CN109565053A - In conjunction with the metal foil film current collector of graphene oxide - Google Patents
In conjunction with the metal foil film current collector of graphene oxide Download PDFInfo
- Publication number
- CN109565053A CN109565053A CN201780047369.XA CN201780047369A CN109565053A CN 109565053 A CN109565053 A CN 109565053A CN 201780047369 A CN201780047369 A CN 201780047369A CN 109565053 A CN109565053 A CN 109565053A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- graphene
- collector
- graphite
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 787
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 563
- 239000011888 foil Substances 0.000 title claims abstract description 218
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 125
- 239000002184 metal Substances 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 claims abstract description 91
- 238000010438 heat treatment Methods 0.000 claims abstract description 61
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 27
- 239000012530 fluid Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 230000008021 deposition Effects 0.000 claims abstract description 10
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 238
- 239000010439 graphite Substances 0.000 claims description 238
- 229910052760 oxygen Inorganic materials 0.000 claims description 71
- 239000001301 oxygen Substances 0.000 claims description 70
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 69
- 239000002245 particle Substances 0.000 claims description 46
- 238000007254 oxidation reaction Methods 0.000 claims description 45
- 239000013078 crystal Substances 0.000 claims description 43
- 230000003647 oxidation Effects 0.000 claims description 43
- 229910052744 lithium Inorganic materials 0.000 claims description 41
- 239000011248 coating agent Substances 0.000 claims description 40
- 238000000576 coating method Methods 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 30
- 150000001336 alkenes Chemical class 0.000 claims description 30
- 229910001416 lithium ion Inorganic materials 0.000 claims description 30
- 239000000853 adhesive Substances 0.000 claims description 29
- 239000012528 membrane Substances 0.000 claims description 28
- 230000001070 adhesive effect Effects 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 24
- 239000003990 capacitor Substances 0.000 claims description 24
- 239000007770 graphite material Substances 0.000 claims description 24
- 230000002829 reductive effect Effects 0.000 claims description 24
- 239000004575 stone Substances 0.000 claims description 24
- 239000000839 emulsion Substances 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 20
- 238000005087 graphitization Methods 0.000 claims description 20
- 229910021382 natural graphite Inorganic materials 0.000 claims description 19
- 238000002161 passivation Methods 0.000 claims description 17
- 238000005259 measurement Methods 0.000 claims description 16
- 239000013081 microcrystal Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 238000002050 diffraction method Methods 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 10
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 9
- 230000001965 increasing effect Effects 0.000 claims description 9
- 238000003486 chemical etching Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 239000005030 aluminium foil Substances 0.000 claims description 7
- 239000012456 homogeneous solution Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 238000002003 electron diffraction Methods 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000007766 curtain coating Methods 0.000 claims description 5
- 230000003247 decreasing effect Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000571 coke Substances 0.000 claims description 4
- 229910021385 hard carbon Inorganic materials 0.000 claims description 4
- 239000011302 mesophase pitch Substances 0.000 claims description 4
- 229910021384 soft carbon Inorganic materials 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- ZVSWQJGHNTUXDX-UHFFFAOYSA-N lambda1-selanyllithium Chemical compound [Se].[Li] ZVSWQJGHNTUXDX-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 229940069016 go-dry Drugs 0.000 abstract 1
- 239000010408 film Substances 0.000 description 192
- 239000000499 gel Substances 0.000 description 141
- 239000010410 layer Substances 0.000 description 138
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 24
- -1 graphite alkene Chemical class 0.000 description 21
- 239000011149 active material Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000004840 adhesive resin Substances 0.000 description 17
- 229920006223 adhesive resin Polymers 0.000 description 17
- 238000005229 chemical vapour deposition Methods 0.000 description 16
- 238000009830 intercalation Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 230000007547 defect Effects 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 15
- 230000002687 intercalation Effects 0.000 description 15
- 238000012545 processing Methods 0.000 description 15
- 239000000523 sample Substances 0.000 description 13
- 239000002356 single layer Substances 0.000 description 13
- 230000004087 circulation Effects 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000005611 electricity Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000000306 component Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 238000004220 aggregation Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005411 Van der Waals force Methods 0.000 description 7
- 229920001721 polyimide Polymers 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 230000010354 integration Effects 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000012286 potassium permanganate Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 4
- 239000002134 carbon nanofiber Substances 0.000 description 4
- 239000006182 cathode active material Substances 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 239000002931 mesocarbon microbead Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 229910020003 Mg1.03Mn0.97SiO4 Inorganic materials 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical class O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 230000010415 tropism Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 description 1
- 238000006087 Brown hydroboration reaction Methods 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound 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 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002981 Li4.4Si Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910018688 LixC6 Inorganic materials 0.000 description 1
- 229910008293 Li—C Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 229940126208 compound 22 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 102000057593 human F8 Human genes 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000001540 jet deposition Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021402 lonsdaleite Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229940047431 recombinate Drugs 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
Abstract
A method of for producing the metal foil collector for being used for the combination film graphene oxide of battery or supercapacitor, which comprises (a) preparation has the graphene oxide gel of graphene oxide (GO) molecule being dissolved in fluid media (medium)；(b) at least one of two main surfaces of metal foil one layer of GO gel of upper deposition to form wet oxidation Graphene gel layer, wherein the deposition procedure includes the shear-induced desaturation of the GO gel；(c) fluid media (medium) is removed partially or even wholly from the wet layer deposited to form GO dry film, does the dry film have the interplanar spacing d of the 0.4nm to 1.2nm such as measured by X-ray diffraction? 002#191；And it is heat-treated the graphene oxide dry film under the heat treatment temperature from 80C to 2,500C (d) to form the metal foil collector of the combination film graphene oxide.
Description
Cross reference to related applications
This application claims the preferential of the U.S. Patent Application No. 15/231486 and 15/231498 submitted on the 8th of August in 2016
The application is incorporated herein by power by quoting mode.
Technical field
The present invention provides a kind of for lithium battery or the collector of supercapacitor.The collector is combined with by oxygen
The metal foil of the graphene oxide film of graphite alkene gel production.It is electrolyte-that this, which combines the thin metal foil of graphene oxide,
It is compatible, non-reacted, etch-proof, contact resistance is low, thermal conductivity, it is ultra-thin and light-weight so that battery
Or capacitor is capable of providing higher output voltage, higher energy density, high magnification ability and much longer circulation longevity
Life.
Background technique
Present patent application is related to a kind of collector, and the collector and lithium cell are (for example, lithium-ion electric core, lithium-metal electricity
Core or lithium-ion capacitor), supercapacitor, non-lithium battery (such as zinc-air battery core, nickel metal hydride battery, sodium ion
Battery core and magnesium ion battery core) and other electrochemical energy storage battery cores anode electrode (anode active material layers) or cathode
Electrode (cathode active material) works together.The application is not related to anode active material layers or cathode active material itself.
Lithium-metal battery core includes conventional lithium-metal rechargeable battery core (for example, using lithium foil as anode and making
Use MnO2Particle is as active material of cathode), lithium-air battery core (Li- air), lithium-sulphur battery core (Li-S) and emerging lithium-
Graphene battery core (Li- graphene, use graphene film as active material of cathode), (Li-CNT makes lithium-carbon nanotube battery core
Use CNT as cathode) and lithium-nano-sized carbon battery core (Li-C, use carbon nano-fiber or other nano-carbon materials as yin
Pole).Anode and/or cathode active material can contain some lithiums, or can before battery core assembling prelithiation or later
Prelithiation immediately.
Rechargable lithium ion (Li ion), lithium metal, lithium-sulphur and Li metal-air battery are considered as electronic
The promising electricity of vehicle (EV), hybrid electric vehicle (HEV) and portable electronic device (such as laptop computer and mobile phone)
Source.With as active material of positive electrode any other metal or metal-intercalation compound (in addition to Li4.4Si has 4,
The specific capacity of 200mAh/g) it compares, the lithium as metallic element has highest lithium storage volume (3,861mAh/g).Therefore,
In general, Li metal battery (with lithium anodes) is with being significantly higher than traditional lithium-ion battery (with graphite anode)
Energy density.
In history, rechargeable lithium metal battery be using the non-lithiated compounds with relatively high specific capacity such as
TiS2、MoS2、MnO2、CoO2And V2O5As active material of cathode production, these active material of cathode and lithium anodes coupling
It closes.When the cell is discharged, lithium ion is transferred to cathode from lithium anodes by electrolyte, and cathode becomes lithiumation.It is unfortunate
Ground is, in duplicate charging and discharging, lithium metal causes to form dendrite at anode, and the dendrite finally causes internal short
Road, thermal runaway and explosion.Due to a series of accidents related with this problem, stopped in early stage nineteen nineties
The production of the secondary cell of these types instead lithium ion battery.Even if now, being filled for EV, HEV and microelectronics
For setting application, cyclical stability and safety issue, which are still, interferes Li metal battery (such as lithium-sulphur and lithium-transition metal
Oxide battery core) further commercialized principal element.
The hair of lithium ion secondary battery is resulted in by the worry promotion of the aforementioned safety to early stage lithium metal secondary cell
Exhibition, in a lithium ion secondary battery, carbonaceous material (for example, natural graphite particles) replace pure lithium metal piece or film living as anode
Property material.Carbonaceous material absorbs lithium respectively during the recharge phase and discharge regime of lithium ion battery operation and (such as passes through
The intercalation of lithium ion or atom between graphene planes) and desorption lithium ion.The carbonaceous material can be mainly comprising can be with
With the graphite of lithium intercalation, and gained graphite intercalation compound can be expressed as LixC6, wherein x is typically less than 1 (wherein graphite
Specific capacity < 372mAh/g).
It is current although lithium ion (Li ion) battery is the promising energy accumulating device for electro-motive vehicle
Cost, safety and performance objective (such as high-energy-density, high-energy density, good has not yet been reached in the Li ion battery of technical level
Cyclical stability and long circulation life).Li ion battery core typically uses lithium transition-metal oxide or phosphate as opposite
The deintercalation/be embedded in Li again under high potential in carbon negative electrode (anode)+Positive electrode (cathode).Based on lithium transition-metal oxide
Or the specific capacity of phosphatic active material of cathode is typically in the range of 140-170mAh/g.Therefore, with graphite anode and
Specific energy (weight energy based on the commercially available Li ion battery core that lithium transition-metal oxide or phosphatic cathode are characterized
Density) typically 120-220Wh/kg, most typically in the range of 150-200Wh/kg.Corresponding exemplary energy density
(volume energy density) range is from 300Wh/L to 400Wh/L.These energy values ratios are in order to make battery powered electric vehicle
It is two to three times low to be widely accepted required energy values.
Typical battery battery core is made of following item: anode collector, anode electrode (also referred to as anode active material layers,
Typically comprise active material of positive electrode, conductive filler and binder resin component), electrolyte/diaphragm, cathode electrode (also referred to as
Cathode active material typically comprises active material of cathode, conductive filler and adhesive resin), cathode current collector, connection
To external cabling (external wiring) metal tabs and be wrapped in every other component in addition to the tab
The shell of surrounding.The weight summation and volume summation of these components are battery core total weight and battery core total volume respectively.By battery core institute
The energy total amount of storage is controlled by the amount of active material of cathode and the amount of corresponding active material of positive electrode.The specific energy and energy of battery core
Metric density is then respectively defined as the energy total amount stored by battery core total weight and battery core total volume.It means that making electricity
Maximumlly a kind of method is to make active material under the constraint of other battery design Considerations to the specific energy and energy density of core
The amount of material maximizes and minimizes the amount of every other component (non-active material).
In other words, the collector at the anode and cathode in battery battery core is non-active material, must be reduced (
In terms of weight and volume) to increase the weight and volume energy density of battery.Collector (typically aluminium foil (at cathode) and
Copper foil (at anode)) it accounts for the by weight about 15%-20% of lithium ion battery and counts 10%-15% at cost.Therefore, more
Thin, lighter foil will be preferred.However, in the presence of several main problems relevant to the collector of the present art:
(1) due to being easy corrugation and tearing, thinner foil tends to more expensive and is more difficult to work together.
(2) due to technological constraint, it is difficult to (if not impossible) a large amount of manufactures (for example, the Cu) or ratio thinner than 6 μm
12 μm thinner (for example, Al, Ni, stainless steel foil) metal foil.
