导电连接的锂离子的电解质,
作为组分的(B)包含无定形相的纳米多孔玻璃陶瓷膜,
作为组分的(C)包含至少一种溶剂和至少一种锂盐的液体电解质,
作为组分的(D)包含硫作为阴极活性物质的电极。
2.根据权利要求1的锂-硫电化学电池,其中所述无定形相占组分(B)的5-40体积%,优选5-30体积%,最优选10-25体积%。
3.根据前述权利要求中任一项的锂-硫电化学电池,其中组分(B)具有40体积%或更小,优选30体积%或更小,更优选20体积%或更小,最优选5体积%或更小的平均孔隙率和/或其中组分(B)具有至少1体积%的孔隙率。
4.根据前述权利要求中任一项的锂-硫电化学电池,其中组分(B)具有500μm或更小,优选400μm或更小,更优选200μm或更小,甚至更优选100μm或更小,最优选50μm或更小的平均厚度。
5.根据前述权利要求中任一项的锂-硫电化学电池,其中组分(B)包含一种或多种选自Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Y,Zr,Nb,Mo,Tc,Ru,Rh,Pd,Ag,Cd,La,Hf,Ta,W,Re,Os,Ir,Pt,Au,Hg,Al,Ga,In,Tl,Si,Ge,Sn,Pb的金属。
6.根据前述权利要求中任一项的锂-硫电化学电池,其中组分(B)的表面在与组分(C)接触时带正电或带负电。
7.根据前述权利要求中任一项的锂-硫电化学电池,其中组分(B)在与组分(C)接触时能够释放阳离子,所述阳离子在组分(B)的表面处被组分(C)的溶剂溶剂化。
8.根据前述权利要求中任一项的锂-硫电化学电池,其中组分(B)能够经由氧原子与锂离子配位。
9.根据前述权利要求中任一项的锂-硫电化学电池,其中组分(C)的所述至少一种锂盐选自LiNO3,LiPF6,LiBF4,LiClO4,LiAsF6,Li2SiF6,LiSbF6,LiAlCl4,二草酸硼酸锂,LiCF3SO3,LiN(SO2F)2,LiC(CnF2n+1SO2)3,,其中n为1-20的整数,以及(CnF2n+1SO2)mXLi,其中n为1-20的整数,m在X选自氧或硫时为1,m在X选自氮或磷时为2,以及m在X选自碳或硅时为3。
10.根据前述权利要求中任一项的锂-硫电化学电池,其中组分(D)包含元素硫作为电活性物质。
11.根据前述权利要求中任一项的锂-硫电化学电池,进一步包含作为组分的(E)接触组分(A)的集电器。
12.根据前述权利要求中任一项的锂-硫电化学电池,进一步包含作为组分的(F)接触组分(A)或接触组分(E)的载体基板。
13.根据权利要求10的锂-硫电化学电池,其中所述载体基板选自聚合物薄膜、金属化聚合物薄膜、陶瓷薄膜和金属薄膜。
14.一种包括至少一个根据前述权利要求中任一项的锂-硫电化学电池的电池组。
15.如权利要求1-8中任一项所定义的玻璃陶瓷膜在(i)锂-硫电化学电池或(ii)包括至少一个锂-硫电化学电池作为隔片的用途。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15168691 | 2015-05-21 | ||
EP15168691.2 | 2015-05-21 | ||
PCT/EP2016/060561 WO2016184750A1 (en) | 2015-05-21 | 2016-05-11 | Glass-ceramic electrolytes for lithium-sulfur batteries |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107820642A true CN107820642A (zh) | 2018-03-20 |
CN107820642B CN107820642B (zh) | 2021-01-08 |
Family
ID=53191518
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201680028992.6A Active CN107820642B (zh) | 2015-05-21 | 2016-05-11 | 锂-硫电池组用玻璃-陶瓷电解质 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10847833B2 (zh) |
EP (1) | EP3298643B1 (zh) |
JP (1) | JP6932083B2 (zh) |
KR (1) | KR102602322B1 (zh) |
CN (1) | CN107820642B (zh) |
WO (1) | WO2016184750A1 (zh) |
Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7061065B2 (ja) | 2015-11-13 | 2022-04-27 | シオン・パワー・コーポレーション | 電気化学電池用の添加剤 |
EP3472173B1 (en) | 2016-06-21 | 2021-10-27 | Sion Power Corporation | Coatings for components of electrochemical cells |
US11183690B2 (en) | 2016-12-23 | 2021-11-23 | Sion Power Corporation | Protective layers comprising metals for electrochemical cells |
US11024923B2 (en) | 2017-03-09 | 2021-06-01 | Sion Power Corporation | Electrochemical cells comprising short-circuit resistant electronically insulating regions |
WO2018170413A1 (en) | 2017-03-17 | 2018-09-20 | Sion Power Corporation | Electrode edge protection in electrochemical cells |
US10868306B2 (en) | 2017-05-19 | 2020-12-15 | Sion Power Corporation | Passivating agents for electrochemical cells |
WO2018213661A2 (en) | 2017-05-19 | 2018-11-22 | Sion Power Corporation | Passivating agents for electrochemical cells |
