EP3903370A1 - Composite structure and method for producing the composite structure - Google Patents
Composite structure and method for producing the composite structureInfo
- Publication number
- EP3903370A1 EP3903370A1 EP19827758.4A EP19827758A EP3903370A1 EP 3903370 A1 EP3903370 A1 EP 3903370A1 EP 19827758 A EP19827758 A EP 19827758A EP 3903370 A1 EP3903370 A1 EP 3903370A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- sulfur
- carbon
- shell
- core
- 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.)
- Withdrawn
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 104
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 267
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 190
- 239000011593 sulfur Substances 0.000 claims abstract description 190
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 153
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 132
- 239000011258 core-shell material Substances 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 50
- 239000011148 porous material Substances 0.000 claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims description 127
- 229910052751 metal Inorganic materials 0.000 claims description 101
- 239000002184 metal Substances 0.000 claims description 101
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 62
- 229910021389 graphene Inorganic materials 0.000 claims description 58
- 239000002041 carbon nanotube Substances 0.000 claims description 52
- 125000000524 functional group Chemical group 0.000 claims description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 239000005077 polysulfide Substances 0.000 claims description 47
- 229920001021 polysulfide Polymers 0.000 claims description 47
- 150000008117 polysulfides Polymers 0.000 claims description 47
- 229910044991 metal oxide Inorganic materials 0.000 claims description 39
- 150000004706 metal oxides Chemical class 0.000 claims description 39
- -1 polyoxyethylene Polymers 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 31
- 229910052744 lithium Inorganic materials 0.000 claims description 29
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 26
- 150000004692 metal hydroxides Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 19
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052796 boron Inorganic materials 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 239000002134 carbon nanofiber Substances 0.000 claims description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 15
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 230000002776 aggregation Effects 0.000 claims description 12
- 238000004220 aggregation Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 10
- 239000000084 colloidal system Substances 0.000 claims description 9
- 150000001247 metal acetylides Chemical class 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 229920001940 conductive polymer Polymers 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 150000002826 nitrites Chemical class 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- 238000007385 chemical modification Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims 4
- 229910003472 fullerene Inorganic materials 0.000 description 92
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 90
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 32
- 239000002245 particle Substances 0.000 description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 27
- 239000002082 metal nanoparticle Substances 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 239000000126 substance Substances 0.000 description 19
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 17
- 238000009792 diffusion process Methods 0.000 description 17
- 238000005530 etching Methods 0.000 description 17
- 229910052742 iron Inorganic materials 0.000 description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 16
- 230000007547 defect Effects 0.000 description 16
- 229910052725 zinc Inorganic materials 0.000 description 15
- 239000011701 zinc Substances 0.000 description 15
- 229910052804 chromium Inorganic materials 0.000 description 14
- 239000011651 chromium Substances 0.000 description 14
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 13
- 229910052697 platinum Inorganic materials 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 12
- 229910052793 cadmium Inorganic materials 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 229910052750 molybdenum Inorganic materials 0.000 description 11
- 229910052758 niobium Inorganic materials 0.000 description 11
- 239000010955 niobium Substances 0.000 description 11
- 229910052763 palladium Inorganic materials 0.000 description 11
- 229910052703 rhodium Inorganic materials 0.000 description 11
- 239000010948 rhodium Substances 0.000 description 11
- 229910052707 ruthenium Inorganic materials 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 229910052713 technetium Inorganic materials 0.000 description 11
- 229910052718 tin Inorganic materials 0.000 description 11
- 239000011135 tin Substances 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 229910052721 tungsten Inorganic materials 0.000 description 11
- 229910052720 vanadium Inorganic materials 0.000 description 11
- 229910052726 zirconium Inorganic materials 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
- 239000006260 foam Substances 0.000 description 10
- 229910052737 gold Inorganic materials 0.000 description 10
- 239000010931 gold Substances 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 241000234282 Allium Species 0.000 description 9
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 229910052735 hafnium Inorganic materials 0.000 description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 9
- 229910052746 lanthanum Inorganic materials 0.000 description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 9
- 239000011133 lead Substances 0.000 description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 9
- 150000004767 nitrides Chemical class 0.000 description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 150000004763 sulfides Chemical class 0.000 description 9
- 229910052715 tantalum Inorganic materials 0.000 description 9
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 9
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 9
- 229910052714 tellurium Inorganic materials 0.000 description 9
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 9
- 239000010937 tungsten Substances 0.000 description 9
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 9
- 229910052727 yttrium Inorganic materials 0.000 description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 238000007669 thermal treatment Methods 0.000 description 8
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- 229910052693 Europium Inorganic materials 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
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- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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Classifications
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Definitions
- the invention relates to a composite structure and a method for producing the composite structure.
- Metal-sulfur batteries comprise lithium-sulfur (Li-S) batteries, sodium-sulfur (Na-S) batteries, magnesium-sulfur (Mg-S) batteries, aluminum-sulfur (Al-S) batteries, potassium-sulfur (K-S) batteries, calcium-sulfur (Ca-S) batteries, zinc-sulfur (Zn-S) batteries, iron-sulfur (Fe-S) batteries, Barium-sulfur (Ba-S) batteries, Chromium-sulfur (Cr-S) batteries, and so forth.
- the metal-based electrodes work as the anodes (negative electrodes) and sulfur-based electrodes serve as cathodes (positive electrodes).
- Metal-sulfur batteries own high gravimetric and volumetric energy densities and low cost, which are promising in future electrochemical energy storages.
- lithium-sulfur batteries exhibit a specific energy density as high as 2600 Wh/kg, which are ⁇ 6-8 folds of the conventional Li-ion batteries.
- the volumetric energy density is around 2800 Wh/L, which is 2-3 times of the conventional Li-ion batteries.
- metal-sulfur batteries such as Na-S batteries, Mg-S batteries, Al-S batteries, K-S batteries, Ca-S batteries suffer from similar problems due to the electrically and ionically insulating nature of sulfur, diffusion and migration of polysulfides and slow kinetics of electrochemical reactions.
- Encapsulation of sulfur and polysulfides by host materials is a common strategy to overcome these issues.
- the utilization and specific capacity of sulfur, energy densities, power densities, and discharge-charge cyclic performances are still need to be improved due to the relatively large size of sulfur and host materials, serious aggregation of host materials encapsulating sulfur and the abovementioned intrinsic properties of sulfur and polysulfides.
- the invention provides a composite structure, which can be suitable for an electrode, the structure comprising: an electrically conductive supporting material, a plurality of core-shell structures, said core-shell structures comprising, a shell comprising carbon, a cavity enclosed by the shell, a core in the cavity, said core comprising sulfur.
- the shell comprises a layered structure, said the layered structure comprises at least one of graphene, graphene-like carbon and graphitic carbon nitride.
- the shell comprises pores connecting the cavity and outside of the shell, said pores have an average size ranging from 0.2 nm to 5 nm, preferably from 0.4 nm to 2 nm, more preferably from 0.4 nm to 1 nm.
- the plurality of core-shell structures are dispersed in the composite structure by the electrically conductive supporting material between the plurality of core-shell structures to prevent the aggregation of the plurality of core-shell structures.
- the carbon weight percentage in the shell can be in the range of 30 - 100%, preferably in the range of 39 - 100%, more preferably in the range of 80 - 100%.
- the shell can be pure carbon.
- the shell comprises a layered structure that may be graphene-like carbon or graphitic carbon nitride.
- the layer-structured shell contains pores, said pores can be induced by the structural defects in the layers of graphene-like carbon or graphite-like carbon nitride, and said pores can be also the intrinsic in-plane holes of carbon-nitrogen rings in the graphite-like carbon nitride layer.
- the structural defects can be at least one of the following types of defects: vacancy defects caused by missing at least one or more carbon atoms in a carbon hexagon ring of graphene or one or more carbon and nitrogen atoms in the triazine or tri-s-triazine/heptazine rings of graphitic carbon nitride, Stone-Wales defects that are the adjacent pairs of pentagonal and heptagonal rings of graphene caused by the rotation of a single pair of carbon atoms, line defects caused by the grain boundaries between different crystallographic orientations of graphene during the randomness of growth, doped graphene and graphitic carbon nitride crystals with foreign adatoms including at least one of nitrogen, oxygen, sulfur, phosphorus, boron, hydrogen, fluorine, selenium, selenium, silicon, nickel, iron, copper, zinc, titanium, vanadium, chromium, manganese, cobalt, aluminium, germanium, zirconium,
- the sulfur weight percentage in the core can be in the range of 70 - 100%, preferably in the range of 90 - 100%.