(3) collector must be electrochemically stable relative to battery core component within the scope of the operation potential window of electrode.
In fact, the internal resistance that mainly the lasting corrosion of the collector as caused by electrolyte may cause battery is gradually increased, which results in
The continuous loss of apparent capacity.
(4) oxidation of metal collector is strong exothermal reaction, and the heat that the reaction may facilitate lithium battery significantly is lost
Control.
Therefore, for the cost of battery, weight, safety and performance, collector is vital.Instead of metal,
The solid metal or plastics of graphene or graphene coating have been considered as potential current collector material, as being listed below
It is summarized in bibliography:
1.Li Wang、Xiangming He、Jianjun Li、Jian Gao、Mou Fang、Guangyu Tian、
Jianlong Wang, Shoushan Fan, " Graphene-coated plastic film as current collector
For lithium/sulfur batteries is [as graphene-coating plastics for lithium/sulphur battery collector
Film] ", J.Power Source [power supply magazine], 239 (2013) 623-627.
2.S.J.Richard Prabakar、Yun-Hwa Hwang、Eun Gyoung Bae、Dong Kyu Lee、
Myoungho Pyo, " Graphene oxide as a corrosion inhibitor for the aluminum
Current collector in lithium ion batteries is [as the corruption for the aluminium collector in lithium ion battery
The graphene oxide of corrosion inhibitor] ", Carbon [carbon], 52 (2013) 128-136.
3.Yang Li et al. people, 104600320 A of China Patent Publication No. CN (on May 6th, 2015).
4.Zhaoping Liu et al. people, (Ningbo Institute of Materials and Energy, China [in
State's Ningbo material and Energy Research Institute]), 2012/151880 A1 of WO (on November 15th, 2012).
5.Gwon,H.；Kim,H-S；Lee,KE；Seo,D-H；Park,YC；Lee,Y-S；Ahn,BT；Kang,K；
" Flexible energy storage devices based on graphene paper [the flexible energy based on graphene paper
Measure storage device] ", Energy and Environmental Science [energy and environment science], 4 (2011) 1277-
1283。
6.Ramesh C.Bhardwaj and Richard M.Mank, " Graphene current collectors in
Batteries for portable electronic devices is [for the graphene in the battery of portable electronic device
Collector] ", 20130095389 A1 of US, on April 18th, 2013.
Currently, there are three types of different forms for graphene collector: the substrate [bibliography 1-4] of graphene coating, stand alone type
Then metal loses for graphene paper [bibliography 5] and the chemical vapor deposition (CVD) being catalyzed by transition metal (Ni, Cu)
The single layer graphene film [bibliography 6] carved and produced.
In the preparation of the substrate of graphene coating, by graphene oxide (GO) or the graphene oxide (RGO) of reduction
On small isolated piece or platelet jet deposition to solid substrate (for example, plastic foil or Al foil).In graphene layer, structure list
Member is isolated graphene film/platelet (typically length/width is 0.5-5 μm and with a thickness of 0.34-30nm), the graphite
Alkene piece/platelet combines [bibliography 1,3 and 4] typically via adhesive resin such as PVDF.Although individual graphene
Piece/platelet can have relatively high conductivity (in 0.5-5 μm of the limitation), but gained graphene-adhesive resin
Composite layer is relative mistake (typically < 100S/cm and more typically < 10S/cm) in terms of conductivity.In addition, using bonding
Another purpose of agent resin is integrated to graphene-adhesive composite layer on substrate (for example, Cu foil)；It means that
There are adhesive resin (adhesive) layers between Cu foil and the graphene-adhesive composite layer.Unfortunately, this adhesive tree
Rouge layer is electrical isolation and the ill-effect of generation seems fully to be ignored by work at present person.
Although Prabakar et al. [reference paper 2] does not appear to be formed using adhesive resin coated with discrete oxidation
The aluminium foil of graphene film, but Al foil the problem of having its own of this graphene oxide coating.It is well known in the art to be, alumina
Object (Al2O3) be easy to be formed on the surface of aluminium foil, and this aluminum oxide or aluminium oxide cannot be removed with acetone or alcohol cleaning
Passivation layer.What this al oxide layer was not only electrically and thermally to insulate, and actually certain form of electrolyte is not tolerated.
For example, most common lithium ion battery electrolyte is dissolved in the LiPF in organic solvent6.Trace H in this electrolyte2O may
Trigger it is a series of be related to being formed the chemical reactions of HF (high corrosiveness acid), the HF be easy to decompose the al oxide layer and
Continue to corrode Al foil and consumes electrolyte.Capacity attenuation typically becomes brighter after 200-300 charge-discharge cycles
It is aobvious.
It is prepared by GO or RGO piece/platelet that free-standing graphene paper suspends in water typically via vacuum assisted filtration.
In free-standing paper, structural unit is the isolated graphene film/platelet loosely to overlap.Again, although individually
Graphene film/platelet can have relatively high conductivity (in 0.5-5 μm of the limitation), but gained graphene paper has
Low-down conductivity；Such as 8,000S/m or 80S/cm [bibliography 5], than the conductivity (8x 10 of Cu foil5S/cm) low
4 orders of magnitude.
The CVD process of catalysis is related in the vacuum chamber at a temperature of appropriate hydrocarbon gas is introduced into 500 DEG C -800 DEG C.It is stringent at these
Under the conditions of, the appropriate hydrocarbon gas is decomposed, wherein the decomposition reaction is catalyzed by transition metal substrate (Ni or Cu).Then using strong
Acid chemically etches away the Cu/Ni substrate, this is not environmental-friendly program.The whole process is slow, tediously long and consume
Can, and gained graphene be typically single-layer graphene or few layer graphene (up to 5 layers because following Cu/Ni layer loses
Go its effect as catalyst).
Bhardwaj et al. [bibliography 6] suggests stacking multiple CVD- graphene films to 1 μm or several μm of thickness；So
And this will need the hundreds of or thousands of films being stacked (each film typically 0.34nm to 2nm is thick).Although Bhardwaj
Et al. claim " graphene can reduce manufacturing cost and/or increase battery battery core energy density ", but without present experiment
Data support their claim.It is claimed with this on the contrary, CVD graphene is notoriously expensive process, and even single
The CVD graphene film of layer will be significantly more more expensive than Cu foil or Al paillon, it is assumed that area is identical (for example, identical 5cm x 5cm).
As the stacked body of Bhardwaj et al. hundreds of or thousands of single layers suggested or the graphene film of few layer will imply that than Cu foil collection
Fluid is more expensive hundreds of or thousands of times.This cost will be excessively high.Further, hundreds of CVD graphenes in stacked body
The relatively low conductivity of high contact resistance and CVD graphene between film will lead to high total internal resistance, so that using compared with film
(relative to 10 μm of Cu foil, 1 μm of graphene stacked body) is become with any potential benefit for reducing battery core total weight and total volume
It obtains in vain.Seem, the patent application [bibliography 6] of Bhardwaj et al. (being free of any data) only concept paper.
It is described above to be clearly shown, all three graphene enhancing or the collector based on graphene forms
Performance used in battery or supercapacitor and cost requirement is not satisfied.Exist to the different kind of material for being used as collector
Tight demand.
Summary of the invention
The present invention provides a kind of metal foil (film) affluxs of the combination graphene oxide in battery or supercapacitor
Body.The collector includes: (a) stand alone type, non-loading type thin metal foil, and the thin metal foil has the thickness from 1 μm to 30 μm
Degree and two opposite but substantially parallel main surfaces；(b) it is chemically combined without using adhesive or adhesive
Graphene oxide sheet film on at least one of described two opposite main surfaces, wherein at least one described main surface
Without passive metal oxide skin(coating) (for example, there is no alumina layer in this main surface of Al foil), and the wherein graphite oxide
Alkene film has thickness from 10nm to 10 μm, by weight from 0.1% to 10% oxygen content, 0.335nm to 0.50nm's
Spacing between graphene planes, from 1.3g/cm3To 2.2g/cm3Phsyical density, all graphene oxide sheets are oriented to substantially phase
It is mutually parallel and be parallel to the main surface and show and be greater than when independent measurement in the case where no thin metal foil
The thermal conductivity of 500W/mK and/or conductivity greater than 1,500S/cm.Described film GO layers in itself not using adhesive tree
Rouge or adhesive, and there is no adhesive resin/adhesive or passivation gold between the metal foil layer at described film GO layers
Belong to oxide skin(coating).
The thin metal foil (for example, Cu foil, Al foil, stainless steel foil, Ni foil and Ti foil) must be free-standing films (for example,
Be not supported on another metal plate), so as to reduce film thickness and thus reduce it is being collected from electrode active material or
It is transferred to the path length that electronics therein must advance.The thickness that the thin metal foil preferably has from 4 μm to 10 μm.It is excellent
Selection of land, the graphene oxide film have the thickness of from 20nm to 2 μm (further preferred < 1 μm).
Preferably, two main surfaces it is each it is comfortable without using adhesive or adhesive in the case where with graphene oxide sheet film
It is chemically combined；Wherein the graphene oxide film have thickness from 10nm to 10 μm, by weight from 0.1% to
Spacing between 10% oxygen content, the graphene planes of 0.335nm to 0.50nm, from 1.3g/cm3To 2.2g/cm3Phsyical density,
All graphene oxide sheets, which are oriented to, is substantially parallel to each other and is parallel to the main surface, when in no thin metal foil
In the case where independent measurement when, show thermal conductivity greater than 500W/mK and be greater than the conductivity of 1,500S/cm.
The thin metal foil is preferably chosen from Cu, Ti, Ni, stainless steel and the Al foil through chemical etching.Chemical etching with
Such mode carries out on Al foil, that is, so that the surface of the Al foil through chemical etching in conjunction with graphene oxide molecule it
The preceding passivation Al not being formed on2O3Film.
We also have surprisingly been observed that graphene oxide gel (contains the graphite of heavy oxidation in acid medium
The GO gel of alkene molecule, the acid medium has 5.0 or lower, preferably and typically < 3.0 and most typically <
2.0 pH value) passivation Al on Al foil surface can be removed2O3Phase.These GO molecules in GO gel have typically by weight
Meter > 20%, more typically by weight > 30% and most typically ground oxygen content by weight > 40%.In contrast, discrete
The simple suspension of graphene or graphene oxide sheet in liquid medium (for example, water or organic solvent) (but is not in GO
Gel state) do not have this etch capabilities.If restore from gel state and dry and then redisperse into liquid medium,
Even if the GO piece of heavy oxidation may also lose this etch capabilities.The GO piece, even if being only slightly reduced into the oxygen of reduction
Graphite alkene (RGO), may also equally lose this etch capabilities.These observation results are really unexpected.
In certain embodiments, the graphene oxide sheet film has by weight from 1% to 5% oxygen content.?
In certain other embodiments, graphene oxide film in collector of the invention has oxygen content less than 1%, is less than
Spacing and the conductivity not less than 3,000S/cm between the graphene of 0.345nm.Preferably, in collector of the invention,
The graphene oxide film has the oxygen content less than 0.1%, spacing and is not less than between the graphene less than 0.337nm
The conductivity of 5,000S/cm.It is further preferred that the graphene oxide film has the oxygen content, small no more than 0.05%
Between the graphene of 0.336nm spacing, no more than 0.7 inlay latitude of emulsion value and the conductivity not less than 8,000S/cm.
In certain embodiments, the graphene oxide film have less than 0.336nm graphene between spacing, be not more than
0.4 inlays latitude of emulsion value and the conductivity greater than 10,000S/cm.In some collectors of the invention, the oxidation stone
Black alkene film shows spacing between the graphene less than 0.337nm and inlays latitude of emulsion value less than 1.0.It is preferably and typical
Ground, the graphene oxide film show the degree of graphitization not less than 80% and/or inlay latitude of emulsion value no more than 0.4.
The present invention also provides a kind of methods for producing collector of the invention.In this method, the graphene oxide
Piece film obtains in the following manner: under the influence of tropism control stress, graphene oxide gel being made to deposit to metal foil
In one main surface or two main surfaces, the tropism control stress arranges GO molecule or piece along main surface plane direction；
And deposited graphene oxide gel is then heat-treated under the heat treatment temperature from 80 DEG C to 1,500 DEG C.Preferably, institute
Stating heat treatment temperature is from 80 DEG C to 500 DEG C.It is further preferred that the heat treatment temperature is from 80 DEG C to 200 DEG C.