US10608278B2 (en) | 2017-06-09 | 2020-03-31 | Sion Power Corporation | In situ current collector |
DE102018102387B3 (de) * | 2018-02-02 | 2019-06-27 | Schott Ag | Glaskeramik mit ionenleitender Restglasphase und Verfahren zu ihrer Herstellung |
JP2021533714A (ja) | 2018-07-31 | 2021-12-02 | シオン・パワー・コーポレーション | 多重化された充電放電バッテリ管理システム |
KR102101271B1 (ko) * | 2018-08-16 | 2020-04-16 | 아주대학교산학협력단 | 이온 전도성 고체 전해질 화합물, 이의 제조방법 및 이를 포함하는 전기화학 장치 |
US11637353B2 (en) | 2018-12-27 | 2023-04-25 | Sion Power Corporation | Electrodes, heaters, sensors, and associated articles and methods |
US11322804B2 (en) | 2018-12-27 | 2022-05-03 | Sion Power Corporation | Isolatable electrodes and associated articles and methods |
WO2020136960A1 (ja) * | 2018-12-28 | 2020-07-02 | パナソニックIpマネジメント株式会社 | レドックスフロー電池 |
US11710828B2 (en) | 2019-05-22 | 2023-07-25 | Sion Power Corporation | Electrochemical devices including porous layers |
WO2020237015A1 (en) | 2019-05-22 | 2020-11-26 | Sion Power Corporation | Electrically coupled electrodes, and associated articles and methods |
US11056728B2 (en) | 2019-10-31 | 2021-07-06 | Sion Power Corporation | System and method for operating a rechargeable electrochemical cell or battery |
US11424492B2 (en) | 2019-10-31 | 2022-08-23 | Sion Power Corporation | System and method for operating a rechargeable electrochemical cell or battery |
US11791511B2 (en) | 2019-11-19 | 2023-10-17 | Sion Power Corporation | Thermally insulating compressible components for battery packs |
US11984575B2 (en) | 2019-11-19 | 2024-05-14 | Sion Power Corporation | Battery alignment, and associated systems and methods |
US11978917B2 (en) | 2019-11-19 | 2024-05-07 | Sion Power Corporation | Batteries with components including carbon fiber, and associated systems and methods |
CN114667638A (zh) | 2019-11-19 | 2022-06-24 | 赛昂能源有限公司 | 电池组以及相关联的系统和方法 |
US12068461B2 (en) | 2019-12-20 | 2024-08-20 | Sion Power Corporation | Systems and methods for providing, assembling, and managing integrated power bus for rechargeable electrochemical cell or battery |
WO2021183858A1 (en) | 2020-03-13 | 2021-09-16 | Sion Power Corporation | Application of pressure to electrochemical devices including deformable solids, and related systems |
JP2023538829A (ja) | 2020-08-03 | 2023-09-12 | シオン・パワー・コーポレーション | 電気化学セルクランプおよび関連方法 |
US11826861B1 (en) | 2020-08-12 | 2023-11-28 | Sion Power Corporation | Joining systems, clamping fixtures, and related systems and methods |
KR20230058692A (ko) * | 2020-09-01 | 2023-05-03 | 시온 파워 코퍼레이션 | 다중화된 배터리 관리 시스템 |
US11705554B2 (en) | 2020-10-09 | 2023-07-18 | Sion Power Corporation | Electrochemical cells and/or components thereof comprising nitrogen-containing species, and methods of forming them |
CN113871799B (zh) * | 2021-10-27 | 2024-01-30 | 中南大学 | 一种功能隔膜及其制备和在锂硫电池中的应用 |
DE102021128377A1 (de) | 2021-10-29 | 2023-05-04 | Schott Ag | Lithiumionenleitendes Material mit verbesserter Dendritenstabilität |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1894821A (zh) * | 2003-10-14 | 2007-01-10 | 波利普拉斯电池有限公司 | 活性金属/含水电化学电池和系统 |