- the composite structure of the plurality of core-shell structures are dispersed by the electrically conductive supporting material with an average separation distance between the plurality of core-shell structures ranging from 0.5 nm to 150 nm, preferably from 0.7 to 50 nm, more preferably from 1 nm to 10 nm.
- the composite structure of the plurality of core-shell structures, wherein the electrically conductive supporting material comprises at least one of the following for reducing aggregation of the core-shell structures: carbon nanotubes, graphene, thin graphite, carbon nanofibers, reduced graphene oxides, graphene oxides, activated carbon, porous graphene, porous carbon, porous metals, porous conductive polymers.
- the composite structure of the plurality of core-shell structures wherein the cavity has an average size ranging from 1 nm to 30 nm, preferably from 1 nm to 20 nm, more preferably from 1 nm to 10 nm, wherein the shell has an average wall thickness ranging from 0.4 nm to 10 nm, preferably from 0.4 nm to 3.5 nm, more preferably from 0.4 nm to 2 nm.
- the composite structure of one of the plurality of core shell structures, wherein the cavity enclosed by the shell comprises an average pore volume ranging from 1.0 to 25.0 cm 3 /g, and the composite structure comprises an average specific surface area ranging from 200 to 3500 m 2 /g.
- the composite structure of the plurality of core-shell structures wherein the core-shell structures comprise a sulfur content ranging from 50 to 98 wt.%; wherein the core-shell structures comprise an average area loading of sulfur ranging from 0.5 to 200 mg/cm 2 , preferably from 0.5 to 100 mg/cm 2 .
- the composite structure of the plurality of core-shell structures wherein the shell can be functionalized at an internal surface of the shell with at least one of the following: oxygen contained functional group, nitrogen contained functional group, sulfur contained functional group, boron contained functional group, halogen contained functional group, said functional groups are used for trapping soluble and polar polysulfides and lowering activation barrier energy of oxidation of U2S and other non-lithium metal sulfides.
- the composite structure of the plurality of core-shell structures wherein the shell encloses catalyst nanoparticles, such as metal, metal oxides, metal nitrites, metal sulfides, metal carbides, metal hydroxides, alloys, said catalyst nanoparticles are used for trapping soluble and polar polysulfides and lowering activation barrier energy of oxidation of U2S and other non-lithium metal sulfides.
- catalyst nanoparticles such as metal, metal oxides, metal nitrites, metal sulfides, metal carbides, metal hydroxides, alloys
- an electrode comprising the composite structure of the plurality of core-shell structures.
- a current collector of an electrode for a metal-sulfur battery containing the composite structure of the plurality of core-shell structures.
- a method for producing a composite structure wherein said structure can be suitable for use in an electrode of the metal-sulfur batteries, the method comprising the steps of: dissolving carbon-based organics in a colloid of at least one of metal, metal hydroxides and metal oxide nanoparticles, and adding a conductive supporting material to form a mixed colloid; drying the mixed colloid to obtain a composite of solid-carbon wrapped at least one of metal, metal hydroxides and metal oxide nanoparticles, said composite dispersed by the conductive supporting material; heat-treating the obtained composite at a temperature from 200 °C to 900 °C under inert gas protection to obtain graphene-like carbon coated at least one of metal nanoparticles and metal oxides nanoparticles by catalytic conversion of the solid-carbon to graphene-like carbon or growth of graphitic carbon nitride; removing one of metal and oxide nanoparticles to obtain a plurality of shell structures, said plurality of shell structures are dispersed by the conductive
- the method for producing a composite structure comprising the shell of graphene-like carbon for an electrode, wherein the metal hydroxides and metal oxides nanoparticles may be at least one of transition metal oxides, transition metal hydroxides, magnesium hydroxides, magnesium oxide, aluminium hydroxides, aluminium oxides, calcium hydroxide, calcium oxide, and a combination of two or more from the list, said nanoparticles can be non-porous structure.
- the method for producing a composite structure comprising the shell of graphitic carbon nitride for an electrode, wherein the metal hydroxides and metal oxides nanoparticles may be at least one of transition metal oxides, transition metal hydroxides, magnesium hydroxides, magnesium oxide, aluminium hydroxides, aluminium oxides, calcium hydroxide, calcium oxide, and a combination of two or more from the list, said nanoparticles can be non-porous structure.
- the method for producing a composite structure for an electrode wherein the carbon-based organics or/and the solid carbon comprises at least one of polyvinylpyrrolidone, hydrocarbon, sugar, sucrose, polyvinyl alcohol, polyethylene oxide (PEO), polyoxyethylene, poly(methyl methacrylate), triethylene glycol, lignin, dicyandiamide, melamine, urea, proteins, nylon, rubber.
- the carbon-based organics or/and the solid carbon comprises at least one of polyvinylpyrrolidone, hydrocarbon, sugar, sucrose, polyvinyl alcohol, polyethylene oxide (PEO), polyoxyethylene, poly(methyl methacrylate), triethylene glycol, lignin, dicyandiamide, melamine, urea, proteins, nylon, rubber.
- the method for producing a composite structure for an electrode further comprising synthesizing sulfur in the cavity by placing the plurality of shell structures with the supporting material in liquid sulfur at a temperature ranging from 100 to 600 °C under an atmosphere comprising at least one of Argon and Nitrogen.
- the method for producing a composite structure for an electrode further comprising functionalising by surface chemical modifications such as oxidation, reaction with oxygen/nitrogen/sulfur/boron/halogen contained functional groups at an internal surface of the shell with at least one of the following: oxygen contained functional group, nitrogen contained functional group, sulfur contained functional group, boron contained functional group, halogen contained functional group, for trapping soluble and polar polysulfides and lowering activation barrier energy of U S and other non-lithium metal sulfides.
- surface chemical modifications such as oxidation, reaction with oxygen/nitrogen/sulfur/boron/halogen contained functional groups at an internal surface of the shell with at least one of the following: oxygen contained functional group, nitrogen contained functional group, sulfur contained functional group, boron contained functional group, halogen contained functional group, for trapping soluble and polar polysulfides and lowering activation barrier energy of U S and other non-lithium metal sulfides.
- the method for producing a composite structure for an electrode further comprising enclosing catalyst nanoparticles, such as metal, metal oxides, metal nitrites, metal sulfides, metal carbides, metal hydroxides, alloys, for trapping soluble and polar polysulfides and lowering activation barrier energy of U S and other non-lithium metal sulfides.
- catalyst nanoparticles such as metal, metal oxides, metal nitrites, metal sulfides, metal carbides, metal hydroxides, alloys, for trapping soluble and polar polysulfides and lowering activation barrier energy of U S and other non-lithium metal sulfides.
- Figure 1-3 are schematic, cross-sectional view of examples of a method for making the composite structure disclosed herein;
- Figure 4 shows a schematic illustration of the synthesis of fullerenes or carbon onions-sulfur composites anchored on carbon nanotube (CNT) networks in the assistance of Ni nanoparticles (NPs) and used for lithium-sulfur batteries according to an embodiment of the invention.
- Figure 5a shows an HRTEM image of Ni(OH)2 nanoparticles.
- Figure 5b shows a SEM image of fullerene@Ni NPs.
- Figure 5c shows a TEM image of fullerene@Ni NPs.
- Figure 5d shows an HRTEM image of fullerene@Ni NPs.
- Figure 5e shows a TEM image of fullerene-like carbon.
- Figure 5f shows an HRTEM image of fullerene-like carbon.
- Figure 6a shows an HRTEM image of fullerene@CNT composites.
- Figure 6b shows an HRTEM image of the CNT.
- Figure 6c shows an opening of CNT according to an embodiment of the invention.
- Figure 6d shows an HRTEM image of a monolayer fullerene sphere (marked with white arrow) anchored on CNT.
- Figure 6e shows an HRTEM image of multilayer fullerene spheres (marked with orange arrows) anchored on CNT.
- Figure 7a shows a TEM image of fullerene@S NPs@CNT.
- Figure 7b shows an HRTEM image of fullerene@S NPs@CNT.
- Figure 7c shows an HRTEM image of fullerene@S NPs@CNT
- Figure 7d shows an HRTEM image of sulfur encapsulated in tubular cavities of
- Figure 8a shows the cycling performances of fullerene@S NPs@CNT at 0.2 C (334 mA/g) and a physical mixture of fullerene@S NPs with CNT.
- Figure 8b shows the cycling performances of fullerene@S NPs@CNT at 5 C (8.35 A/g).
- Figure 9 shows a schematic illustration of the charge and discharge processes of fullerene@S NPs@CNT according to an embodiment of the invention.
- Figure 10a and b show the fullerenes or carbon nanoonions embed with CeC>2 nanoparticles.