We also unexpectedly observe, can promote down to 80 DEG C to 200 DEG C of heat treatment temperatures height-oriented
The edge-to-edge of GO piece merge the GO molecule of (being connected chemically, extending for sheet molecule) or the heavy oxidation arranged well
" polymerization or the chain growth " of (coming from GO gel).Therefore, in certain embodiments, the graphene oxide film contains puts down each other
The graphene planes that capable chemically combined graphene molecules or chemistry merge.
In some embodiments, from having maximum original graphite crystallite dimension, (generation has the graphene oxide gel
The GO piece of maximum length) graphite material obtain, and the graphene oxide film has than this maximum initial grain size
Or the bigger crystallite dimension of maximum GO length.This is the reflection of following viewpoint: height-oriented, severe oxygen from gel state
The GO piece or molecule of change can edge-to-edge merge or be connected chemically to form longer or broader graphene film or molecule.
The present invention also provides a kind of for producing the combination film graphene oxide for being used for battery or supercapacitor
The method of metal foil collector.The described method includes: (a) preparation has the graphene oxide molecule being dissolved in fluid media (medium)
Graphene oxide gel, wherein the graphene oxide molecule contains by weight of from more than 20% oxygen content；(b) in metal foil
At least one of two main surfaces on distribute and deposit one layer of graphene oxide gel, with formed be deposited thereon it is wet
Graphene oxide gel layer, wherein the distribution and deposition procedure include the shear-induced desaturation of graphene oxide gel；(c) from
It is dry to form graphene oxide that the fluid media (medium) is partially or even wholly removed in the graphene oxide gel wet layer deposited
Film, the dry film have the interplanar spacing d of the 0.4nm to 1.2nm such as measured by X-ray diffraction002By weight not
Oxygen content less than 20%；And it is dry that the graphene oxide (d) is heat-treated under the heat treatment temperature from 80 DEG C to 2,500 DEG C
For film to form the metal foil collector of the combination film graphene oxide, degree is so that interplanar spacing d002It is reduced to
Value and oxygen content from 0.335nm to 0.5nm be reduced to by weight less than 10% and the graphene oxide film have
The thickness that has from 10nm to 10 μm, from 1.3g/cm3To 2.2g/cm3Phsyical density, and all graphene oxide sheets are oriented to
It is substantially parallel to each other and is parallel at least one main surface.
In certain embodiments, step (b) includes: above to distribute simultaneously in each of two main surfaces of the metal foil
And one layer of graphene oxide gel of deposition, to form the wet oxidation graphene being deposited in each of described two main surfaces
Gel layer, wherein the metal foil has the thickness from 1 μm to 30 μm.The metal foil can selected from Cu, Ti, Ni, stainless steel,
And the Al foil through chemical etching, wherein before in conjunction with the graphene oxide, the table of the Al foil through chemical etching
The passivation Al that face is not formed on2O3。
In certain embodiments, step (c) includes forming the interplanar spacing d with 0.4nm to 0.7nm002By weight
The graphene oxide layer of oxygen content of the meter not less than 20%；And step (d) includes being heat-treated the graphene oxide layer, journey
Degree is so that interplanar spacing d002It is reduced to the value from 0.3354nm to 0.36nm and the oxygen content is reduced to by weight
Less than 2%.
In certain embodiments, when being measured at 20 DEG C before the shear-induced desaturation, the graphene oxide
Gel has the viscosity greater than 2,000 centipoise, and during or after shear-induced desaturation, the viscosity is decreased to less than 2,
000 centipoise.Preferably, when measuring at 20 DEG C before shear-induced desaturation, the graphene oxide gel has from 500
Centipoise to 500,000 centipoises viscosity.In some preferred embodiments, measured at 20 DEG C when before shear-induced desaturation
When, the graphene oxide gel has the viscosity not less than 5,000 centipoise, and during or after shear-induced desaturation,
The viscosity is decreased to less than 2,000 centipoises.Typically, when increasing shear rate at 20 DEG C, the graphene oxide is solidifying
Glue has the viscosity for reducing at least 10 times.The graphene oxide gel has less than 5.0, preferably < 3.0 and more preferably <
2.0 pH value.The shear-induced desaturation can be carried out by the program selected from following item: coating, curtain coating, printing are (for example, spray
Ink print, silk-screen printing etc.), air auxiliary spraying, ultrasound spraying or squeeze out.Preferably, step (d) is included in compression stress
The lower heat treatment graphene oxide layer.
The graphene oxide gel can be prepared in the following manner: will be in powder or fiber shape in the reaction vessel
The graphite material of formula, which immerses in oxidation liquid, forms initially optically opaque and dark suspension, soaks at the reaction temperatures
Enough a period of times are steeped to obtain homogeneous solution and or optically transparent, translucent or brown oxidation stone
Black alkene gel, wherein the graphene oxide gel by be dissolved in have not higher than 5 pH value acid medium in oxidation stone
Black alkene molecule is constituted, and the graphene oxide molecule has the oxygen content for being not less than 20% by weight.The graphite material
Material can selected from natural graphite, artificial graphite, mesocarbon, mesophase pitch, carbonaceous mesophase spherules, soft carbon, hard carbon, coke,
Carbon fiber, carbon nano-fiber, carbon nanotube, or combinations thereof.
The method can be reel-to-reel method, and wherein step (b) and (c) include: to feed the metal foil from roller
One layer of graphene oxide gel is deposited to crystallizing field, at least one main surface described in the metal foil to be formed on
Graphene oxide gel wet layer, the dry graphene oxide gel wet layer is to form the dry oxidation stone being deposited in main surface
Black alkene layer, and the metal foil that the dry graphene oxide layer of collection deposits on collector roller.
In certain embodiments, the heat treatment temperature includes the temperature in 80 DEG C -500 DEG C of thermal reduction scheme, and
And the graphene oxide membrane has the oxygen content less than 5%, spacing and/or at least 100W/mK between the graphene less than 0.4nm
Thermal conductivity.In certain embodiments, the heat treatment temperature is included in 500 DEG C -1, the temperature within the scope of 000 DEG C, and institute
Integral piece grapheme material is stated with the oxygen content less than 1%, spacing, at least 1,300W/mK between the graphene less than 0.345nm
Thermal conductivity and/or conductivity not less than 3,000S/cm.In certain embodiments, the heat treatment temperature is included in 1,000
DEG C -1, the temperature within the scope of 500 DEG C, and the graphene oxide membrane has oxygen content less than 0.01%, is less than 0.337nm
Graphene between spacing, at least thermal conductivity of 1,500W/mK and/or the conductivity not less than 5,000S/cm.
In certain embodiments, the graphene oxide membrane shows spacing between the graphene less than 0.337nm and is less than
1.0 inlay latitude of emulsion value.In certain embodiments, the graphene oxide membrane show degree of graphitization not less than 40% and/
Or latitude of emulsion value is inlayed less than 0.7.In certain embodiments, the graphene oxide membrane shows the graphitization not less than 80%
It spends and/or inlays latitude of emulsion value no more than 0.4.
Typically, the graphene oxide membrane contains what chemically combined graphene molecules or chemistry parallel to each other merged
Graphene planes.
In certain embodiments, the graphene oxide gel is obtained by the graphite material with multiple graphite microcrystals, institute
It states graphite microcrystal and does not show preferred crystal orientation (as measured by X-ray diffraction or electron diffraction), and wherein
The graphene oxide membrane has preferred crystal orientation (as measured by the X-ray diffraction or electron diffraction).
The graphene oxide gel can obtain in the following manner: in the reaction vessel, will be at the reaction temperatures
The graphite material of powder or fibers form, which immerses in oxidation liquid medium, continues enough a period of times to obtain by being dissolved in
The homogeneous solution that the graphene oxide molecule in liquid medium is constituted is stated, wherein the homogeneous solution is optically transparent, semi-transparent
It is bright or brown, and when being in gel state, the graphene oxide molecule has is not less than 20% by weight
Oxygen content and molecular weight less than 43,000 grams/mol.In some GO gels, when being in gel state, graphite oxide
Alkene molecule has the molecular weight less than 4,000 grams/mol.In some other GO gels, when being in gel state, stone is aoxidized
Black alkene molecule has the molecular weight between 200 grams/mol and 4,000 grams/mol.
In the method for the invention, the heat treatment step causes being connected chemically, merge or changing for graphene oxide molecule
It learns and combines and/or being graphitized again of graphite-structure (re-graphitization) or recombinate.
The method, which typically generates, to be had the conductivity for being greater than 3,000S/cm, the thermal conductivity greater than 600W/mK, is greater than
The graphene oxide membrane of the phsyical density of 1.8g/cm3 and/or the tensile strength greater than 40MPa.More typically, the oxidation stone
Black alkene film has conductivity, the thermal conductivity greater than 1,000W/mK, the phsyical density greater than 1.9g/cm3 greater than 5,000S/cm
And/or the tensile strength greater than 60MPa.In many cases, the graphene oxide membrane has the electricity greater than 15,000S/cm
Conductance, is greater than 2.0g/cm at the thermal conductivity greater than 1,500W/mK3Phsyical density and/or be greater than 80MPa tensile strength.
It additionally provides a kind of for producing the metal foil for being used for the combination film graphene oxide of battery or supercapacitor
The method of collector, which comprises (a) preparation has the oxidation stone for the graphene oxide molecule being dissolved in fluid media (medium)
Black alkene coagulation bath, wherein the graphene oxide molecule contains by weight of from more than 20% oxygen content and the graphite oxide
Alkene gel has the pH value less than 5.0；(b) metal foil is fed in the GO coagulation bath and moves the metal foil
The bath (shear stress is generated near main surface) out, makes it possible to each of two main surfaces in the metal foil
Upper deposited oxide Graphene gel wet layer；(c) it is partially or even wholly removed from the graphene oxide gel wet layer deposited
For the fluid media (medium) to form graphene oxide dry film, the dry film has the 0.4nm such as measured by X-ray diffraction extremely
The interplanar spacing d of 1.2nm002It is not less than 20% oxygen content by weight；And (d) in the heat from 80 DEG C to 2,500 DEG C
The graphene oxide dry film is heat-treated under treatment temperature to form the metal foil collector of the combination film graphene oxide,
Its degree is so that interplanar spacing d002It is reduced to value and oxygen content from 0.335nm to 0.5nm to be reduced to small by weight
In 10% and the graphene oxide film there is thickness from 10nm to 10 μm, from 1.3g/cm3To 2.2g/cm3Physics
Density, and all graphene oxide sheets are oriented to and are substantially parallel to each other and are parallel at least one described main surface.This
Aluminium foil of the method especially suitable for production GO coating, because GO gel itself can remove the passive oxidation aluminium on Al foil surface
Layer, and the method also prevents from re-forming such passive oxidation aluminium layer.
In certain embodiments, the graphene oxide gel is by natural or artificial graphite particle manufacture, and described
Grain is by with the initial length L in crystallography a- axis directiona, original width L in b- axis directionbAnd the thickness in c- axis direction
Spend LcGraphite microcrystal constitute, and the graphene oxide film have greater than the graphite microcrystal initial LaAnd LbStone
Black alkene farmland or crystal length or width.
Typically, the graphene oxide film contains with sp2And sp3The combined graphene planes of electron configuration.It is excellent
Selection of land, the graphene oxide film are continuous length films, have not less than 5cm (preferably not less than 10cm and further
Preferably not less than 20cm) length and be not less than 1cm (preferably not less than 10cm) width.To graphene oxide of the invention
The length and width of continuous length film is without practical limitation.
In certain embodiments, when independent measurement, the graphene oxide film has the physics greater than 1.8g/cm3
Density and/or tensile strength greater than 40MPa；Preferably have greater than the phsyical density of 1.9g/cm3 and/or the drawing greater than 60MPa
Intensity is stretched, and more preferably has and is greater than 2.0g/cm3Phsyical density and/or tensile strength greater than 80MPa.