WO2010149265A1 (de) * | 2009-06-25 | 2010-12-29 | Schott Ag | Batterieseparator |
CN102010183A (zh) * | 2009-09-03 | 2011-04-13 | 日本碍子株式会社 | 陶瓷材料及其制造方法 |
CN103153891A (zh) * | 2010-10-07 | 2013-06-12 | 肖特公开股份有限公司 | 电化学能蓄电池和玻璃基材料用于生产所述蓄电池用隔膜的用途 |
CN103402939A (zh) * | 2011-03-04 | 2013-11-20 | 肖特公开股份有限公司 | 传导锂离子的玻璃陶瓷以及所述玻璃陶瓷的用途 |
CN103490027A (zh) * | 2013-08-12 | 2014-01-01 | 中国科学院化学研究所 | 锂-硫电池用隔膜及其制备方法 |
US20140045032A1 (en) * | 2012-08-09 | 2014-02-13 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery |
US20140162138A1 (en) * | 2012-12-06 | 2014-06-12 | Samsung Electronics Co., Ltd. | Solid-state battery |
US20140186678A1 (en) * | 2012-12-27 | 2014-07-03 | Hyundai Motor Company | Lithium secondary battery cell structure |
US20150024248A1 (en) * | 2013-07-22 | 2015-01-22 | Hui He | Non-flammable quasi-solid electrolyte-separator layer product for lithium battery applications |
CN104638215A (zh) * | 2013-08-21 | 2015-05-20 | 通用汽车环球科技运作有限责任公司 | 锂基电池的柔性膜和涂覆电极 |
Family Cites Families (82)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5648187A (en) | 1994-02-16 | 1997-07-15 | Moltech Corporation | Stabilized anode for lithium-polymer batteries |
US5961672A (en) | 1994-02-16 | 1999-10-05 | Moltech Corporation | Stabilized anode for lithium-polymer batteries |
US5919587A (en) | 1996-05-22 | 1999-07-06 | Moltech Corporation | Composite cathodes, electrochemical cells comprising novel composite cathodes, and processes for fabricating same |
SE512906C2 (sv) * | 1998-10-02 | 2000-06-05 | Ericsson Telefon Ab L M | Förfarande vid lödning av ett halvledarchip samt RF-power transistor för genomförande därav |
US6225002B1 (en) * | 1999-02-05 | 2001-05-01 | Polyplus Battery Company, Inc. | Dioxolane as a proctector for lithium electrodes |
US6797428B1 (en) | 1999-11-23 | 2004-09-28 | Moltech Corporation | Lithium anodes for electrochemical cells |
US6733924B1 (en) | 1999-11-23 | 2004-05-11 | Moltech Corporation | Lithium anodes for electrochemical cells |
US20070221265A1 (en) | 2006-03-22 | 2007-09-27 | Sion Power Corporation | Rechargeable lithium/water, lithium/air batteries |
US20110165471A9 (en) | 1999-11-23 | 2011-07-07 | Sion Power Corporation | Protection of anodes for electrochemical cells |
US7247408B2 (en) | 1999-11-23 | 2007-07-24 | Sion Power Corporation | Lithium anodes for electrochemical cells |
JP4201459B2 (ja) * | 2000-03-31 | 2008-12-24 | 三洋電機株式会社 | 非水電解質二次電池及びその製造方法 |
KR20050070053A (ko) * | 2002-10-15 | 2005-07-05 | 폴리플러스 배터리 컴퍼니 | 활성 금속 애노드를 보호하기 위한 이온 전도성 합성물 |
US7390591B2 (en) | 2002-10-15 | 2008-06-24 | Polyplus Battery Company | Ionically conductive membranes for protection of active metal anodes and battery cells |
US10629947B2 (en) | 2008-08-05 | 2020-04-21 | Sion Power Corporation | Electrochemical cell |