- Metal-sulfur batteries including Li-S batteries, Na-S batteries, Mg-S batteries, Al-S batteries, K-S batteries, Ca-S batteries, Zn-S batteries, Fe-S batteries, Ba-S batteries, Cr-S batteries have high energy densities and relatively low costs.
- Metal- sulfur batteries are promising in the applications of future electrochemical energy storages for portable electronics such as computers, mobile phones, and also for electrical grids and electrical transportations such as electrical vehicles.
- the metal-based electrodes work as the anodes (negative electrodes), while the sulfur-based electrodes serve as the cathodes (positive electrodes).
- the metal-sulfur batteries suffer from rapid capacity decay and low capacities that hamper their commercialization mainly due to the common issues from sulfur cathodes, polysulfides species and slow kinetics of electrochemical reactions.
- the sulfur cathodes of lithium-sulfur batteries have highly poor electrical and ionic conductivity of both sulfur and lithium sulfide (end product after fully discharge);
- the intermediate polysulfides formed during the discharge have “shuttle phenomenon” that the polysulfides can pass through the separator, deposit onto lithium anodes, corrode lithium and then result in the fast capacity decay.
- Li2S4 ⁇ Li2S2 ⁇ Li2S The phase transformation between long-chain polysulfides and lithium sulfide (Li2S4 ⁇ Li2S2 ⁇ Li2S) is a slow liquid-to-solid reaction in kinetics, which reduces the rate performances of Li-S cells.
- the Al current collectors are heavy and not stable comparing with carbon materials.
- the Al current collectors can reduce the gravimetric/volumetric capacities of sulfur electrodes.
- These technical problems have been partly addressed in various ways in previous studies. For example, various kinds of conductive additives or porous materials were introduced to improve the electric conductivity of sulfur cathodes, for example carbon black, graphite, activated carbon, carbon nanotube, graphene, porous carbon and graphene, metals oxides, metal sulfides, metals, conductive polymers etc. Although the conductivities of sulfur and lithium sulfide are increased, but the contact between sulfur and carbon is still needed to be improved.
- a method for solving the electrically and ionically insulating nature problems of sulfur cathodes and trapping polysulfide ions is by encapsulation of sulfur in a conductive matrix, which comprises metals, carbons, polymers and so forth. Due to the good chemical stability, high electric conductivity and light weight, carbonaceous matrixes are those of the most attractive ones. These carbonaceous matrixes including graphite, carbon black, ketjen black, activated carbon, ordered mesoporous carbon, hollow carbon spheres, carbon nanotubes, carbon nanofibers, graphene, fullerene, their mixtures and the like.
- Normally two types of encapsulation of sulfur in carbon matrix includes (i) filling sulfur in the micropores, mesopores and marcropores of carbon, and (ii) cover sulfur particles with carbon materials such as graphene layers, carbon black particles, carbon nanotube, and polymers.
- carbon materials such as graphene layers, carbon black particles, carbon nanotube, and polymers.
- the pore sizes of carbon matrix have been decreased from macroporous to mesoporous and microporous, meanwhile the sulfur filled in the pores also decreased from tens microns to few nanometers.
- the particle size of sulful-conductive matrix composites can be rather big.
- the particle sizes of S-C composites can be from 50 nm to several or tens microns. The large particle size could increase the electric resistivity of S-C composites and diffusion length for ions, and reduce the diffusivity of lithium/non-lithium metallic cations.
- the electrodes with large particle sizes of S-C composites exhibit much lower specific capacity than the theoretical specific capacity of sulfur (1675 mAh/g) and poor cyclic performances.
- the utilization of sulfur can be dramatically increased.
- the sulfur nanoparticles are exposed to electrolyte and the polysulfides are still dissolved fast. Encapsulation of sulfur nanoparticles with sub-dozens nanometers into individual nanometer-sized cavities enclosed by carbon-based shell can be a rational design to achieve the high specific capacity of sulfur and good cyclic stability.
- Zhou et al. (US 2015/221935 A1) describes a core-shell structure for sulfur cathodes of Li-S batteries in which a sulfur core is enclosed by a porous carbon shell.
- the method for synthesis of porous carbon shell is by using porous templates such as mesoporous silica. Carbon precursors are then deposited on the surface and into the pores of porous templates. In following, the mixture is pyrolyzed below 1000 °C, the porous carbon shell and the hollow core are obtained after removal of the porous templates. After that, an additional polymer coating on the carbon shells is synthesized by polymerization.
- the shell is indeed an amorphous carbon and created by removal of the porous templates.
- the pore size of the shell is 1-20 nm and the hollow core is in sub-micron.
- Sub-micron sulfur particles encapsulated by the porous carbon shell are still too large to be fully utilized for cathode.
- the relative low diffusivity of lithium ions and long diffusion length also limit the rate performances of the batteries. For example, Zhou et al. obtained a much lower specific capacity (the highest initial specific capacity 1141 mAh/g) than the theoretical specific capacity of sulfur (1675 mAh/g). In addition, Zhou et al.
- multi-walled carbon nanotubes as host material for sulfur cathodes of Li-S batteries (Wang et al., Infiltrating sulfur in hierarchical architecture MWCNT@meso C core shell nanocomposites for lithium-sulfur batteries, Phys. Chem. Chem. Phys., 2013, 15, 9051-9057).
- the electrically conductive MWCNT is the core and meso-C coating is the porous shell.
- the architecture has a one dimensional structure. After infiltration with sulfur, sulfur distributed in the meso-C shell. However, the sulfur particles are not encapsulated but exposed directly to the electrolyte of batteries, leading to fast capacity decay and much lower specific capacity than the theoretical specific capacity of sulphur.
- a core-shell structure with a sub-dozens nanometer-sized core and layered shell with sub-nanometer pores are neither disclosed nor suggested in this reference.
- Muldoon et al. (US 2016/0087266 A1) describes a core-shell sub-micron particle, which contains a sub-micron sulfur core enclosed by a first shell of an ionically charged conductive copolymer and a second conductive polymer layer.
- the functionalized carbon black added to improve the conductivity is optionally dispersed inside the sulfur core and on or embedded in an outermost conductive polymer layer.
- the sub-micron sulfur particles are formed by precipitation from solution. In fact, the sub-micron sulfur particles are still too large to achieve a close-to-theoretical specific capacity and good rate performances.
- a core-shell structure with a sub-dozens nanometer core and layered shell with sub-nm pores are neither disclosed nor suggested in this reference.
- the interlayer includes carbon nanotube, Super P carbon black, graphene (oxides), porous graphene, metal oxides, metal organic frameworks, and their mixtures.
- Lithiated Nafion, PEO, Li-PFSD (lithium peril uorinated sulfonyl dicyanomethide), PAH [poly(allylamine hydrochloride)] and PAA [poly(acrylic acid)] etc. modified separators have effective improvements in the performances of lithium-sulfur batteries.
- the use of interlayer cannot fully solve the low utilization of sulfur and dissolution and diffusion of polysulfides. It can also increase the weight of the cells because of the thick interlayers used.
- the present invention provides a novel composite structure of sulfur cathodes for metal-sulfur (Me-S) batteries such as lithium-sulfur (Li-S) batteries.
- the novel composite structure comprises an electrically conductive supporting material and a plurality of core-shell structures.
- the core-shell structures comprise a layered carbon- based shell and a small cavity enclosed by the shell, while a small core comprises small nanoparticles in the cavity.
- the size of the cavity is smaller than 30 nm, preferably from 1 nm to 20 nm, more preferably from 1 nm to 10 nm.
- the shell comprises a layered structure consisted of graphene-like carbon or graphitic carbon nitride.
- the shell has a thickness from 0.34 nm to 5 nm, preferably from 0.68 nm to 2 nm, more preferably from 1 nm to 2 nm.
- the pores on the shell have an average size ranging from 0.2 nm to 5 nm, preferably from 0.4 nm to 2 nm, more preferably from 0.4 nm to 1 nm.
- the core-shell structures are uniformly dispersed in the composite structure by the conductive supporting material between the core-shell structures that reduce the aggregation of core-shell structures.
- the shell of the core-shell structures may contain defects that can be at least one of the following types of defects: vacancy defects caused by missing at least one or more carbon atoms in a carbon hexagon ring of graphene or one or more carbon and nitrogen atoms in the triazine or tri-s-triazine/heptazine rings of graphitic carbon nitride, Stone-Wales defects that are the adjacent pairs of pentagonal and heptagonal rings of graphene caused by the rotation of a single pair of carbon atoms, line defects caused by the grain boundaries between different crystallographic orientations of graphene during the randomness of growth, doped graphene and graphitic carbon nitride crystals by foreign adatoms including at least one of nitrogen, oxygen, sulfur, phosphorus, boron, hydrogen, fluorine, selenium, selenium, silicon, nickel, iron, copper, zinc, titanium, vanadium, chromium, manganese, cobalt, aluminium, germanium, zi
- catalysts nanoparticles for metal-sulfur batteries can be also embedded into the cavities enclosed by the shell.