The present invention also provides a kind of lithium rechargeable battery or lithium ion batteries, contain collector conduct of the invention
Anode collector and/or cathode current collector.The lithium rechargeable battery can be lithium-sulphur battery core, lithium-selenium battery core, lithium sulphur/selenium
Battery core, lithium-air battery core, lithium-graphene battery core or lithium-carbon battery core.
The present invention also provides a kind of capacitor, the capacitor contain collector of the invention as anode collector or
Cathode current collector, the capacitor are symmetrical supercapacitor, asymmetric super capacitor electric core, hybrid super capacitor
Device-battery battery core or lithium-ion capacitor battery core.
Detailed description of the invention
Fig. 1 (A) illustrates to produce expanded graphite product (soft graphite foil and Flexible Graphite Composites) and pyrolytic graphite (bottom
Portion part) various art methods, together with for produce graphene oxide gel 21 and orientation GO wet film 35, with
And it is integrated to the flow chart of the method for the film 37 of the GO of metal foil surface；
Fig. 1 (B) illustrates paper, felt and the film of graphite or graphene (NGP) thin slice/platelet for producing simple aggregation
Conventional method schematic diagram.All methods start from intercalation and/or the oxidation of graphite material (such as natural graphite particles)
Processing.
Fig. 1 (C) illustrates the schematic diagram of the metal foil collector of the graphene coating of the prior art, wherein graphene layer and gold
There are adhesive resin layer (or passivation al oxide layers) between category foil such as Cu foil (or Al foil).
Fig. 1 (D) illustrates the schematic diagram for preferably combining the metal foil collector of graphene, wherein graphene oxide membrane and Cu
There is no adhesive resin layer or passivation al oxide layers between foil or Al foil.
Graphite worm sample of the Fig. 2 (A) after the hot extruding of graphite intercalation compound (GIC) or graphite oxide powder
SEM image；
The SEM image of the cross section of Fig. 2 (B) soft graphite foil has it illustrates many and is not parallel to the flexible stone
The graphite flake of the orientation on black foil surface, and many defects are also shown, kink or folding thin slice.
The SEM image of Fig. 3 (A) GO gel derived graphene monolithic, wherein multiple graphenes in graphite particle are flat
Face (with 30nm -2 μm of original length/width) has been oxidized, extruding, reorientation and is seamlessly merged into extensible
Hundreds of centimetres wide or long continuous length graphene sheet or layer.
Fig. 3 (B) is using papermaking process (for example, vacuum assisted filtration) by the conventional stone of discrete graphene film/platelet preparation
The SEM image of the cross section of black alkene paper/film.Described image shows the discrete stone that many was folded or interrupted (not being integration)
Black alkene piece has and is not parallel to film/paper surface orientation, and has many defects or flaw；
Fig. 3 (C) illustrates the schematic diagram of the forming method of integrated GO entity, the GO entity by it is parallel to each other and
Multiple graphenes that are being connected chemically on graphene planes direction and also combining on thickness direction or crystallography c-axis direction are flat
Face is constituted；
A kind of plausible mechanism that is connected chemically of Fig. 3 (D) (illustrates only 2 GO molecules as example；A large amount of GO molecule
It can be connected chemically together to form big graphene farmland).
The gel derived graphene layer of GO, the GO piece that Fig. 4 (A) is drawn as the function of graphited final heat treatment temperature
The heat conductivity value of brilliant paper and FG foil；
PG derived from pyrolytic graphite (PG) derived from Fig. 4 (B) GO gel derived graphene layer, polyimides and CVD carbon
Heat conductivity value, be all that the function of graphitization temperature is drawn as final graphitization or again；
Fig. 4 (C) GO that the function of graphitization temperature is drawn as final graphitization or again gel derived graphene layer, GO
The conductivity value of platelet paper and FG foil；
The X-ray diffraction curve of Fig. 5 (A) GO film (dry GO gel)；
Fig. 5 (B) heat-treats the X-ray diffraction curve of the GO film of (partial reduction) at 150 DEG C,
Fig. 5 (C) height reduction and the X-ray diffraction curve of graphited GO film again,
Fig. 5 (D) height it is graphited again and recrystallization GO crystal X-ray diffraction curve, show high intensity
(004) peak, and
Fig. 5 (E) HTT is up to the X-ray diffraction curve of HOPG derived from 3,000 DEG C of polyimides.
Spacing between the graphene planes that Fig. 6 (A) is measured by X-ray diffraction；
Oxygen content in Fig. 6 (B) GO gel derived GO film；
Correlation between Fig. 6 (C) graphene between spacing and oxygen content；And
The thermal conductivity of Fig. 6 (D) GO gel derived GO film and soft graphite (FG) foil, is all as final heat treatment
What the function of temperature was drawn.
Fig. 7 (A) is derived from the paper and flexibility of the GO film of GO gel, discrete GO platelet (being not from GO gel state)
Tensile strength of the graphite foil in heat-treatment temperature range；
The scratch resistance for the GO film that Fig. 7 (B) is drawn as the function of heat treatment temperature.
The Graphene gel that Fig. 8 (A) is drawn as the function of viscosimeter spinner velocity (directly proportional to shear rate) is glued
Angle value (Linear-Linear scale)；
Fig. 8 (B) is in the viscosity number of Log-Linear scale, and
The viscosity number of Fig. 8 (C) Log-Log scale.
The discharge capacity value of Fig. 9 (A) three kinds of Li-S battery cores, the individually function as charge/discharge cycle number；First electricity
Core has the Cu foil respectively as the combination GO of anode and cathode collector and combines the Al foil of GO；Second battery core (the prior art
Battery core) have respectively as anode and cathode collector GO/ resin coating Cu foil and GO coating Al foil (do not lose in advance
It carves)；Third battery core (battery core of the prior art) has Cu foil anode collector and Al foil cathode current collector.
The Ragone curve graph of Fig. 9 (B) three kinds of battery cores below: the first battery core has respectively as anode and cathode collector
Combination GO Cu foil and combine GO Al foil；Second battery core (battery core of the prior art) has respectively as anode and cathode collection
The Cu foil of the GO/ resin coating of fluid and the Al foil (not having pre-etched) of GO coating；Third battery core (battery core of the prior art) tool
There are Cu foil anode collector and Al foil cathode current collector.
The battery core capability value of three kinds of magnesium metal battery cores of Figure 10 or less: the first battery core has respectively as anode and cathode afflux
The Cu foil of the combination GO of body and the Al foil for combining GO；Second battery core (battery core of the prior art) has respectively as anode and cathode
The Cu foil of the GO/ resin coating of collector and the Al foil (not having pre-etched) of GO coating；Third battery core (battery core of the prior art)
With Cu foil anode collector and Al foil cathode current collector.
Specific embodiment
The present invention provides a kind of metal foil film current collectors of the combination graphene oxide in battery or supercapacitor
(for example, as Fig. 1 (D) is schematically shown).The collector includes: (a) stand alone type, non-loading type thin metal foil (Fig. 1
(D) 214 in), the thin metal foil has thickness and two opposite but substantially parallel main surfaces from 1 μm to 30 μm；
(b) described two opposite at least one of main surfaces are chemically bonded in the case where not using adhesive or adhesive
On graphene oxide film 212.Fig. 1 (D) illustrates only a main surface and graphene oxide film for the metal foil 214
212 combine.It is preferable, however, that opposite main surface is also combined with graphene oxide film (being not shown in Fig. 1 (D)).As with
In the end pole for being electrically connected to external circuit, metal tabs 218 typically by melting welding or are soldered in the metal foil 214.
As shown in Fig. 1 (D), the preferred embodiment of the present invention is the metal foil collector in conjunction with graphene oxide,
Wherein there is no adhesive resin layer or passivation al oxide layers between the graphene oxide membrane and the Cu foil or Al foil.Phase
Than under, as schematically shown in Fig. 1 (C), the metal foil collector of the graphene of prior art coating typically and
Necessarily need the adhesive between graphene layer (graphene-resin composite materials) and the metal foil (for example, Cu foil)
Resin layer.In Al foil [Prabakar et al. that the graphene of the prior art coats；Bibliography 2] in the case where, graphene layer
There is naturally passivation aluminum oxide (aluminium oxide) layers between Al metal foil.This is because well-known following facts: when
When manufacturing and being exposed to room air, aluminium foil always forms passivation al oxide layer on Al foil surface.Pass through acetone or alcohol
Easy clean cannot remove this alumina layer.As by set forth in paragraph below, adhesive resin or al oxide layer are (i.e.
Make to be as thin as only 1nm) presence there is tremendous influence to the contact resistance increased between graphene layer and metal foil.We this shy
The discovery of people is ignored completely by the worker of all prior arts, and therefore, the metal foil of the graphene coating of the prior art
It is unsatisfactory for the performance and cost requirement of lithium battery or current collector of super capacitor.
Make the highly significant that graphene oxide sheet and the main surface of Cu, Ni or Ti foil directly contact and unexpected excellent
Point is following viewpoint: graphene oxide molecule can be integrated to these metal foils well under processing conditions of the invention
On, without using external resin binder or adhesive (therefore, not dramatically increasing contact resistance).These processing conditions
Including arranging graphene oxide sheet well in metal foil surface and then (more typically and being wished at 80 DEG C -1,500 DEG C
Hope ground 80 DEG C -500 DEG C and most typically and hopefully 80 DEG C -200 DEG C) at a temperature in the range of be heat-treated two layers of knot
Structure.Optionally, but it is not preferred ground, the heat treatment temperature can be up to 3,000 DEG C.
In the case where the collector based on aluminium foil, these processing conditions be included in coat and be combined with graphene oxide it
It is preceding to chemically etch away passivation al oxide layer, then it is heat-treated under the conditions of comparable temperature described above.It can
Alternatively, the graphene oxide can be prepared with GO gel state, it is characterised in that there is high oxygen content (to reflect a large amount
- OH and-COOH group) and have less than 5.0 (preferably < 3.0 and even more preferably < 2.0) pH value.It can make described
Al foil immerses in GO coagulation bath, and wherein acidic environment eliminates the passivation Al naturally2O3Layer.When the Al foil is shown from bath
When exposing, GO molecule or piece are adhered to naturally on clean, etched Al foil surface, and it is sudden and violent to be effectively prevented Al foil surface
It is exposed in open air (therefore, without passivation Al between Al foil surface and GO layers2O3Layer and no increased contact electricity
Resistance).It is never disclosed or suggested before this strategy.
Other than the chemical bonding ability of GO layer and the chemical etching ability of GO gel of the invention, combination of the invention
Thickness that gained graphene oxide film in the metal foil of graphene oxide has from 10nm to 10 μm, by weight from
Spacing between 0.1% to 10% oxygen content, the graphene planes of 0.335nm to 0.50nm, from 1.3g/cm3To 2.2g/cm3Object
Density is managed, all graphene oxide sheets, which are oriented to, is substantially parallel to each other and is parallel to main surface, when in no thin metal foil
In the case where independent measurement when, show thermal conductivity greater than 500W/mK and/or be greater than the conductivity of 1,500S/cm.This oxidation
Graphene film is chemically inert and provides the highly effective protective layer for resisting the corrosion of following metal foil.
Now, let us detailed examination such as the all-in resistance (including contact resistance) in the three-decker shown in Fig. 1 (C)
Size.Electronics in graphene layer 202 (layer 1) must move around in this layer, move through adhesive resin or passivation
Alumina layer 206 (layer 2), and it is then mobile to terminal tab 208 in metal foil layer 204 (layer 3).For the sake of simplicity, I
Will only consider to move through the thickness of the graphene layer, described adhesive/passivation layer thickness and described for electronics
The all-in resistance of the thickness of metal foil layer.Electronics movement in the face of both graphene or metal foil on direction is rapid and low electricity
Resistance；Therefore, this resistance is ignored in calculating of the invention.
The thickness direction resistance of conductor sheet film is given by: R=(1/ σ) (t/A), wherein conductor described in A=is transversal
Area (length x width), the thickness of conductor described in t=,AndCollector containing the coating of the graphene of adhesive or passive metal oxide skin(coating) can
To be considered as with graphene film, interfacial bonder resin layer (or passive oxidation aluminium layer) and the metal foil being electrically connected in series
The three-decker (Fig. 1 (C)) of layer.