US7688075B2 (en) | 2005-04-20 | 2010-03-30 | Sion Power Corporation | Lithium sulfur rechargeable battery fuel gauge systems and methods |
US8617748B2 (en) | 2006-12-04 | 2013-12-31 | Sion Power Corporation | Separation of electrolytes |
US8084102B2 (en) | 2007-02-06 | 2011-12-27 | Sion Power Corporation | Methods for co-flash evaporation of polymerizable monomers and non-polymerizable carrier solvent/salt mixtures/solutions |
US20080318128A1 (en) | 2007-06-22 | 2008-12-25 | Sion Power Corporation | Lithium alloy/sulfur batteries |
US20090035646A1 (en) | 2007-07-31 | 2009-02-05 | Sion Power Corporation | Swelling inhibition in batteries |
US20120070746A1 (en) | 2007-09-21 | 2012-03-22 | Sion Power Corporation | Low electrolyte electrochemical cells |
US20110006738A1 (en) | 2007-09-21 | 2011-01-13 | Sion Power Corporation | Electrolyte additives for lithium batteries and related methods |
WO2009054987A1 (en) | 2007-10-26 | 2009-04-30 | Sion Power Corporation | Primer for battery electrode |
CN101939862B (zh) | 2008-01-08 | 2014-03-12 | 赛昂能源有限公司 | 多孔电极以及相关联的方法 |
US8264205B2 (en) | 2008-02-08 | 2012-09-11 | Sion Power Corporation | Circuit for charge and/or discharge protection in an energy-storage device |
JP5536996B2 (ja) * | 2008-07-29 | 2014-07-02 | 株式会社オハラ | リチウムイオン伝導性ガラスセラミックスの製造方法 |
EP2365566B1 (en) | 2008-08-05 | 2020-10-14 | Sion Power Corporation | Application of force in electrochemical cells |
US20130244085A1 (en) | 2009-03-16 | 2013-09-19 | Ceramatec, Inc | Battery with non-porous alkali metal ion conductive honeycomb structure separator |
WO2010107499A2 (en) | 2009-03-19 | 2010-09-23 | Sion Power Corporation | Cathode for lithium battery |
JP2010232085A (ja) * | 2009-03-27 | 2010-10-14 | Daihatsu Motor Co Ltd | 電極活物質、二次電池および電極活物質の製造方法 |
US8087309B2 (en) | 2009-05-22 | 2012-01-03 | Sion Power Corporation | Hermetic sample holder and method for performing microanalysis under controlled atmosphere environment |
CN105206793B (zh) | 2009-08-24 | 2017-12-22 | 赛昂能源有限公司 | 用于电化学电池的剥离系统 |
US20110070491A1 (en) | 2009-08-28 | 2011-03-24 | Sion Power Corporation | Electrochemical cells comprising porous structures comprising sulfur |
US20110206992A1 (en) | 2009-08-28 | 2011-08-25 | Sion Power Corporation | Porous structures for energy storage devices |
WO2011147924A1 (en) | 2010-05-28 | 2011-12-01 | Basf Se | Use of expanded graphite in lithium/sulphur batteries |
CN103283064B (zh) | 2010-08-24 | 2017-07-11 | 锡安能量公司 | 用于在电化学电池中使用的电解质材料 |
CN103069609A (zh) | 2010-08-24 | 2013-04-24 | 赛昂能源有限公司 | 用于电化学电池的非导电材料 |
JP5349427B2 (ja) * | 2010-08-26 | 2013-11-20 | トヨタ自動車株式会社 | 硫化物固体電解質材料、正極体およびリチウム固体電池 |
KR20140000235A (ko) | 2010-09-30 | 2014-01-02 | 바스프 에스이 | 이온성 액체 중합체 젤을 갖는 리튬계 애노드 |
WO2012042005A1 (en) | 2010-09-30 | 2012-04-05 | Basf Se | Additive for electrolytes |
EP2647066A1 (en) * | 2010-12-05 | 2013-10-09 | Ramot at Tel Aviv University, Ltd. | Electrophoretic deposition of thin film batteries |
KR101807911B1 (ko) | 2011-06-17 | 2017-12-11 | 시온 파워 코퍼레이션 | 전극 도금 기술 |