- the catalysts nanoparticles can further trap polysulfides, promote the conversion between sulfur and metal sulfides, including the conversion between polysulfides, sulfur and metal sulfide.
- These catalysts nanoparticles include at least one of metal, metal oxide, metal nitride, metal carbide, metal sulfide, metal phosphide, metal hydroxide, metal selenide, metal telluride, metal boride and the heterostructures of two or more listed above.
- the metal of the metal nanoparticles and metallic compounds nanoparticles as the catalysts can be lithium, nickel, iron, copper, zinc, titanium, vanadium, chromium, manganese, cobalt, zirconium, niobium, yttrium, molybdenum, lanthanum, tantalum, hafnium, tungsten, platinum, cadmium, palladium, rhodium, ruthenium, technetium, tellurium, lead, tin, silver, gold, magnesium, calcium, sodium, potassium, cerium, europium, beryllium and the combination of two or more of them.
- the catalysts imbedded in the core-shell structure used for the metal-S batteries the cyclic stability, reversible capacities, energy densities and power densities can be improved.
- the internal or external surfaces of the shell can be optionally tuned by surface functionalization with organic/inorganic materials, which could be oxygen contained functional groups such as hydroxyl, carbonyl, aldehyde, haloformyl, carbonate ester, carboxylate, carboxyl, ester, methoxy, or nitrogen contained functional groups such as amide, amines, imine, nitrile, isonitrile, pyridyl, or sulfur contained functional groups such as sulfhydryl, sulfide, sulfinyl, or boron contained functional groups, or halogen contained functional groups.
- oxygen contained functional groups such as hydroxyl, carbonyl, aldehyde, haloformyl, carbonate ester, carboxylate, carboxyl, ester, methoxy, or nitrogen contained functional groups such as amide, amines, imine, nitrile, isonitrile, pyridyl, or sulfur contained functional groups such as sulfhydryl, s
- These functional groups can trap soluble and polar polysulfides and lower the activation barrier energy oxidation of U2S and other non-lithium metal sulfides.
- the cyclic stability, reversible capacities, energy densities and power densities can be improved.
- the metal-sulfur batteries comprising the composite structure are but not limit to lithium-sulfur (Li-S) batteries, sodium-sulfur (Na-S) batteries, magnesium-sulfur (Mg-S) batteries, aluminum-sulfur (Al-S) batteries, potassium-sulfur (K-S) batteries, calcium-sulfur (Ca-S) batteries, zinc-sulfur (Zn-S) batteries, iron-sulfur (Fe-S) batteries, barium-sulfur (Ba-S) batteries, chromium-sulfur (Cr-S) batteries, and so forth.
- Li-S lithium-sulfur
- Na-S sodium-sulfur
- Mg-S magnesium-sulfur
- Al-S aluminum-sulfur
- K-S potassium-sulfur
- Ca-S calcium-sulfur
- Zn-S zinc-sulfur
- Fe-S iron-sulfur
- Ba-S barium-sulfur
- Cr-S chro
- One example of the as-disclosed composite structure is the fullerene-sulfur core-shell particles anchored on carbon nanotubes (CNT) for metal-sulfur (Me-S) batteries such as lithium-sulfur (Li-S) batteries.
- CNT carbon nanotubes
- Me-S metal-sulfur
- Li-S lithium-sulfur
- sulfur nanoparticles are encapsulated in the cavities of fullerenes (also named as carbon nanoonions), which is different from the previously disclosed structures.
- the shell is graphene-like carbon and has layered structure of graphene.
- the size of the cavity is smaller than 30 nm, preferably from 1 nm to 20 nm, more preferably from 1 nm to 10 nm.
- the shell has a thickness from 0.34 nm to 5 nm, preferably from 0.68 nm to 2 nm, more preferably from 1 nm to 2 nm.
- the pores on the shell have an average size ranging from 0.2 nm to 5 nm, preferably from 0.4 nm to 2 nm, more preferably from 0.4 nm to 1 nm.
- the fullerene-sulfur core-shell structures are uniformly dispersed in the composite structure by the CNT between the fullerene-sulfur core-shell structures that reduce the aggregation of fullerene-sulfur core-shell structures.
- the fullerene-sulfur composite as cathodes exhibit very excellent performances, including high specific capacities (both based on sulfur and electrodes), long-term cycling life, good rate performances, etc.
- the initial specific capacity of the composites can reach the theoretical value of sulfur (1675 mAh/g).
- the lithium ions can diffuse and pass through the graphene walls of fullerenes because of the holes on graphene walls induced by the defects.
- the defective graphene walls can prevent the diffusion and shuttling of long-chain polysulfides.
- the diffusion lengths of the lithium ions in a fullerene-sulfur particle are very short during charge and discharge.
- the shell of the core-shell structure of the fullerene-sulfur composite can be doped with foreign adatoms on the external or internal surface of graphene-like carbon shells.
- the foreign adatoms includes at least one of nitrogen, oxygen, sulfur, phosphorus, boron, hydrogen, fluorine, selenium, selenium, silicon, nickel, iron, copper, zinc, titanium, vanadium, chromium, manganese, cobalt, aluminium, germanium, zirconium, niobium, yttrium, molybdenum, lanthanum, tantalum, hafnium, tungsten, platinum, tin, cadmium, palladium, calcium, magnesium, sodium, potassium, rhodium, ruthenium, silver, gold, technetium, tellurium, iodine, arsenic, antimony, lead, cerium, europium, beryllium, bromine.
- catalysts for metal-sulfur batteries can be also embedded into the cavities of the fullerenes.
- the catalysts can further trap polysulfides and promote the conversion between sulfur and lithium sulfides, including the conversion between polysulfides, sulfur and lithium sulfide.
- These catalysts nanoparticles include at least one of metal, metal oxide, metal nitride, metal carbide, metal sulfide, metal phosphide, metal hydroxide, metal selenide, metal telluride, metal boride and the heterostructures of two or more listed above.
- the metal of the catalytic metal nanoparticles and metallic compound nanoparticles can be lithium, nickel, iron, copper, zinc, titanium, vanadium, chromium, manganese, cobalt, zirconium, niobium, yttrium, molybdenum, lanthanum, tantalum, hafnium, tungsten, platinum, cadmium, palladium, rhodium, ruthenium, technetium, tellurium, lead, tin, silver, gold, magnesium, calcium, sodium, potassium, cerium, europium, beryllium and the combination of two or more of them.
- fullerenes can be optionally tuned by surface functionalization with organic/inorganic materials, which could be oxygen contained functional groups such as hydroxyl, carbonyl, aldehyde, haloformyl, carbonate ester, carboxylate, carboxyl, ester, methoxy, or nitrogen contained functional groups such as amide, amines, imine, nitrile, isonitrile, pyridyl, or sulfur contained functional groups such as sulfhydryl, sulfide, sulfinyl, or boron contained functional groups, or halogen contained functional groups.
- oxygen contained functional groups such as hydroxyl, carbonyl, aldehyde, haloformyl, carbonate ester, carboxylate, carboxyl, ester, methoxy, or nitrogen contained functional groups such as amide, amines, imine, nitrile, isonitrile, pyridyl, or sulfur contained functional groups such as sulfhydryl, sulfide
- Another example of the as-disclosed composite structure is the sulfur core shell of graphitic carbon nitride particles anchored on carbon nanotubes (CNT) for metal-sulfur (Me-S) batteries.
- sulfur nanoparticles are encapsulated in the cavities enclosed by the graphitic carbon nitride (g-C3N4) shell that has one or more layers.
- the size of the cavity is smaller than 30 nm, preferably from 1 nm to 20 nm, more preferably from 1 nm to 10 nm.
- the shell has a thickness from 0.32 nm to 5 nm, preferably from 0.6 nm to 3 nm. On the shell there are pores that connect the cavity and outside of the shell.
- the pores on the shell have an average size ranging from 0.4 nm to 5 nm, preferably from 0.4 nm to 2 nm, more preferably from 0.4 nm to 1 nm.
- the S core-g-C3N4 shell structures are uniformly dispersed in the composite structure by the CNT between the core-shell structures that reduce the aggregation.
- catalysts for metal- sulfur batteries can be also embedded into the cavities of the g-C3N4 hollow structure.