All-in resistance is the summation of the resistance value of three layers: R=R1+R2+R3=ρ1(t1/A1)+ρ2(t2/A2)+ρ3(t3/
A31/ σ of)=(1)(t1/A1)+(1/σ2)(t2/A2)+(1/σ3)(t3/A3), wherein ρ=resistivity, σ=conductivity, t=thickness,
And A=layers of area, and approximatively, A1=A2=A3.Scanning electronic microscope examination disclose, described adhesive resin or
Passive oxidation aluminium layer is typically 5-100nm thick.The resistivity and aluminium oxide of most common adhesive resin (PVDF)
(Al2O3) resistivity typically 1013-1015In the range of ohm-cm.Assuming that A1=A2=A3=1cm2, graphene layer
Thickness direction electricalresistivityρ1=0.1 ohm-cm, adhesive or alumina layer electricalresistivityρ2=1 × 1014Ohm-cm, and
And metal foil layer resistivity is ρ3=1.7 × 10-6Ohm-cm (Cu foil) or ρ3=2.7 × 10-6Ohm-cm (Al foil).
It is also supposed that following optimum condition, wherein Cu foil or Al foil thickness=6 μm, graphene layer thickness=1 μm, and adhesive resin layer
Thickness is only 0.5nm (actually it is from 5nm to 100nm).Then the all-in resistance of the three-decker will be 5 × 106Ohm is simultaneously
And whole conductivity will be down to 1.4 × 10-10S/cm (referring to the first data line in the following table 1).If we assume that adhesive tree
Rouge layer is 10nm thickness, and the all-in resistance of the three-decker will be 1 × 108Ohm and whole conductivity will be down to 7.0 × 10- 12S/cm (referring to the 4th data line in the following table 1).Such 3 layers of composite construction will not be for the good of battery or supercapacitor
Good collector, because high internal resistance will imply that the inside heat production of low output voltage and a large amount.For based on Ni foil, Ti foil and not
The collector of rust steel foil, observed similar result (the data line 7-10 in table 1).
Table 1:
In contrast, if there is no adhesive resin or alumina layer (t2=0) (the feelings of collector such as of the invention
Condition), have 1.0 × 10 in conjunction with the all-in resistance of the Cu foil of graphene oxide-5Ohm value (with containing 1- μm of adhesive resin layer
The 1.0 × 10 of 3-tier architecture+7Ohm is compared).Refer to the following table 2.This represents the difference of 12 orders of magnitude (not being 12 times)！With phase
The 7.0 × 10 of the 3-tier architecture answered-11S/cm is compared, and for 2 layers of structure of the invention, conductivity will be 7.0 × 10+1S/cm.Again
Once, difference is 12 orders of magnitude.In addition, we have found that, compared with the collector based on graphene of the prior art, with
The lithium battery and supercapacitor that the metal foil collector of combination graphene oxide of the invention is characterized always show higher
Voltage output, higher energy density, higher power density, more stable charge-discharge cycles respond and continue more
Long without capacity attenuation or etching problem.
Table 2:
Since the collector that graphene of the invention is realized is produced by graphene oxide gel, presently describes and beg for
By term graphene, graphene oxide (GO), the prior art GO suspension and GO gel of the invention.
Block natural flake graphite is 3-D graphite material, wherein each particle by multiple crystal grain (crystal grain be graphite monocrystalline or
Crystallite) it constitutes, these crystal grain have the crystal boundary (amorphous or defect area) for defining neighbouring graphite monocrystalline.Each crystal grain by putting down each other
Multiple graphene planes of row orientation are constituted.Graphene planes in graphite microcrystal are by occupying the carbon atom structure of two-dimentional hexagoinal lattice
At.In given crystal grain or monocrystalline, graphene planes are stacked at the direction crystallography c- (perpendicular to graphene planes or basal plane)
And it is combined by Van der Waals force.Although all graphene planes in a crystal grain be it is parallel to each other, typically one
The graphene planes in graphene planes and neighboring die in crystal grain are different in orientation.In other words, in graphite particle
Different crystal grain orientation it is typically different from a crystal grain to another crystal grain.
Graphite monocrystalline (crystallite) is anisotropic in itself, wherein direction (crystallography a- axis or the b- axis direction) along basal plane
The characteristic of measurement and the characteristic measured along crystallography c- axis direction (thickness direction) are dramatically different.For example, the thermal conductivity of graphite monocrystalline
Rate (crystallography a- and b- axis direction) in basal plane can be up to about 1,920W/mK (theoretical value) or 1,800W/mK (experiment
Value), but 10W/mK (typically less than 5W/mK) is less than along crystallography c- axis direction.Further, multiple in graphite particle
Crystal grain or crystallite are typically orientated all along different directions.Therefore, the natural stone being made of multiple crystal grain of different orientation
Black particle is shown between the two limiting values (that is, in 5W/mK and 1, between 800W/mK, but typically < 100W/mK)
Average characteristics.
Be highly desirable in numerous applications be production have enough large scales and with all graphene planes along
The block graphite object that one desired direction is substantially parallel to each other.Such as, it is highly desirable to be that there is a kind of large scale stone
Black entity (for example, layer of the completely integrated of multiple graphene planes), the entity have the c- axis of all graphene planes
Direction is substantially parallel to each other, and has sufficiently large length and/or width (for example, for small-sized for specific application
It is used as collector in battery core, > 10cm2, and for being used as collector in large-scale battery core, > 200cm2) and answered for expection
Use (for example, as the thin layer being integrated in metal foil surface) that there is desired thickness (for example, 10nm to 10 μm).So far, also
It can not be by large scale integration graphene-metal foil entity of existing natural or synthetic graphite particle production this type.
The composition graphene planes (typically 30nm -2 μm of width/length) of graphite microcrystal can be by extruding and from the graphite
It extracts or is isolated to obtain the individual graphene film of carbon atom, premise is that overcoming interplanar Van der Waals force in crystallite.Six
The isolation of square carbon atom, individual graphene film is commonly known as single-layer graphene.Graphene planes with 0.3354nm
Between spacing in a thickness direction multilayer stone is commonly known as by the stacked body of multiple graphene planes that Van der Waals force combines
Black alkene.Multi-layer graphene platelet has up to 300 layers of graphene planes (on thickness < 100nm) but more typically up to
30 graphene planes (on thickness < 10nm), be even more typically up to 20 graphene planes (on thickness < 7nm),
And most typically it is up to 10 graphene planes (commonly known as lacking layer graphene in scientific circles).Single-layer graphene film and
Multi-layer graphene piece is collectively referred to as " nano-graphene platelet " (NGP).Graphene film/platelet or NGP are and 0-D fullerene, 1-D
The different a new class of carbon nanomaterial of CNT with 3-D graphite (2-D nano-sized carbon).
Early in 2002, our research group started the exploitation of grapheme material and related methods of production: (1)
B.Z.Jang and W.C.Huang, " Nano-scaled Graphene Plates [nanoscale graphite alkene plate] ", U.S. Patent number
7,071,258 (07/04/2006), the application submitted on October 21 in 2002；(2) B.Z.Jang et al. " Process for
Producing Nano-scaled Graphene Plates [method for producing nanoscale graphite alkene plate] ", United States Patent (USP)
Application number 10/858,814 (06/03/2004)；(3) B.Z.Jang, A.Zhamu and J.Guo, " Process for
Producing Nano-scaled Platelets and Nanocomposites is [multiple for producing nanoscale platelet and nanometer
The method of condensation material] ", U.S. Patent Application No. 11/509,424 (08/25/2006).
Intercalation is carried out to obtain graphite intercalation compound to natural graphite particles typically via with strong acid and/or oxidant
(GIC) or graphite oxide (GO) obtains NGP, as shown in Fig. 1 (A) (process flow chart) and Fig. 1 (B) (schematic diagram).
The presence of chemical species or functional group is for increasing spacing (d between graphene in clearance space between graphene planes002, such as
Pass through what X-ray diffraction measured), it thereby dramatically reduces and otherwise graphene planes keeps together along c- axis direction
Van der Waals force.GIC or GO immerses sulphur most often by by natural graphite powder (100 in 20 and Fig. 1 (B) in Fig. 1 (A))
It is produced in the mixture of acid, nitric acid (oxidant) and another oxidant (for example, potassium permanganate or sodium perchlorate).Gained
GIC (22 or 102) is actually certain type of graphite oxide (GO) particle.Then the GIC is repeatedly washed in water
With rinsing to remove excessive acid, graphite oxide suspension or dispersion are generated, the suspension or dispersion, which contain, to be dispersed in
Discrete in water and visually recognizable graphite oxide particle.There are two processing routes after this rinsing step:
Route 1 is related to going water removal to obtain " expansible graphite " from suspension, is substantially a large amount of dry GIC or dry
Dry graphite oxide particle.The constant temperature about 30 within the scope of typically 800 DEG C -1,050 DEG C is exposed in expansible graphite
When second to 2 minutes, GIC is subjected to 30-300 times of rapid expanding to form " graphite worm " (24 or 104), and the graphite worm is each
Naturally extruding but still interconnection the unsegregated graphite flake of major part aggregate.Graphite worm is presented in Fig. 2 (A)
SEM image.
In a possible subsequent step, can by these graphite worms (expanded graphite or " interconnection/do not separate
Graphite flake network ") recompression to obtain flexible graphite platelet or foil (26 or 106), typically have in 0.1mm (100
μm) thickness in -0.5mm (500 μm) range.Alternatively, in order to produce the mesh of so-called " exfoliated graphite sheet " (108)
, it can choose using low-intensity air mill or cutter simply to decompose the graphite worm, the expanded graphite is thin
Piece mainly contains the graphite flake or platelet (therefore, according to definition be not nano material) thicker than 100nm.
Expanded graphite worm, exfoliated graphite sheet and graphite worm recompression substance (commonly referred to as flexible graphite platelet or
Soft graphite foil) it is entirely 3-D graphite material, it is being fundamentally different from and is being clearly distinguished from 1-D nano-carbon material
(CNT or CNF) or 2-D nano-carbon material (graphene film or platelet, NGP).Soft graphite (FG) foil may be used as radiating equipment
Material, but show in the largest face of typically less than 500W/mK (more typically < 300W/mK) thermal conductivity and no more than 1,
The face internal conductance rate of 500S/cm.These low conductivity values are the direct results of following item: the stone of many defects, fold or folding
Black thin slice, interruption or gap and nonparallel thin slice (such as SEM image in Fig. 2 (B)) between graphite flake.It is many
Thin slice is angled with respect to each other (for example, misorientation of 20-40 degree) with very big angle.
In another possible subsequent step, expanded graphite is made to be subjected to high-strength mechanical shearing (for example, using ultrasound
Generator, high-shear mixer, high-intensitive air-jet mill or high-energy ball mill) to form isolated single layer and multilayer stone
Black alkene piece (it is referred to as NGP, 33 or 112), such as in our U.S. Application No. 10/858, disclosed in 814.Single-layer graphene
It can be as thin as 0.34nm, and multi-layer graphene can have the thickness of up to 100nm but more typically less than 20nm.
For the purpose of the individual graphene oxide sheet of separation/isolation from graphite oxide particle, route 2 is required to oxidation
Graphite suspension is ultrasonically treated.This is based on following viewpoint: the interval between graphene planes is from natural graphite
0.3354nm increases to the 0.6-1.1nm in highly oxidized graphite oxide, reduces significantly adjacent plane being maintained at one
The Van der Waals force risen.It is separation, isolation or discrete to be formed that ultrasonic power can be enough further separation graphene planes piece
Graphene oxide (GO) piece.It then can be by these graphene oxide sheets chemistry or thermal reduction to obtain " the graphite oxide of reduction
Alkene " (RGO) typically has 0.001%-10% by weight, more typically by weight 0.01%-5% and most allusion quotation
Oxygen content of the type ground by weight less than 2%.
In order to limit the purpose of claims hereof, NGP includes single layer and multilayer raw graphite alkene, graphene oxide
Or discrete patch/platelet of the graphene oxide of reduction.Raw graphite alkene has substantially 0% oxygen.Graphene oxide (including
RGO it) can have the oxygen of 0.01%-50% by weight.RGO has 0.01%-10% by weight, more typically by weight
With the counting 0.01%-5% and most typically oxygen content of 0.01%-2% by weight.