JP2013051127A (ja) * | 2011-08-31 | 2013-03-14 | Aisin Seiki Co Ltd | リチウムイオン伝導性複合膜、複合負極および電池 |
WO2013055573A1 (en) | 2011-10-13 | 2013-04-18 | Sion Power Corporation | Electrode structure and method for making the same |
KR20130053817A (ko) * | 2011-11-16 | 2013-05-24 | 현대자동차주식회사 | 리튬황 배터리 |
WO2013123131A1 (en) | 2012-02-14 | 2013-08-22 | Sion Power Corporation | Electrode structure for electrochemical cell |
JP5970060B2 (ja) * | 2012-03-02 | 2016-08-17 | 日本碍子株式会社 | 固体電解質セラミックス材料及びその製造方法 |
WO2013134655A1 (en) | 2012-03-09 | 2013-09-12 | Sion Power Corporation | Porous support structures, electrodes containing same, and associated methods |
WO2013152030A1 (en) | 2012-04-02 | 2013-10-10 | Ceramatec, Inc. | Battery with non-porous alkali metal ion conductive honeycomb structure separator |
DE102012205934A1 (de) * | 2012-04-12 | 2013-10-17 | Robert Bosch Gmbh | Lithium-Schwefel-Zelle |
KR20150043407A (ko) * | 2012-08-14 | 2015-04-22 | 바스프 에스이 | 리튬-황 배터리용 복합 물질 |
WO2014071160A1 (en) | 2012-11-02 | 2014-05-08 | Sion Power Corporation | Electrode active surface pretreatment |
KR102008554B1 (ko) | 2012-11-02 | 2019-08-07 | 바스프 에스이 | 전기화학 전지의 보호층 및 다른 구성요소로 사용하기 위한 중합체 |
US9577289B2 (en) | 2012-12-17 | 2017-02-21 | Sion Power Corporation | Lithium-ion electrochemical cell, components thereof, and methods of making and using same |
CN105190966B (zh) | 2012-12-19 | 2018-06-12 | 锡安能量公司 | 电极结构及其制造方法 |
WO2014110136A1 (en) | 2013-01-08 | 2014-07-17 | Sion Power Corporation | Passivation of electrodes in electrochemical cells |
US9559348B2 (en) | 2013-01-08 | 2017-01-31 | Sion Power Corporation | Conductivity control in electrochemical cells |
WO2014138242A1 (en) | 2013-03-05 | 2014-09-12 | Sion Power Corporation | Electrochemical cells comprising fibril materials, such as fibril cellulose materials |
WO2014151385A1 (en) | 2013-03-15 | 2014-09-25 | Sion Power Corporation | Protected electrode structures and methods |
KR20150132427A (ko) | 2013-03-15 | 2015-11-25 | 바스프 에스이 | 보호된 전극 구조물 |
US20140272594A1 (en) | 2013-03-15 | 2014-09-18 | Sion Power Corporation | Protective structures for electrodes |
US20140272595A1 (en) | 2013-03-15 | 2014-09-18 | Basf Se | Compositions for use as protective layers and other components in electrochemical cells |
JP2014183021A (ja) * | 2013-03-21 | 2014-09-29 | Imura Zairyo Kaihatsu Kenkyusho:Kk | 金属―空気電池 |
JP6003831B2 (ja) | 2013-06-28 | 2016-10-05 | トヨタ自動車株式会社 | 硫化物固体電解質材料、硫化物ガラス、リチウム固体電池、および、硫化物固体電解質材料の製造方法 |
KR101736013B1 (ko) | 2013-07-03 | 2017-05-24 | 시온 파워 코퍼레이션 | 재충전형 리튬 배터리를 비롯한 전기화학 전지에서의 전극 보호를 위한 세라믹/중합체 매트릭스 |
WO2015021373A1 (en) | 2013-08-08 | 2015-02-12 | Sion Power Corporation | Self-healing electrode protection in electrochemical cells |
WO2015082670A1 (en) | 2013-12-05 | 2015-06-11 | Basf Se | Separator, method for its fabrication and lithium sulfur battery comprising it |