- the catalysts can further trap polysulfides and promote the conversion between sulfur and lithium sulfides, including the conversion between polysulfides, sulfur and lithium sulfide.
- These catalysts nanoparticles include at least one of metal, metal oxide, metal nitride, metal carbide, metal sulfide, metal phosphide, metal hydroxide, metal selenide, metal telluride, metal boride and the heterostructures of two or more listed above.
- the metal of the metal nanoparticles and metallic compounds nanoparticles as the catalysts can be lithium, nickel, iron, copper, zinc, titanium, vanadium, chromium, manganese, cobalt, zirconium, niobium, yttrium, molybdenum, lanthanum, tantalum, hafnium, tungsten, platinum, cadmium, palladium, rhodium, ruthenium, technetium, tellurium, lead, tin, silver, gold, magnesium, calcium, sodium, potassium, cerium, europium, beryllium and the combination of two or more of them.
- the internal or external surfaces of the g-CsN4 hollow structure can be optionally tuned by surface functionalization with organic/inorganic materials, which could be oxygen contained functional groups such as hydroxyl, carbonyl, aldehyde, haloformyl, carbonate ester, carboxylate, carboxyl, ester, methoxy, or nitrogen contained functional groups such as amide, amines, imine, nitrile, isonitrile, pyridyl, or sulfur contained functional groups such as sulfhydryl, sulfide, sulfinyl, or boron contained functional groups, or halogen contained functional groups.
- oxygen contained functional groups such as hydroxyl, carbonyl, aldehyde, haloformyl, carbonate ester, carboxylate, carboxyl, ester, methoxy, or nitrogen contained functional groups such as amide, amines, imine, nitrile, isonitrile, pyridyl, or sulfur contained functional groups such as s
- the present invention provides a method for producing the composite structure for an electrode, comprising the steps of:
- said plurality of shell structures are dispersed by the conductive supporting material, said shell structures comprise: a shell comprising carbon;
- the shell comprises pores connecting the cavity and outside of the shell, said shell comprise layered structure of graphene-like carbon or graphitic carbon nitride, said pores have an average size ranging from 0.2 nm to 5nm, preferably from 0.4 nm to 2 nm, more preferably from 0.4 nm to 1 nm;
- the method for synthesis of the composite structure are versatile due to the following features:
- solid carbon used for synthesis of the composite structure can be polymers and other hydrocarbon materials such as sugar, sucrose, or sputtered carbon.
- the solid carbon also can contains other elements such as nitrogen, sulfur, boron, phosphorus and so forth.
- the metal nanoparticles can be prepared before mixing with solid carbon, or can be formed during heating with solid carbon.
- the precursors of metal nanoparticles can be metal oxides, metal hydroxides, metal chlorides, metal complex, metal ion coordination compounds, amorphous metal and so forth.
- the core-shell structures of the composite structure have cavities of 1-30 nm, shells of 0.4-10 nm thickness, tunable graphitization and defects contained.
- the core-shell structure of the composite structure can be doped with foreign adatoms on the external of shells or internal surface of shells by chemical approaches.
- the foreign adatoms are referred to the abovementioned elements.
- the chemical approaches involves at least one of synthesis, selective etching, chemical and electrochemical deposition, oxidation, reduction, thermal treatment, photochemical reaction, decomposition, replacement reaction, solid-state reactions, substitution, addition and elimination, complexation, etc.
- the external or internal surface of the shells of the core-shell structure in the composite structure can be optionally surface functionalized with organic/inorganic materials, which can be oxygen contained functional groups such as hydroxyl, carbonyl, aldehyde, haloformyl, carbonate ester, carboxylate, carboxyl, ester, methoxy, or nitrogen contained functional groups such as amide, amines, imine, nitrile, isonitrile, pyridyl, or sulfur contained functional groups such as sulfhydryl, sulfide, sulfinyl, or boron contained functional groups, or halogen contained functional groups.
- the chemical approaches involve at least one of chemical and electrochemical synthesis, deposition, oxidation, reduction, thermal treatment, photochemical reaction, decomposition, replacement reaction, solid-state reactions, substitution, addition and elimination, complexation, etc.
- the cavities enclosed by the shell of the core-shell structure in the composite structure may be optionally filled with catalyst nanoparticles by chemical approaches.
- catalysts nanoparticles include at least one of metal, metal oxide, metal nitride, metal carbide, metal sulfide, metal phosphide, metal hydroxide, metal selenide, metal telluride, metal boride and the heterostructures of two or more listed above.
- the metal of the metal nanoparticles and metallic compounds nanoparticles as the catalysts can be lithium, nickel, iron, copper, zinc, titanium, vanadium, chromium, manganese, cobalt, zirconium, niobium, yttrium, molybdenum, lanthanum, tantalum, hafnium, tungsten, platinum, cadmium, palladium, rhodium, ruthenium, technetium, tellurium, lead, tin, silver, gold, magnesium, calcium, sodium, potassium, cerium, europium, beryllium and the combination of two or more of them.
- the chemical approaches involves at least one of synthesis, selective etching, chemical and electrochemical deposition, oxidation, reduction, thermal treatment, photochemical reaction, decomposition, replacement reaction, solid-state reactions, substitution, addition and elimination, complexation, carburizing, nitriding, chemical vapor deposition, etc.
- a novel method for synthesis of the sulfur core-fullerene shell composite and a novel design of the sulfur core-fullerene shell composites cathodes has been developed by using fullerenes (carbon nanoonions) for metal-sulfur batteries such as lithium-sulfur batteries.
- the new method and products of fullerene-sulfur composites according the invention have one or more of the following advantages:
- the new fullerene-sulfur composite contains a core-shell structure, of which the sulfur is the core and graphene walls of fullerenes are the shell.
- the fullerenes have cavities of 1-30 nm, shell thickness of 0.4-10 nm.
- the sulfur particles encapsulated inside the cavities of fullerenes are very small (below 30 nm), and have intimate contact with graphene walls, thus the electrically conductivity of the sulfur can be significantly improved.
- the new fullerene-sulfur composites have particle size of 1-30 nm, which are the smallest among the reported carbon-sulfur nanoparticles to the best our knowledge.
- the sulfur nanoparticles can be fully activated, which can increase the capacity of sulfur. Owing to the very small particle size of sulfur-carbon composites, the diffusion lengths of lithium ions in each S-fullerene particle are very short. So the rate performances of batteries can be significantly increased.
- the graphene wall of fullerenes contains holes induced by the defects which can allow the diffusion of sulfur molecular.
- the holes on graphene shells also allow the diffusion of lithium ions but effectively restrict the diffusion of polysulfides formed during discharge. This can significantly prolong the service life of batteries.
- the fullerene shells can effectively reduce the volume expansion of sulfur during discharge and charge.
- the functionalized internal surface of fullerenes with functional groups can chemically interact with polysulfides and trap polysulfides.
- the functionalized internal surface of fullerenes or embedding with catalyst nanoparticles inside of the cavities of fullerenes can significantly accelerate the kinetic of transformation between sulfur, polysulfides and lithium sulfides during discharge and charge.
- the electrochemical performances in particular such as the rate performances and service life can be further enhanced synergistically by engineering the internal surface of fullerenes or embedding catalyst inside the cavities of fullerenes.
- support materials such as carbon nanotube, graphite, carbon nanofibers, graphene, activated carbon, carbon cloth and so forth
- the support materials can be also used as conductive networks and current collectors.
- binders and aluminum current collectors may be replaced and omitted.
- the graphene-like carbon shell-sulfur core composite structures are synthesized by using metal or metal oxides nanoparticles as catalysts and solid carbon as carbon precursors.
- metal or metal oxides nanoparticles as catalysts and solid carbon as carbon precursors.
- the time mixing process can be from seconds to several days.
- the metal nanoparticles can be nanoparticles of transition metals such as nickel, iron, copper, zinc, titanium, vanadium, chromium, manganese, cobalt, zirconium, niobium, yttrium, molybdenum, lanthanum, tantalum, hafnium, tungsten, platinum, cadmium, palladium, rhodium, ruthenium, technetium, tellurium, lead, and non-transition metals such as tin, silver, gold.
- transition metals such as nickel, iron, copper, zinc, titanium, vanadium, chromium, manganese, cobalt, zirconium, niobium, yttrium, molybdenum, lanthanum, tantalum, hafnium, tungsten, platinum, cadmium, palladium, rhodium, ruthenium, technetium, tellurium, lead, and non-transition metals such as tin
- the metals of metal hydroxide and oxide nanoparticles can be transition metals such as nickel, iron, copper, zinc, titanium, vanadium, chromium, manganese, cobalt, zirconium, niobium, yttrium, molybdenum, lanthanum, tantalum, hafnium, tungsten, platinum, cadmium, palladium, rhodium, ruthenium, technetium, tellurium, lead, and non-transition metals such as tin, silver, magnesium, calcium, and the combination of two or more of them.