GO molecule in graphene oxide gel (GO gel) (will be described in detail later) is typically from GO gel
Remove oxygen (the more typically 30%- for containing 20%-47% by weight immediately but before subsequent heat treatment after liquid
47%).The GO gel refers to the aromatic molecule of highly-hydrophilic (with oxygen-containing group in planes of molecules or in edge
The graphene oxide molecule of (such as-OH ,-COOH and > O)) homogeneous solution, these molecular meltings (more than dispersing) are in acidity
In liquid (for example, the highly acidic aqueous solution with pH value lower than 5.0, more typically < 3.0 and often < 2.0).It is described
GO gel itself is free of obvious recognizable or discrete graphene or GO particle in solid piece or platelet form.These GO points
The sub and described dispersing liquid medium have comparable refractive index so that gained gel be it is optically transparent or it is translucent (such as
The ratio of fruit GO molecule is set to excessively high), or display light brown color.
In contrast, graphite particle or discrete graphene or graphene oxide sheet/platelet and the simple of acid and/or water mix
It is dark and fully opaque (even if wherein only having < 0.1% solid particle to be suspended in liquid medium that conjunction object looks like optics
In).These particles or graphene or GO piece/platelet simply disperse (not being dissolution) in fluid media (medium) and they are not formed
GO gel state.
These GO molecules in GO gel are highly reactive and are considered " huge molecule living ".It compares
Under, solid piece/platelet of the graphene of the prior art, GO and RGO is substantially " dead " species.The GO can be coagulated
Glue shearing appropriate or compression stress (for example, via curtain coating or molding) form shape in metal foil surface, and drying is (wherein
Liquid component is partly or wholly removed), and be heat-treated under certain conditions to obtain and be chemically bonded to metal foil table
The film of height-oriented graphene film on face.The heat treatment is for being connected chemically these active or living GO molecules to be formed
2-D the or 3-D network of chemically combined graphene molecules with heavy molecular weight, and so that the oxygen content of GO significantly reduces
To being lower than by weight, 10% (heat treatment temperature < 200 DEG C), more typically < 5%, further more typically < 2% (heat treatment is warm
< 500 DEG C of degree) and most typically < < 1% (heat treatment temperature is up to 1,500 DEG C).
Although it is (including " dead that the GO gel itself is free of obvious recognizable/discrete graphene film/platelet or NGP
" GO piece/platelet), but can intentionally fill out discrete graphene film/platelet, exfoliated graphite sheet and other kinds of solid
Material is added in the GO gel to form mixture gel.By this mixture gel drying and identical heat can be subjected to
Processing is converted into the film of the GO piece of height-oriented and chemical merging with the GO molecule that will be lived.Now with filler phase (for example, discrete
NGP, CNT and carbon fiber) enhance grapheme material derived from this graphene oxide gel.
When being stacked film forming, film or the scraps of paper (34 or 114), solid NGP is (including raw graphite alkene, GO and GRO
Discrete patch/platelet) do not show high conductivity typically.In general, the paper made of the platelet of discrete graphene, GO or RGO
Shape structure or felt (for example, passing through those of the vacuum assisted filtration technique preparation scraps of paper) show many defects, fold or folding
Graphene film, interruption or gap and nonparallel platelet (for example, SEM image in Fig. 3 (B)) between platelet cause
Relatively low conductivity and low structural strength.
The low portion of Fig. 1 (A) is illustrated for the typical method by polymer production pyrolytic graphite film.The method is opened
It starts under 400 DEG C -1,000 DEG C of carburizing temperature in 10-15Kg/cm2Typical pressure under carbonized polymers film 46 (for example,
Polyimides) continue 2-10 hours to obtain char-forming material 48, it is followed by 2,500 DEG C -3,200 DEG C in 100-300Kg/
cm2Hyperpressure under carry out graphitization processing continue 1-24 hours to form graphite film 50.It is tieed up under such ultra-high temperature
It is technically extremely challenging for holding such hyperpressure.This is difficult, slow, tediously long, energy consumption and extremely expensive mistake
Journey.In addition, the carbonization of certain polymer (for example, polyacrylonitrile) is related to the discharge of Toxic kind.Further, since production is thinner than 30
μm precursor polyimide film difficulty, it has not been possible to mass production, which is thinner than derived from 15 μm of polyimides, is pyrolyzed film.This is not
Meet the requirement with 1-10 μ m-thick collector.
The graphene film (< 2nm) of specific type on the surface Ni or Cu by carrying out appropriate hydrocarbon gas (for example, C2H4) urge
Change CVD to prepare.In the case where Ni or Cu are catalyst, will via at 800 DEG C -1,000 DEG C decomposing hydrocarbon gas molecule obtain
The carbon atom obtained deposits on Ni or Cu foil surface the piece for being formed as polycrystalline single layer or few layer graphene.These graphenes are thin
Film (being optical clear and conduction) is intended for such as touch screen (replace indium tin oxide or ito glass) or semiconductor
The application of (replace silicon, Si).However, these ultra-thin polycrystalline graphite alkene films do not have enough biographies for being used as collector
The property led (too many crystal grain or too many grain boundary, and all crystal grains are oriented in different directions) and not sufficiently thick
(most preferably from 1 μm to 10 μm).It is put down in addition, the CVD technique of Ni- or Cu- catalysis is not suitable for more than 5-10 graphene of deposition
Face (typically < 2-4nm, more typically < 2nm), is more than so more graphene planes, Ni or Cu catalyst below cannot mention again
For any catalytic effect.Do not have experimental evidence show the CVD graphene layer thicker than 5nm or 10nm be it is possible, needless to say 1 μm
(1,000nm) is to 10 μm (10,000nm).
The present invention also provides a kind of for producing the method for combining the metal foil collector of graphene oxide, the method
It include: the graphene oxide gel of graphene oxide molecule that (a) preparation has dispersion and is dissolved in fluid media (medium), wherein institute
It states graphene oxide molecule and (is typically by weight of from more than 30% and more typically by weight containing by weight of from more than 20%
Between 30% and 47%) oxygen content；(b) it is distributed in the main surface of support metal foil and deposits one layer of graphene oxide
Gel, to be formed thereon the graphene oxide gel of deposition, wherein the distribution and deposition procedure include the graphite oxide
Alkene gel shear-induced desaturation (cause graphene oxide molecule on desired one or more directions accumulation well and
It arranges well, is beneficial to the merging and integration of the GO molecule in subsequent heat treatment process)；(c) from the oxidation deposited
The fluid media (medium) is removed in Graphene gel layer partially or even wholly to form dry graphene oxide layer, the dry oxygen
Graphite alkene layer has the interplanar spacing d of the 0.4nm to 1.2nm such as measured by X-ray diffraction002It is not small by weight
In 20% oxygen content；(d) from 80 DEG C to 1, the graphene oxide layer, journey are heat-treated under 500 DEG C of heat treatment temperature
Degree is so that spacing d between the graphene oxide membrane layer plane002It is reduced to the value and oxygen content from 0.3354nm to 0.5nm
It is reduced to by weight less than 10%.
In a more preferred embodiment, step (c) includes forming the interplanar spacing d with 0.4nm to 0.7nm002With press
Poidometer is not less than the graphene oxide layer of 20% oxygen content；And step (d) includes being heat-treated the graphene oxide layer,
Degree is so that interplanar spacing d002It is reduced to the value from 0.3354nm to 0.36nm and the oxygen content is reduced to by weight
Meter is less than 2%.
Contained by the graphene oxide film that heat-treatment oxidation Graphene gel at a certain temperature obtains chemically combined
Graphene molecules.The aromatic molecule or graphene planes (carbon atom of hexagonal structure) of these planes are parallel to each other.These are flat
The lateral dimension (length or width) in face be it is huge, typically compared with the maximum crystallite dimension of beginning graphite particle (or maximum structure
At graphene planes size) the several times greater or even several orders of magnitude.Film is made of many " huge graphene oxide farmlands ", is had
All composition graphene planes are substantially parallel to each other, and there is GO thin layers of molecules to be chemically bonded in following metal foil.This is
A kind of unique and new material that may be present was not found, developed or suggested in the past.
The graphene oxide gel is a kind of very unique and novel material, and the material unexpectedly has greatly
Cohesive force (self-bonding, auto polymerization and self-crosslinking ability) and adhesion strength (the diversified surface of solids can be chemically bonded to
On).Do not teach or imply in the prior art these features.The GO gel is by that will originate graphite material in the reaction vessel
The powder or long filament of material immerse acquisition in oxidation liquid medium (for example, mixture of sulfuric acid, nitric acid and potassium permanganate).It is described
Originate graphite material can selected from natural graphite, artificial graphite, mesocarbon, mesophase pitch, carbonaceous mesophase spherules, soft carbon,
Hard carbon, coke, carbon fiber, carbon nano-fiber, carbon nanotube, or combinations thereof.
When originating powdered graphite or long filament mixes in oxidation liquid medium, gained slurry (non-uniform suspension) is most
It is complete dark and opaque at first sight.When the oxidation of graphite carries out enough under the conditions of controlled pH at the reaction temperatures
When the time of length, reactive material can be eventually become without recognizable or visually identifiable dispersion solid particle
Homogeneous solution (different from containing the initial non-uniform suspension of identifiable solid particle).The solution can be optics half
It is transparent or transparent or brown, also seem and behaves like polymer gel.The oxidation of this heavy oxidation induction
Graphene gel is made of the graphene oxide molecule for dissolving in liquid medium.It is described before any subsequent heat treatment
Graphene oxide molecule have by weight not less than 20% (typically by weight from the oxygen content of 30%-50%), and
When be in gel state when, their molecular weight be typically less than 43,000 gram/mol (frequently less than 4,000 gram/mol but
It is typically greater than 200 grams/mol).The graphene oxide gel is by the graphene oxide molecule structure that is dissolved in acid medium
At, the acid medium have typically not higher than 5.0 (more typically < 3.0 and most typically < 2.0) pH value.
When measuring at 20 DEG C before shear-induced desaturation, the graphene oxide gel has from 500 centipoises
(cP) to 500,000cP typical viscosities.When being measured at 20 DEG C before the shear-induced desaturation program, the viscosity
More preferably greater than 2,000cP and be less than 300,000cP.Preferably as the precursor of integral piece grapheme material, the GO
The viscosity of gel is in the range of 2,000-50,000cP.Preferably, the GO gel is made to be subjected to shear stress field, so that cutting
During or after cutting induction desaturation, the viscosity decreases below 2,000cP (or even lower than 1,000cP).In embodiment,
When measuring at 20 DEG C before shear-induced desaturation, the graphene oxide gel has the viscosity greater than 5,000cP, but
During or after shear-induced desaturation, viscosity decreases below 5,000cP (preferably and typically lower than 2,000cP or very
To lower than 1,000cP).The viscosity data measured at 20 DEG C is (as example, shown in Fig. 8 (A), 8 (B) and 8 (C)
) clearly illustrate, even if hyperviscosity value (for example, 300,000cP) can also be decreased under sufficiently high shear rate
1,000-2,000cP.This is greater than the reduction of 2 orders of magnitude, this is unusually unexpected observation result.When right with logarithm-
When number scale, the straight line of data indicates shear-thinning fluid flow behavior.
In step (b), the GO gel preferably forms shape under the influence of shear stress.Such shearing program
One example is to be cast or coated GO gel (gel state fluid) film using coating machine.This program is similar on solid substrate
Coat one layer of varnish, paint, coating or ink.When forming the film, or when in roller/blade/wiper and supporting base material
Between when applying relative motion, the roller, " doctor blade " or wiper generate shear stress.Quite unexpectedly and show
It lands, such shear action reduces the effective viscosity of the GO gel and enables plane oxidation graphene (GO) molecule
It is arranged well along such as shear direction.Further unexpectedly, when the liquid component in then removal GO gel is with shape
When at the GO substance well accumulated being at least partially dried, such molecules align state or preferred orientation are not destroyed.It is described
Dry GO substance direction in face and perpendicular between in-plane have high birefringence coefficient.Another reality of such program
Example is to inject GO substance under the influence of shear stress or die casting is into cavity body of mould or molding die/tool.It then will be
The liquid component of clipped GO substance in cavity body of mould partially or even wholly goes divided by obtaining portion point ground or fully to do
Dry GO substance contains accumulation well and well-arranged " living " GO molecule.