US10020512B2 (en) | 2013-12-19 | 2018-07-10 | Sion Power Corporation | Polymer for use as protective layers and other components in electrochemical cells |
DE102014100684B4 (de) | 2014-01-22 | 2017-05-11 | Schott Ag | lonenleitende Glaskeramik mit granatartiger Kristallstruktur, Verfahren zur Herstellung und Verwendung einer solchen Glaskeramik |
US10490796B2 (en) | 2014-02-19 | 2019-11-26 | Sion Power Corporation | Electrode protection using electrolyte-inhibiting ion conductor |
US9653750B2 (en) | 2014-02-19 | 2017-05-16 | Sion Power Corporation | Electrode protection using a composite comprising an electrolyte-inhibiting ion conductor |
US9755268B2 (en) | 2014-03-27 | 2017-09-05 | Sion Power Corporation | Gel electrolytes and electrodes |
CN106256034B (zh) | 2014-05-01 | 2019-04-23 | 锡安能量公司 | 电极制造方法及相关制品 |
US9735411B2 (en) | 2014-05-30 | 2017-08-15 | Sion Power Corporation | Polymer for use as protective layers and other components in electrochemical cells |
CN107078277B (zh) | 2014-09-09 | 2022-07-22 | 赛昂能源有限公司 | 锂离子电化学电池中的保护层及相关电极和方法 |
JP6800844B2 (ja) | 2014-10-23 | 2020-12-16 | シオン・パワー・コーポレーション | 電気化学セル用イオン伝導性複合物 |
US20160118638A1 (en) | 2014-10-24 | 2016-04-28 | Sion Power Corporation | Compositions for use as protective layers and other components in electrochemical cells |
US10164289B2 (en) * | 2014-12-02 | 2018-12-25 | Polyplus Battery Company | Vitreous solid electrolyte sheets of Li ion conducting sulfur-based glass and associated structures, cells and methods |
CN107848247B (zh) | 2015-05-20 | 2021-06-01 | 锡安能量公司 | 电极的保护层 |
US20170141385A1 (en) | 2015-11-04 | 2017-05-18 | Sion Power Corporation | Layer composite and electrode having a smooth surface, and associated methods |
JP7061065B2 (ja) | 2015-11-13 | 2022-04-27 | シオン・パワー・コーポレーション | 電気化学電池用の添加剤 |
KR20180077287A (ko) | 2015-11-24 | 2018-07-06 | 시온 파워 코퍼레이션 | 이온 전도성 화합물 및 관련 용도 |
JP7049269B2 (ja) | 2016-05-20 | 2022-04-06 | シオン・パワー・コーポレーション | 電極用保護層および電気化学電池 |
-
2016
- 2016-05-11 CN CN201680028992.6A patent/CN107820642B/zh active Active
- 2016-05-11 KR KR1020177036696A patent/KR102602322B1/ko active IP Right Grant
- 2016-05-11 JP JP2017560673A patent/JP6932083B2/ja active Active
- 2016-05-11 EP EP16721445.1A patent/EP3298643B1/en active Active
- 2016-05-11 US US15/567,534 patent/US10847833B2/en active Active
- 2016-05-11 WO PCT/EP2016/060561 patent/WO2016184750A1/en active Application Filing
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1894821A (zh) * | 2003-10-14 | 2007-01-10 | 波利普拉斯电池有限公司 | 活性金属/含水电化学电池和系统 |
WO2010149265A1 (de) * | 2009-06-25 | 2010-12-29 | Schott Ag | Batterieseparator |
CN102010183A (zh) * | 2009-09-03 | 2011-04-13 | 日本碍子株式会社 | 陶瓷材料及其制造方法 |
CN103153891A (zh) * | 2010-10-07 | 2013-06-12 | 肖特公开股份有限公司 | 电化学能蓄电池和玻璃基材料用于生产所述蓄电池用隔膜的用途 |
CN103402939A (zh) * | 2011-03-04 | 2013-11-20 | 肖特公开股份有限公司 | 传导锂离子的玻璃陶瓷以及所述玻璃陶瓷的用途 |
US20140045032A1 (en) * | 2012-08-09 | 2014-02-13 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery |
US20140162138A1 (en) * | 2012-12-06 | 2014-06-12 | Samsung Electronics Co., Ltd. | Solid-state battery |
US20140186678A1 (en) * | 2012-12-27 | 2014-07-03 | Hyundai Motor Company | Lithium secondary battery cell structure |
US20150024248A1 (en) * | 2013-07-22 | 2015-01-22 | Hui He | Non-flammable quasi-solid electrolyte-separator layer product for lithium battery applications |
CN103490027A (zh) * | 2013-08-12 | 2014-01-01 | 中国科学院化学研究所 | 锂-硫电池用隔膜及其制备方法 |
CN104638215A (zh) * | 2013-08-21 | 2015-05-20 | 通用汽车环球科技运作有限责任公司 | 锂基电池的柔性膜和涂覆电极 |
Non-Patent Citations (1)
Title |
---|
谢凯等编著: "《新一代锂二次电池技术》", 31 August 2013, 北京:国防工业出版社 * |
Also Published As
Publication number | Publication date |
---|---|
CN107820642B (zh) | 2021-01-08 |
KR102602322B1 (ko) | 2023-11-17 |
EP3298643A1 (en) | 2018-03-28 |
KR20180011196A (ko) | 2018-01-31 |
JP2018518805A (ja) | 2018-07-12 |
JP6932083B2 (ja) | 2021-09-08 |
US20180138542A1 (en) | 2018-05-17 |
EP3298643B1 (en) | 2019-06-12 |
WO2016184750A1 (en) | 2016-11-24 |
US10847833B2 (en) | 2020-11-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107820642A (zh) | 锂‑硫电池组用玻璃‑陶瓷电解质 | |
Jeong et al. | Revisiting polymeric single lithium-ion conductors as an organic route for all-solid-state lithium ion and metal batteries | |
US12074289B2 (en) | Additives for electrochemical cells | |
US10461337B2 (en) | Oxide all-solid-state battery | |
CN106169630B (zh) | 锂空气电池和制造其的方法 | |
CN106935907B (zh) | 锂金属电池 | |
Grünebaum et al. | Synthesis and electrochemistry of polymer based electrolytes for lithium batteries | |
KR102592147B1 (ko) | 복합분리막, 그 제조방법 및 이를 포함하는 리튬이차전지 | |
CN107546412B (zh) | 聚合物电解质、制备所述聚合物电解质的方法和包括其的锂金属电池 | |
KR101446812B1 (ko) | 낮은 용해율을 가지는 코팅된 금속 산화물 입자, 이의 제조방법 및 전기 화학 시스템에서의 이의 용도 | |
Li et al. | Developments of electrolyte systems for lithium–sulfur batteries: A review | |
EP3200260B1 (en) | Polymer electrolyte for lithium secondary battery and lithium secondary battery comprising the same | |
KR102255538B1 (ko) | 이차전지용 폴리머 전해질 및 이를 포함하는 이차전지 | |
KR20180077287A (ko) | 이온 전도성 화합물 및 관련 용도 | |
JP2016219411A (ja) | リチウム金属電池 | |
KR20060020625A (ko) | 폴리이미드 기반 전해질 및 그것으로부터 제조된 개선된전지 | |
CN104798244A (zh) | 锂二次电池 | |
US10014555B2 (en) | Lithium secondary battery and production method therefor | |
Abraham et al. | Room temperature polymer electrolytes and batteries based on them | |
JP2759479B2 (ja) | 全固態リチウム二次電池 | |
CN113924676B (zh) | 用于锂离子电池和其它用途的电极 | |
CN112514108B (zh) | 制造用于锂二次电池的负极的方法和使用该方法制造的用于锂二次电池的负极 | |
Iojoiu et al. | Solid-State Batteries with Polymer Electrolytes | |
CN113906585A (zh) | 包含含有钾和金属的层状氧化物的电极材料、包含该材料的电极及其在电化学中的用途 | |
EP4432414A1 (en) | Solid polymer electrolyte and method for producing same |
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 | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20231123 Address after: Germany Mainz Patentee after: SCHOTT AG Address before: Ludwigshafen, Germany Patentee before: BASF SE Patentee before: SION POWER Corp. Patentee before: SCHOTT AG |