- the metal nanoparticles, metal hydroxides or metal oxides nanoparticles can be pre-treated with acid, alkaline solution or oxidants to modify the surface of them.
- the electrically conductive supporting material comprises at least one of the following: carbon nanotubes, graphene, thin graphite, carbon nanofibers, reduced graphene oxides, graphene oxides, activated carbon, porous graphene, porous carbon, porous metals, porous conductive polymers and the combination of two or more of them.
- the content of the electrically conductive supporting material in the composite of the graphene-like carbon hollow structure on the supporting material is from 1 % to 80% by weight.
- the carbon precursors in the above mixing process can be at least one of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene oxide, polyoxyethylene, poly(methyl methacrylate), triethylene glycol, sugar, glucose, sucrose, lignin, dicyandiamide, melamine, urea, proteins, nylon, rubber, polyacrylonitrile, polycarbonate, polyphenylene oxide, polyurethane, polyetherimide, polyamide-imide, fructose, maltose, xylose, starch, cellulose, polyaniline, polyethylenimine, polyamide imides, carboxymethyl cellulose, polyethersulfone, and other hydrocarbon.
- the solvent used in the above mixing process can be at least one of water, ethanal, toluene, butyl or amyl acetate, ethyl acetate, butanol, acetone, 2- ethoxyethanol, pyrobenzene, xylene, cyclohexanone, methyl acetate, hexane, 1 ,4- dioxane, chloroform, diethyl ether, dichloromethane, benzene, cyclohexane, hexane, cyclopentane, pentane, tetrahydrofuran, dimethylformamide, acetonitrile, propylene carbonate, formic acid, n-Butanol, isopropyl alcohol, n-Propanol, methanol, acetic acid, carbon disulphide, o-xylene, pyridine, methylene chloride, N-methyl-2- pyrrolidone,
- the drying temperature can be at from 0 °C to 400 °C.
- the pressure can be from 10 6 mbar to 1 bar.
- freeze drying also known as lyophilisation or cryodesiccation, can be a good method for drying the mixture abovementioned.
- the temperature can be at from -60 °C to 10 °C, meanwhile the pressure can be from 10 6 mbar to 1 bar.
- the drying time can be from few minutes to few days.
- the obtained dried mixture is heat treated under protection by inert gas of at least one of argon, nitrogen.
- inert gas of at least one of argon, nitrogen.
- solid carbon is catalytically converted into layered graphene-like carbon in the assistance of metal nanoparticles or metal oxide nanoparticles, leading to graphene coated metal nanoparticles.
- graphene-like carbon hollow structures or fullerenes are obtained.
- the as-obtained graphene-like carbon hollow structures or fullerenes (carbon nanoonions) contain monolayer or multilayer graphene.
- Other supporting materials such as carbon nanotube, graphite, carbon nanofibers, graphene, activated carbon, carbon cloth and so forth can be used to support and disperse fullerenes, reducing the aggregation of fullerene nanoparticles.
- metal atoms can participate into the growth of graphene and bond with C atoms of graphene, causing metal atoms doped-/bond with graphene crystals and leading to metal atoms doped- or surface-functionalized graphene-like shells after the etching process.
- other atoms such as nitrogen, oxygen, sulfur, phosphorus, boron, hydrogen, fluorine, silicon, iodine, bromine from the solid carbon and metallic compounds can also dope in graphene crystals during growth of graphene.
- residual metal or metal oxides nanoparticles can be left in the cavities enclosed by the shells. These residual metal or metal oxides nanoparticles can sever as catalyst nanoparticles. Furthermore, these residual metal or metal oxides nanoparticles can be used for synthesis of other metallic compounds nanoparticles as catalyst nanoparticles by the chemical conversion approaches such as synthesis, chemical and electrochemical deposition, oxidation, reduction, thermal treatment, photochemical reaction, decomposition, replacement reaction, solid-state reactions, substitution, addition and elimination, complexation, carburizing, nitriding, chemical vapor deposition, etching, etc.
- the C/S composites are then synthesized by using molten sulfur method, which is filling the liquid sulfur into the cavities of graphene-like carbon hollow structures such as fullerenes driven by capillary effect at a temperature from 100 °C to 600 °C for 0.1 hour to 48 hours. After cooling, the sulfur nanoparticles are solidified from liquid sulfur. The pathway for the diffusion of liquid sulfur is the holes in graphene walls induced by the defects. The sulfur content can be adjustable from 50% to 98% by weight. [00101] In addition, the composite structure of the S core-g-C3N4 shell can be also synthesized by the method including the abovementioned steps:
- metal nanoparticles uniformly mix one of the metal nanoparticles, metal hydroxides, and metal oxides nanoparticles with carbon precursors and electrically conductive supporting materials in solution under stirring and/or ultrasonication at a temperature from -30°C to 350 °C.
- other non-porous metallic nanoparticles with size smaller than 30 nm can replace metal nanoparticles, metal hydroxides, and metal oxides nanoparticles for growth of g-CsN4.
- the metallic compounds nanoparticles can be at least one of metal nitrides, metal carbides, metal sulfide, metal phosphide, metal hydroxide, metal selenide, metal telluride, metal boride and the heterostructures of two or more listed above.
- the nitrogen-rich carbon precursors can be at least one of dicyandiamide, melamine, urea, cyanamide, melam, melem and thiourea.
- the obtained dried mixture is heat treated at the temperature from 200 °C to 900 °C under protection by inert gas of at least one of argon, nitrogen and kept for 0.1 h to 24 h.
- inert gas of at least one of argon, nitrogen and kept for 0.1 h to 24 h.
- g-CsN4 layers grow on the surface of the metal, metal and metal oxide nanoparticles, and then coat the nanoparticles to form the layered shell.
- g-CsN4 hollow structures After etching away the metal or metallic compounds nanoparticles in acid, alkaline solution or other etchants, g-CsN4 hollow structures are obtained.
- the as-obtained g-CsN4 hollow structures contain a monolayer or multilayer shell.
- Other supporting materials such as carbon nanotube, graphite, carbon nanofibers, graphene, activated carbon, carbon cloth and so forth can be used to support and disperse g-CsN4 hollow structures, reducing the aggregation of hollow structures.
- the shell of hollow the g-CsN4 structures can be doped with foreign adatoms during growth of g-CsN4.
- residual metal and metallic compounds nanoparticles can be left in the cavities enclosed by the shell of the composites. These residual metal and metallic compounds nanoparticles can sever as catalyst nanoparticles.
- these residual metal and metallic compounds nanoparticles can be used for synthesis of other metallic compounds nanoparticles as catalyst nanoparticles by the chemical conversion approaches such as synthesis, chemical and electrochemical deposition, oxidation, reduction, thermal treatment, photochemical reaction, decomposition, replacement reaction, solid-state reactions, substitution, addition and elimination, complexation, carburizing, nitriding, chemical vapor deposition, etching, etc.
- the g-C3l ⁇ l4/S composites are then synthesized by using the molten sulfur method.
- the pathway for the diffusion of liquid sulfur is the holes in g-CsN4 walls.
- the sulfur content can be adjustable from 50% to 98% by weight.
- the above synthesized core-shell composite structure on the basis of graphene-like carbon shell and g-CsN4 shell can be used for the preparation of sulfur cathodes of metal-sulfur batteries such as lithium-sulfur batteries.
- Lithium-ion batteries are the important renewable energy sources, which are widely used for various commercial applications such as portable electronics, electric vehicles, and the grid.
- the sate-of-the-art lithium batteries still have many unresolved issues such as low energy density, high cost, and short life.
- Li-S batteries represent a promising energy storage system with a superior theoretical energy density of 2600 Wh/kg, up to a five-fold increase compared with the state-of- the-art Li-ion batteries.
- sulfur is endowed with a theoretical specific capacity of 1675 mAh/g and can be one of the most promising next generation cathode materials.
- the above as-disclosed core-shell composite structure can be used for sulfur cathodes and effectively solve these problems to obtain high- performance metal-sulfur batteries.
- the preparation of sulfur cathodes with using the as-disclosed core shell composite structure may comprise the following steps:
- the electrical conductive additives for slurry are used to improve the electrical conductivity of the electrodes, and can be at least one of carbon nanotube, graphite, carbon nanofibers, graphene, activated carbon, carbon cloth, carbon black and so forth.