Then the GO substance for drying this is subjected to the heat treatment of appropriately programmed.For 80 DEG C -500 DEG C of temperature range,
The GO substance undergoes the chemistry merging being subjected between some GO molecules with the chemical reaction of metal foil surface, and oxygen first
Content is reduced from typically 30%-50% (dry original sample) heat to 5%-6%.Spacing is from about between this processing leads to graphene
0.6-1.0nm (as former state dry) is reduced to about 0.4nm, and thermal conductivity from about 100W/mK increases to 500W/mK simultaneously in face
And conductivity increases to > 2,000S/cm from 800S/cm.Even if can also occur in the case where so low temperature range
It is connected chemically.GO molecule keeps good arrangement, but spacing keeps relatively large (0.4nm or bigger) between GO.Many good fortunes of functional group containing O
It leaves and.
For 500 DEG C -1,500 DEG C of heat-treatment temperature range, occur between adjacent GO molecule extensive chemical combination, polymerization,
And crosslinking.Oxygen content is reduced to typically < 2.0% (more typically < 1.0%), and spacing between graphene is caused to be reduced to about
0.345nm.This means that some starting graphiteizations start at such lower temperatures, and up to 2,500 are typically needed
DEG C temperature come start the graphitizable material of graphited routine (such as polyimide film of carbonization) formed sharp contrast.This is
The metal foil of combination graphene film of the invention and its another distinguishing characteristics of production method.These, which are connected chemically reaction, causes
Thermal conductivity increases to 1,400-1,500W/mK in the face of graphene film and/or face internal conductance rate increases to > 5,000S/cm.
X-ray diffraction pattern is obtained with the x-ray diffractometer radiated equipped with CuKcv.The displacement of diffraction maximum and broadening make
It is calibrated with silicon powder reference substance.Use Mering equation, d002=0.3354g+0.344 (1-g) is calculated by X-ray figure and is graphitized
G is spent, wherein d002It is the graphite or graphene crystal interlayer spacing in terms of nm.Only work as d002Equal to or less than about 0.3440nm
When, this equation is just effective.With the d for being higher than 0.3440nm002Graphene oxide membrane or mild oxidation graphite crystal material it is anti-
It has reflected and has served as interval base to increase the oxygen-containing functional group (- OH, > O on such as graphene molecules plane surface of spacing between graphene
With the presence of-COOH).
Another knot of the degree of order of integral piece grapheme material and ordinary graphite crystal of the invention can be used to characterize
Structure index is " inlaying the latitude of emulsion ", by the full width at half maximum (FWHM) table of the rocking curve (x-ray diffraction intensity) of (002) or (004) reflection
Show.This degree of order characterization graphite or graphene crystalline size (or crystallite dimension), the amount of crystal boundary and other defect and preferably
Degree of grain alignment.The almost ideal monocrystalline of graphite is characterized by having that 0.2-0.4's inlays latitude of emulsion value.Our one integral piece
(wherein heat treatment temperature is not less than most of latitude of emulsion values of inlaying having in the range of this 0.2-0.4 of formula grapheme material
2,000℃).However, then some values are in 0.4-0.7 if maximum heat treatment temperature (HTT) is between 1,000 DEG C and 1,500 DEG C
In the range of, and if HTT is between 500 DEG C and 1,000 DEG C, then some values are in the range of 0.7-1.0.
The temperature condition of heat treatment of GO is so that the graphene oxide film relative non-porous of coating on metal foil, has extremely
Few 1.5g/cm3Phsyical density or porosity level lower than 20%.Under more typical processing conditions, the film has
At least 1.7g/cm3Phsyical density or porosity level lower than 10%.In most cases, the film has and is greater than
1.8g/cm3Phsyical density or porosity level less than 5%.Chemically combined graphene planes in the film are typically
Contain sp2And sp3Electron configuration combination (especially for lower than 1,500 DEG C maximum treatment temperature prepare those of film).
Have following characteristics (single in conjunction with the gel derived graphene oxide film of graphene oxide (GO) on metal foil
Solely or in combination):
(1) if being formed under the conditions of desired shear stress field, then carrying out appropriate heat treatment, graphene oxide is thin
Film is integrated graphene phase.The film has wide/long chemically combined graphene planes, and the graphene planes are basic
On be oriented parallel to one another.In other words, all crystal grains and its all crystallography c- axis direction for constituting graphene planes are primarily directed to
Identical direction.This conclusion is using SEM, TEM, selected diffraction (with TEM), X-ray diffraction, atomic force microscope
(AFM), it is obtained after the extensive research of the combination of Raman spectroscopy and FTIR.
(2) felt of the paper-like piece (that is, soft graphite foil), exfoliated graphite sheet (thickness 100nm) of expanded graphite worm, with
And the paper or film of graphene or GO platelet be graphene, GO or RGO multiple discrete graphite flakes or discrete platelet it is simple
, unbonded aggregation/stacked body.In contrast, the graphene oxide film of the invention from GO gel is complete one
The single graphene entity or monolithic of body are free of discrete sheet or platelet.
(3) in the prior art method, the original for constituting graphite particle can be obtained by expansion, extruding and separating treatment
The discrete graphene film (thickness<<100nm) or exfoliated graphite sheet (>100nm) of beginning structure.By by these discrete patch/thin slices
Film is simply mixed and be re-compressed into, can attempt to be orientated these piece/thin slices hopefully along a direction.However,
With these conventional methods, the composition thin slice or piece of gained film (aggregation, paper, film or felt) will stay in that discrete sheet/piece/
Platelet, the discrete sheet/piece/platelet can hold with the naked eye or under low magnifying power optical microscopy (x100-x1000)
It changes places and distinguishes or be clearly observed.
In contrast, the preparation of GO film of the invention is related to original graphite particle heavy oxidation, and degree is practical
Each upper original graphite alkene plane has been oxidized and has been isolated from each other to become individual molecule, and the individual molecule is on side
Also at edge and mainly there is highly reactive property functional group (for example,-OH, > O and-COOH) on graphene planes.These lists
Only hydrocarbon molecule (element for also containing such as O and H other than carbon atom) is dissolved in reaction medium (for example, water is mixed with sour
Close object) in form spawn (referred to herein as GO gel).It then, will typically under the conditions of shear stress field
This gel is cast on smooth substrate surface or is injected into cavity body of mould, and then goes to do divided by formation by liquid component
It is GO layers dry.When heated, these highly reactive property molecules are mainly along graphene planes in transverse direction (length or width
Direction) on also react with each other and be connected chemically between graphene planes (in a manner of edge-to-edge) and in some cases.
Fig. 3 (D) illustrate it is plausible be connected chemically mechanism, wherein as example illustrate only 2 arrangement GO molecules,
Although a large amount of GO molecule can be connected chemically together to form integral piece graphene layer.It can also be with face in addition, being connected chemically
Occur to opposite, rather than just edge-to-edge.These connections and merging reaction carry out in this way, that is, so that described point
Sub- chemistry merges, connects and integrally turn to single an entity or monolithic.The molecule loses the original of their own completely
Beginning identity, and they are no longer discrete piece/platelet/thin slices.There is only a single layer structure, (integral piece graphene is real
Body), it is a giant molecule or is only the network (have substantial infinite molecular weight) for interconnecting huge molecule.All structures
It is very big in lateral dimension (length and width) at graphene planes, and if is generated under the conditions of shear stress
(particularly into film, thickness<20 μm) and be heat-treated under higher temperature (such as>1,000 DEG C or much higher), then this
A little graphene planes are substantially parallel to each other.
Use the combined further investigation of SEM, TEM, selected diffraction, X-ray diffraction, AFM, Raman spectroscopy and FTIR
Show the graphene monolithic by several huge graphene planes (wherein length/width be typically > > 100 μm, more typical
Ground > > 1mm, and most typically > > 1cm) constitute.These huge graphene planes often not only (are such as existed by Van der Waals force
In conventional graphite microcrystal like that) but also by covalent bond stacks and combine along thickness direction (crystallography c- axis direction).
Without being limited by theory, but Raman and FTIR spectrum method research seem to indicate that sp2(leading) and sp3(weak but presence) electron configuration
Coexist, rather than just the conventional sp in graphite2。
(4) this integrated graphene entity is not by with resin binder or adhesive that discrete sheet/platelet is glued
Or made of being combined together.On the contrary, the GO molecule in the GO gel is merged by being connected with each other or being formed covalent bond
Integrated graphene entity, without the use of any external binder molecule or polymer added.
(5) typically there is this one chip graphene entity the crystallography c- axis in all crystal grains to be substantially parallel to each other.
This entity is derived from GO gel, and the GO gel is correspondingly by initially with the natural or artificial graphite of multiple graphite microcrystals
Particle obtains.Before by chemical oxidation, these starting graphite microcrystals have the initial length (L in crystallography a- axis directiona)、
Original width (the L in b- axis directionb) and the thickness (L in c- axis directionc).After heavy oxidation, these initially discrete graphite
Particle is chemically converted the height virtue of functional group's (such as-OH ,-COOH etc.) for edge or surface carrying with significant concentration
Fragrant race's graphene oxide molecule.These aromatic series GO molecule in the GO gel has lost it as graphite particle or thin
The original identity of a part of piece.After removing liquid component in the GO gel, gained GO molecule is formed substantially without fixed
The structure of shape.After heat treatment, these GO molecular chemistries merge and connect into the integral piece or one chip graphite of high-sequential
Alkene entity.
Gained graphene oxide film typically has the L of noticeably greater than original crystalliteaAnd LbLength or width.This is thin
The length/width of film is typically greater than the L of original crystalliteaAnd Lb.Independent crystal grain even in this graphene entity also has significantly
Greater than the L of original crystalliteaAnd LbLength or width.
(6) due to these unique chemical compositions (including oxygen content), form, crystal structure (including between graphene between
Away from) and structure feature (for example, very close to each other and in graphite between few defects, good chemical bonding and graphene film
Alkene plane is interrupted), one chip graphene oxide membrane derived from graphene oxide gel has outstanding thermal conductivity, conductance
The unique combination of rate, mechanical strength and scratch resistance.In the case where not using adhesive or adhesive, this film is also tied well
It closes in following metal foil.
Features described above will be further described and be explained as follows: as shown in Fig. 1 (B), graphite particle (for example, 100)
Typically it is made of multiple graphite microcrystals or crystal grain.
Due to the weak Van der Waals force of keeping parallelism graphene layer, natural graphite can be handled, so that can be by graphene
Spacing between layer is obviously opened in order to provide the significant expansion in c- axis direction, and to form intumesced graphite structure,
Wherein the Lamellar character of carbon-coating is substantially retained.In general, by natural graphite flake (such as 100 in Fig. 1 (B)) in acid solution
Middle intercalation is to produce graphite intercalation compound (GIC, 102).By GIC washing, dry and then by being exposed to high temperature
Continue short period and extruding.This leads to that thin slice expands in the c- axis direction of graphite or extruding is up to its original size
80-300 times.Expanded graphite thin slice is vermiform in appearance, and is therefore commonly known as worm 104.It can not make
With these graphite flake worms of significant expansion are configured to cohesion or integrated Expandable graphite sheet in the case where adhesive,
Such as the typical density having for most of applications is about 0.04-2.0g/cm3Net, paper, item, band, foil, felt etc. (typically
Referred to as " soft graphite " 106).
The upper left of Fig. 1 (A) shows flow chart, and the flow chart is illustrated for manufacturing soft graphite foil and resin
The art methods of the Flexible Graphite Composites of dipping.These methods are typically begun with intercalator (typically, strong acid
Or acid blend) to (for example, the natural graphite or synthetic graphite) intercalation of graphite particle 20 to obtain graphite intercalation compound 22
(GIC).After being rinsed in water to remove excessive acid, the GIC becomes " expansible graphite ".Then by the GIC or can be swollen
Swollen graphite is exposed under hot environment (for example, the tube furnace being set in advance in 800 DEG C -1, at a temperature in the range of 050 DEG C
In) continue short duration (typically, from 15 seconds to 2 minute).This heat treatment allows the graphite in its c- axis direction
To hundred times to obtain vermiform myrmekitic texture 24 (graphite worm), the structure contains extruding but unsegregated stone for expansion 30
Black thin slice has the macropore being inserted between these interconnection thin slices.The example of graphite worm is presented in Fig. 2 (A).