- the weight content of the electrical conductive additives in the dried coating on the current collector is from 0 to 10%.
- the binders can be at least one of polyvinylidene fluoride (PVDF), polyethylene oxide (PEG), poly(vinylpyrrolidone) (PVP), ethylene propylene diene monomer (EPDM) rubber, carboxymethyl cellulose (CMC), styreneebutadiene rubber (SBR), acrylonitrile multi-copolymer, polyvinyl alcohol (PVA), polyethylene oxide (PEO), poly(methyl methacrylate) (PMMA), polyacrylic acid, polyethyleneimine, b-Cyclodextrin, ammonium polyphosphate.
- PVDF polyvinylidene fluoride
- PEG polyethylene oxide
- PVP poly(vinylpyrrolidone)
- EPDM ethylene propylene diene monomer
- CMC carboxymethyl cellulose
- SBR styreneebutadiene rubber
- PVA polyvinyl alcohol
- PEO polyethylene oxide
- PMMA poly(methyl meth
- the solvent for making the slurry can be at least one of water, N-methyl- 2-pyrrolidone (NMP), ethanol, acetone, butanol, 2-ethoxyethanol, 1 ,4-dioxane, diethyl ether, tetrahydrofuran, dimethylformamide, acetonitrile, propylene carbonate, n- butanol, isopropyl alcohol, n-propanol, methanol, acetic acid, pyridine, ethylene glycol, triethylene glycol, diethyl ether, diethylene glycol, methyl t-butyl ether, nitromethane.
- NMP N-methyl- 2-pyrrolidone
- ethanol acetone
- butanol 2-ethoxyethanol
- 1 ,4-dioxane diethyl ether
- tetrahydrofuran dimethylformamide
- acetonitrile propylene carbonate
- the current collector coated by the slurry can be at least one of the Al foil or foam, Ni foam, iron foam, carbon nanotube membrane, or carbon nanofiber membrane or porous graphene foam, graphene coated Al foil or foam, carbon coated Al foil or foam, porous carbon foams, other metal mesh networks or metal nanowire networks and so forth.
- the loading of the sulfur on electrodes is from 0.5 to 100 mg/cm 2 .
- the metal-sulfur batteries consist of the above sulfur cathodes as positive electrodes.
- the metal-sulfur batteries also consist of the negative electrodes.
- the active materials of the negative electrodes include at least one of the metals of Li, Mg, Al, Fe, Zn, Na, K, Ca, Ba, Cr.
- the negative electrodes can be pure metal foils of Li, Mg, Al, Fe, Zn, Na, K, Ca, Ba, Cr, or coatings, mixtures or composites containing active materials of the metals of Li, Mg, Al, Fe, Zn, Na, K, Ca, Ba, Cr.
- the negative electrodes may comprise a current collector made in forms of foils, foams or porous membranes of copper, iron, nickel, graphite, carbon black, carbon nanotube, amorphous carbon, carbon nanofibers, carbon nanobelts, graphene and the combination of two or more of the list.
- the negative electrodes may also comprise binders such as at least one of polyvinylidene fluoride (PVDF), polyethylene oxide (PEG), poly(vinylpyrrolidone) (PVP), ethylene propylene diene monomer (EPDM) rubber, carboxymethyl cellulose (CMC), styreneebutadiene rubber (SBR), acrylonitrile multi-copolymer, polyvinyl alcohol (PVA), polyethylene oxide (PEO), poly(methyl methacrylate) (PMMA), polyacrylic acid, polyethyleneimine, b - cyclodextrin, ammonium polyphosphate.
- the ratio of the binder to the active materials is from 0 to 1 :8.
- the negative electrodes may also comprise electrical conductive additives including at least one of carbon nanotube, graphite, carbon nanofibers, graphene, activated carbon, carbon cloth, carbon black and so forth.
- the ratio of the electrical conductive additives to the active materials is from 0 to 1 :8.
- the metal-sulfur batteries also consist of the separators, which can be but not limit to polypropylene (PP), polyethylene (PE), polyimide (PI).
- separators which can be but not limit to polypropylene (PP), polyethylene (PE), polyimide (PI).
- the metal-sulfur batteries also consist of the electrolyte, which may contain the salts containing metallic cations of the same element with the active materials of the anode and anions at least one of CIOT, PF 6 , CF3SO3 , AsF 6 , N(CF 3 S0 2 ) 2 -, B O d H d , BF 4 -, SCN , and so forth.
- the electrolyte can be a liquid containing solvents or in solid state that comprises ionically conductive solid-state materials.
- FIG. 1-3 are a schematic showing the cross-sectional view of examples of the composite structures as described above;
- Fig. 1 schematically shows the cross- sectional view of the core-shell composite structure as described above;
- Fig. 2 schematically shows the cross-sectional view of the core-shell composite structure with catalysts embedded in the cavity enclosed by the shell as described above;
- Fig. 3 schematically shows the cross-sectional view of the core-shell composite structure with functionalized groups on internal surface of the shell as described above.
- Fig.4 shows a schematic illustration of the synthesis of fullerenes or carbon onions-sulfur composites anchored on CNT networks in the assistance of Ni nanoparticles (NPs) and used for lithium-sulfur batteries as described above.
- the synthesis of defective fullerenes is by thermal conversion of solid-carbon to fullerene- like carbon or graphene-like carbon in the assistance of metal nanoparticles.
- the metal nanoparticles play functions both as catalysts and templates. As catalysts, they help the conversion of solid carbon to sp 2 carbon with graphitic structures. As templates, after etching the metal nanoparticles, cavities are left for hosting sulfur.
- the nickel hydroxides nanoparticles are prepared based on the reaction between alkaline solution and nickel salts.
- the nickel salts can be nickel nitrate, nickel chlorides, nickel sulfides, nickel acetates and so forth.
- the alkaline solution can be sodium hydroxides, potassium hydroxides, calcium hydroxides, ammonia.
- the particle size of nickel hydroxides is around 1 nm to 50 nm.
- NiO nanoparticles or Ni nanoparticles (such as sputtered Ni) with size of around 1 nm to 50 nm can also be used in this step and the following steps.
- the abovementioned nanoparticles can be dried or kept in a liquid solvent such as water or stabilized with surfactants or organics.
- the solid carbon-nickel hydroxides nanoparticles composites above are then heated at a temperature for a duration.
- the holding temperature is in the ranges 200-900 °C, preferably at 300-700 °C, more preferably at 400-600 °C,.
- the holding time is from 1 second to 24 hours and preferably from 0.5h to 10 h.
- the heating up rate is 1 °C/min to 500 °C/min and preferably 1 °C/min to 10 °C/min.
- the cooling rate is from 1 °C/min to 500 °C/min and preferably from 1 °C/min to 50 °C/min.
- the gases can be one of nitrogen, hydrogen, argon or their mixtures but not limited to any of them.
- the gas flow is from 1 ml/min to 1 m 3 /min.
- the product is etched in chemicals to remove the metal nanoparticles and then fullerenes (carbon nanooions) or fullerenes (carbon nanooions) on supporting materials.
- the etchant is depending on the metals used. Typically for Ni, Cu, Co, Fe and zinc nanoparticles, hydrochloride acid with a concentration from 0.1 M to 5 M or the FeC aqueous solution with a concertation from 0.1 M to 12 M can be used.
- the etching time can be 5 min to 24 h. After etching, fullerenes (carbon nanooions) or fullerenes (carbon nanooions) on supporting materials will be obtained.
- the walls of fullerenes can be adjusted from monolayer to multilayer.
- the carbon walls can be doped with heteroatoms such as oxygen, nitrogen, sulfur, boron, phosphorus, metals and so forth on the external of shells or internal surface of shells.
- the temperature and cooling rate the wall thicknesses of fullerenes (carbon nanooions) can also be adjusted.
- the graphitization and defects content can be tuned.
- the size of metallic nanoparticles and parameters of heating treatment temperature, time, gases, cooling
- the size of fullerenes (carbon nanooions) can be adjusted.
- the surface can be functionalized such as contained functional groups of hydroxyl, carbonyl, aldehyde, haloformyl, carbonate ester, carboxylate, carboxyl, ester, methoxy, or nitrogen contained functional groups such as amide, amines, imine, nitrile, isonitrile, pyridyl, or sulfur contained functional groups such as sulfhydryl, sulfide, sulfinyl, or boron contained functional groups, or halogen contained functional groups.
- the metallic nanoparticles can be partially removed.
- the left metallic nanoparticles inside of cavities of fullerenes or carbon onions can be used for synthesis of metal oxides, metal nitrides, metal sulfides, metal phosphides, metal carbides, metal halide or other metal compounds.
- exotic metallic nanopariticles can also be synthesized after etching by chemical reaction in a liquid or a gas system.
- fullerenes or carbon onions for lithium-sulfur batteries they can be as good host materials for sulfur cathodes by fill sulfur inside the cavities of fullerenes or carbon onions. This can be achieved by mixing the fullerenes or carbon onions with sulfur with a weight ratio in the range of 3: 1 to 1 :30 and heating them at a temperature of 100-600 °C, preferably at 155 °C.
- the mixture of fullerenes or carbon onions and sulfur can be obtained by physical mixing like mechanical milling or chemical mixing. Owing to the holes on walls of fullerenes or carbon onions, liquid sulfur molecular can enter the cavities of fullerenes or carbon onions and concrete to sulfur nanoparticles.
- the sulfur filled in the cavities of fullerenes or carbon onions achieves intimate contact with fullerene-like or graphene-like carbon.
- the particle size of C-S composites is very small and can be controlled in the range of 1-30 nm.
- the sulfur electrodes can be prepared by using casting method on Al foil. Typically, mix the fullerene-sulfur composites with binders such as polyvinylidene difluoride (PVDF) or polyvinylpyrrolidone (PVP) or carboxymethyl cellulose (CMC) or poly(3,4- ethylenedioxythiophene) (PEDOT) and conductivity additives such as Super P carbon black or carbon nanotube or carbon nanofibers in a liquid solvent such as N-Methyl- 2-pyrrolidone (NMP) to make a slurry.
- PVDF polyvinylidene difluoride
- PVP polyvinylpyrrolidone
- CMC carboxymethyl cellulose
- PEDOT poly(3,4- ethylenedioxythiophene)
- conductivity additives such as Super P carbon black or carbon nanotube or carbon nanofibers in a liquid solvent such as N-Methyl- 2-pyrrolidone (NMP)
- the content of binder in the mixture can be 1-15 wt.%.
- the content of conductive additives in the slurry can be 1-25 wt.%.
- the drying pressure can be atmospheric pressure to 1 c 10 6 mbar.
- the electrodes of fullerene-sulfur composites can be also binder-free and aluminum-free electrodes.
- the fullerene-sulfur composites can also be supported by carbon nanotube networks or carbon nanofiber networks or porous graphene foam or metal mesh networks or metal nanowire networks, or porous carbon foams and so forth.
- pyrolyzed electrospun nanofibers are can be used as current collectors.
- the electrodes can be lighter than Al-based and binder-based electrodes.
- the sulfur loading can be higher.
- the gravimetric and volumetric capacity of electrodes can be higher than Al-based and binder-based electrodes.
- the electrodes of fullerene-sulfur composites can exhibit long-life and high capacities. Owing to the small size of sulfur nanoparticles and C-S particles, the utilization of sulfur can reach 100%. The rate-performances of the Me-S batteries such as Li-S batteries can be significantly improved. Owing to the physical and chemical confinement of sulfur inside the cavities of fullerenes or carbon onions, the dissolution and diffusion of polysulfides (S x 2_ ) can be effectively restricted. Thus the life of batteries can be largely improved. [00139] Fig. 5a shows the HRTEM image of Ni(OH)2 nanoparticles. As can be seen, the particle size is less than 20 nm. Fig.
- FIG. 5b shows the SEM image of composites of fullerene@Ni NPs after thermal treatment of Ni(OH)2-PVP composites.
- the bright points are Ni nanoparticles, which have size less than 20 nm.
- Fig. 5c of TEM image of fullerene@Ni NPs clear demonstrates the Ni NPs.
- Fig. 5d of HRTEM image fullerene@Ni NPs clearly shows the Ni nanoparticles coated with graphitic carbon, which is fullerene-like carbon or graphene-like carbon. The size of the particles is ⁇ 10 nm.
- Fig. 5e shows the fullerene or carbon nanoonions after etching away the Ni nanoparticles. The fullerene or carbon nanoonions are highly aggregated together.
- Fig. 5f shows the HRTEM image of fullerene or carbon nanoonions.
- the cavities of fullerene or carbon nanoonions are 5-10 nm, and walls of fullerene or carbon nanoonions are multilayer. The thickness of walls is 1-3 nm.
- Fig. 6a shows the HRTEM image of carbon nanotube supported fullerene spheres.
- the fullerene spheres are effectively dispersed by introducing CNT.
- the CNT is multilayer CNT as can be seen in Fig. 6b.
- the diameter of MWCNT is 10-15 nm and the thicknesses of walls is 2-4 nm.
- the size of cavities is -5-9 nm.
- the CNT can open as seen in Fig. 6c.
- Fig. 6d shows a single-layer fullerene sphere anchored on MWCNT.
- Fig. 6e shows multilayer fullerene spheres anchored on CNT.
- the size of fullerene spheres is in the range of 3-15 nm.
- Fig. 7a The TEM image of fullerene@S NPs@CNT in Fig. 7a shows the microstructures of fullerene-sulfur composites. As can be seen, the sulfur nanoparticles marked with yellow arrows are embedded inside the fullerenes. The particle size is less than 20 nm, mostly is 5-10 nm.
- Fig. 7b-c clearly shows the sulfur nanoparticles are filled inside the cavities of fullerenes. Except, the sulfur can be also filled in the cavities of carbon nanotubes as shown in Fig. 7d. This can be selective and adjusted by controlling the opening of carbon nanotubes.
- the initial discharge and charge were performed at 0.05C.
- CNT content is -30 wt.%
- the initial discharge capacity of fullerene@S NPs@CNT electrode reaches -1620 mAh/g (based on sulfur), which is very close to the theoretical value of sulfur (1670 mAh/g) due to the unique structure of the core-shell composites.
- the initial capacity could reaches 1200 mAh/g.
- the capacity can still remain at 850 mAh/g.
- the capacity decay at 0.2C is 0.29% per cycle.
- the addition of CNT during the synthesis of fullerene and the content of CNT can influence the electrochemical performances of batteries.
- the fullerene@S NPs@CNT composites with content 10 wt.% CNT and 50 wt.% CNT have lower capacities because the content of CNT is out of the optimal range and influences the dispersivity and efficiency of fullerenes.
- a much lower initial capacity of around 966 mAh/g and fast capacity decay are measured for the physical mixture of fullerene@S NPs with 30% CNT, indicating the significance of introducing CNT during the synthesis production of materials to reduce the aggregation of fullerenes.
- Fig. 8b shows the cyclic performance of fullerene@S NPs@CNT (30 wt. %) at 5 C. It shows the fullerene-sulfur electrode has a long life that it can cycle for 2000 cycles. The initial capacity at 5C is 524 mAh/g. After 2000 cycles, the capacity can remain at 252 mAh/g. The capacity decay is only -0.026% per cycle. It should be pointed out that, the performances of fullerene-sulfur electrode can be further improved by adjusting the walls thicknesses and defect content of fullerenes.
- the plurality of core-shell structures are dispersed with an average distance between the plurality of core-shell structures ranging from 0.04 nm to 150 nm, preferably from 0.04 to 50 nm, more preferably from 0.04 to 10 nm.
- the average distance is measured from shell to shell.
- Fig. 9 schematically illustrates the charge and discharge processes of fullerene@S NPs composites.
- the lithium ions diffuse into the cavities of fullerene via the holes and react with the sulfur.
- the electrons transport through the carbon nanotube and walls of fullerenes to sulfur.
- the sulfur has a high utilization, which helps the batteries achieved a high capacity.
- soluble polysulfides formed during discharge. But, due to the small holes of walls, the polysulfides cannot or severely diffuse out of the cavities. Thus the polysulfides are effectively confined inside the cavities of fullerenes. This aids the Li-S cells working for a long life.
- Fig. 10 shows the fullerenes or carbon nanoonions can also embed with CeC>2 nanoparticles.
- the nanoparticles can be prepared by chemical synthesis. Except metal oxides, metal nitrides, metal sulfides, metal phosphides, metal carbides, metal halide or other metal compounds can also be synthesized in fullerenes.
- these metal based materials can be the oxides, nitrides, sulfides, phosphides, carbides, halide, hydroxides or their hybrids of Ni, Cu, Fe, Co, Zn, Ti, Zr, Nb, Mo, Tc, Rh, Pt, Ir, Os, Re, La, Hf, W, Pt, Au, Ag, Ta, Mn, Cr, Sn, V, Cd, Ru, Pd.
- the functions of these nanoparticles include chemically interact with polysulfides and affect the kinetics of phases transformation between lithium polysulfides and lithium sulfides.
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