In a kind of method of prior art, by using calendering or rolling techniques, by expanded graphite, (or a large amount of graphite is compacted
Worm) recompression is to obtain soft graphite foil (106 in 26 or Fig. 1 (B) in Fig. 1 (A)), typically much than 100 μ m-thicks.
The SEM image that the cross section of soft graphite foil is presented in Fig. 2 (B), it illustrates have to be not parallel to soft graphite foil surface
Orientation many graphite flakes, and there are many defects and flaws.
Largely due to these misorientations of graphite flake and the presence of defect, commercially available soft graphite foil is logical
Often with (thickness direction or side Z- (through-plane) between the face of the face internal conductance rate, 15-30S/cm that have about 1,500S/cm
To) conductivity, 140-300W/mK face in thermal conductivity between thermal conductivity and the face of about 10-30W/mK.These defects and mistake take
To also causing low mechanical strength (for example, defect is potential stress concentration portion position, crackle is preferentially initiated here).These
Characteristic is insufficient for many thermal management applications, and the present invention specifically addresses these problems.
In the method for another prior art, expanded graphite worm 24 can be impregnated with resin and then compress and consolidate
Change to form Flexible Graphite Composites 28, intensity is generally also low.In addition, after resin dipping, the electricity of the graphite worm
Conductance and thermal conductivity can reduce by two orders of magnitude.
Alternatively, high-intensitive air-jet mill, high-intensitive ball mill or Vltrasonic device, which can be used, makes the extruding
Graphite is subjected to high-strength mechanical shearing/separating treatment to generate the nano-graphene platelet 33 (NGP) of separation, wherein all stone
Black alkene platelet is thinner than 100nm, most of to be thinner than 10nm and be single-layer graphene in many cases (also as in Fig. 1 (B)
Shown in 112).NGP is made of a graphene film or multiple graphene films, wherein each is the two dimension of carbon atom, six sides knot
Structure.
Further alternatively, under low-intensity shearing, graphite worm tends to be separated into so-called exfoliated graphite sheet
(108 in Fig. 1 (B), there is > the thickness of 100nm.Papermaking can be used in these thin slices or felt technique be formed as graphite paper or
Felt 106.This expanded graphite paper or felt 106 are the simple aggregation body or stacked body of discrete sheet, there is defect, interrupt and this
Misorientation between a little discrete sheets.
Can be used paper technology will a large amount of multiple NGP (discrete patch/platelet including single layer and/or few layer graphene,
33 in Fig. 1 (A)) graphene paper (114 in 34 or Fig. 1 (B) in Fig. 1 (A)) are made.Fig. 3 (B) is shown using paper maker
The SEM image for graphene paper/film cross section that skill is prepared by discrete graphene film.Described image show in the presence of being folded or
Many discrete graphene films of (not being integration) are interrupted, most of platelet orientations are not parallel to film/paper surface, lack there are many
Sunken or flaw.Even if these NGP aggregations still show relatively low conductivity when by closs packing.
Precursor in conjunction with graphene oxide film on metal foil is graphene oxide gel 21 (Fig. 1 (A)).This GO is solidifying
Glue obtains in the following manner: in the reaction vessel, will immerse Strong oxdiative liquid in the graphite material 20 of powder or fibers form
In to form suspension or slurry, the suspension or slurry are initially optically opaque and dark.This is optically opaque
Degree reflect the fact that: oxidation reaction at the beginning, discrete graphite flake and the discrete graphite oxide in follow-up phase
The scattering of alkene thin slice and/or absorption visible wavelength, lead to the flowing material of opaque and usual dark color.If allowing graphite powder
End carries out sufficiently long a period of time with reacting between oxidant under sufficiently high reaction temperature, then this opaque suspension
It is transformed into brown color and typically translucent or transparent solution, is known as the equal of " graphene oxide gel " now
Uniform flow body (21 in Fig. 1 (A)), the homogeneous (uniform) fluid are free of recognizable discrete graphite flake or graphite oxide platelet.If
It distributes and deposits off field in shear stress, the GO gel experience viscosity reduces and molecularly oriented is to form " GO of orientation " 35,
It can be heat-treated to become the monolithic thin-film entity 37 being integrated in metal foil.
In addition, this graphene oxide gel be typically it is optically transparent or translucent and visually uniform, do not have
Recognizable discrete sheet/platelet of graphite dispersed therein, graphene or graphene oxide.In the GO gel, GO
Molecule is equably dissolved in acidic liquid medium.In contrast, discrete graphene film, graphene oxide sheet and expanded graphite
Conventional suspension liquid of the thin slice in fluid (for example, water, organic acid or solvent) seem color for dark, black or dark-brown,
Even if wherein individual graphene or graphene oxide sheet or exfoliated graphite sheet are with the naked eye or low magnifying power light microscope
(100X-1,000X) is also that can distinguish or identifiable.
The graphene oxide molecule of the dissolution of graphene oxide gel in liquid medium is aromatic series chain, the aromatic series
Chain, which has, is typically less than 1,000, more typically less than 500 and in many cases average phenyl ring in the chain less than 100
Number.From combined atomic force microscope, high-resolution TEM and molecular weight measurement, most of molecules, which have, is more than 5 or 6 phenyl ring
(most of > 10 phenyl ring).Based on our elemental analysis, the aromatic molecule of these phenyl ring types is heavy oxidation, is contained
Have the functional group (such as-COOH and-OH) of high concentration, and therefore in polar solvent (such as water) be " soluble " (more than
It is dispersible).The estimation molecular weight of these graphite oxide alkene polymers in gel state typically 200 grams/mol with
Between 43,000 grams/mol, more typically between 400 grams/mol and 21,500 grams/mol and most typically 400
Gram/mol and 4,000 grams/mol between.The typical viscosities value of GO gel is shown in Fig. 8 (A) to Fig. 8 (C).
These shla molecules behave like polymer and can unexpectedly react with each other and become chemistry even
Connecing has good structural intergrity and high heat conductance (during subsequent heat treatment or graphitization processing again) to be formed
Graphene layer.Conventional discrete graphene film, graphene oxide sheet or graphite flake does not have any autoreaction or cohesive adhesive
Ability.Also extremely surprisingly, during subsequent heat treatment or graphitization processing again, these in the GO gel can
Soluble molecule can be chemically combined metal foil surface.
Once again, definitely and most significantly, continuing when drying at sufficiently high temperature and being heat-treated the gel
When the sufficiently long period, with these graphene oxide molecules existing for GO gel state can mutual chemical combine, connection or
Merge, and becomes integrally to turn to extremely long and wide graphene layer (for example, Fig. 3 (A)).Do not have individual graphene platelet or
Piece is recognizable；They have been chemically converted as chemically active or living GO molecule, and the molecule is fully connected to each other
And chemical integration is to form stratiform integral piece ontology (unitary body) on graphene planes direction, and these are whole
What part formula ontology was seemingly combined along thickness-direction (or the direction Z-) mutual chemical.X-ray diffraction, which is studied, to be had confirmed, d-
Spacing (distance between graphene planes) has been restored to about 0.3354nm (oxygen with by weight 0.01%) to 0.40nm
(oxygen with about 5.0%-10%).Any gap is not appeared between these graphene layers, and therefore, these layers are basic
On be merged into a big integral piece ontology.Fig. 3 (A) depicts the example of such huge integral piece ontology.In Fig. 3 (C)
Further illustrate the forming method for such graphene entity.
It is natural to be selected from by the starting graphite material of heavy oxidation in order to form the purpose of graphene oxide gel
Graphite, artificial graphite, mesocarbon, mesophase pitch, carbonaceous mesophase spherules, soft carbon, hard carbon, coke, carbon fiber, carbon Nanowire
Dimension, carbon nanotube, or combinations thereof.The graphite material preferably in the form of powder or short long filament, have lower than 20 μm, it is more excellent
The size that choosing is lower than 10 μm, is further preferably no larger than 5 μm and more preferably less than 1 μm.
Use the artificial graphite of the average grain diameter with 9.7 μm as example, typical program is related to graphite particle point
Dissipate in typically 0 DEG C -60 DEG C at a temperature of sulfuric acid, nitric acid and potassium permanganate (weight ratio in 3:1:0.05) oxygen
Continue in agent mixture typically at least 3 days, preferably 5 days and 7 days or longer more preferable.Gained in gel aoxidizes stone
The average molecular weight of black alkene molecule is about 20,000-40 if being 3 days if the processing time, 000 gram/mol, if it is 5 days
If be < 10,000 gram/mol, and be < 4,000 gram/mol if being longer than 7 days.Required gel formation time takes
Certainly in the partial size of original graphite material, lesser partial size needs the shorter time.It is important to note that, if not up to critical
The suspension (graphite particle being dispersed in oxidant liquid) of gel formation time, powdered graphite and oxidant seems complete
It is opaque and uneven, it means that discrete graphite particle or thin slice still suspend (but insoluble) in liquid medium.Once
More than this crash time, entire suspension reforms into optical translucent or transparent (if GO content is sufficiently low) and brown
Color, it means that the graphite of heavy oxidation loses its original graphite identity completely and gained graphene oxide molecule is complete
It is dissolved in oxidant liquid, forms uniform solution (being no longer suspension or slurry).
It must further be noted that if by the suspension after the processing time of shorter than required gel formation time
Or slurry rinses and dry, we will only recycle graphite oxide powder or graphite intercalation compound (GIC) powder, can be with
Afterwards by extruding and separate to generate discrete nano-graphene platelet (NGP).In the strong oxidizer and enough oxygen of not sufficient amount
In the case where changing the duration, the graphite or graphite oxide particle cannot be converted into GO gel state.
If the graphene oxide gel be by with original graphite crystallite dimension (for example, average grain size, Dg)
Graphite material obtain, gained graphene oxide film be be noticeably greater than this initial grain size crystallite dimension stone
Black alkene structure.The film does not have and can be identified as any crystal grain relevant to any specific particle of graphite material is originated.
It is connected chemically and merges or the one chemical conversion substantially graphene chain of infinite molecular weight when primary granule is converted into
When the graphite oxide molecule of network, they lose its identity completely.
Further, even if graphene oxide gel is by the graphite material with multiple graphite microcrystals (for example, natural stone
Ink powder end) obtain, the graphite microcrystal does not show preferred crystal orientation (as by X-ray diffraction or electron diffraction
Measurement), very high preferred crystal orientation degree, which is also typically shown, in conjunction with gained film on metal foil (such as passes through phase
What same X-ray diffraction or electron diffraction measured).This be and another evidence come show to constitute it is original or starting graphite
The composition graphene planes of the lonsdaleite atom of the particle of material have been chemically modified, have converted, having rearranged, reorientation, company
Connect or be crosslinked, merge and integration, be graphitized and even recrystallize again.
The present invention also provides a kind of rechargeable battery, the battery contains combination graphene oxide film of the invention
Metal foil as anode collector and/or cathode current collector.This can be any rechargeable battery, as zinc air battery core,
Nickel metal hydride battery core, sodium ion battery core, metallic sodium battery core, magnesium ion battery core, magnesium metal battery core, only list.This
The battery of invention can be lithium rechargeable battery, contain integral piece graphene layer as anode collector or cathode collector
Body, the lithium battery can be lithium-sulphur battery core, lithium-selenium battery core, lithium sulphur/selenium battery core, lithium-ion electric core, lithium-air battery core, lithium-
Graphene battery core or lithium-carbon battery core.Another embodiment of the invention is a kind of capacitor, and the capacitor contains the present invention
Collector as anode collector or cathode current collector, the capacitor is symmetrical supercapacitor, asymmetric super
Capacitor battery core, hybrid super capacitor-battery battery core or lithium-ion capacitor battery core.
As example, the present invention provides a kind of rechargeable lithium-metal battery core, the lithium-metal battery core is by anode
The collector at place, porous septum/electrolyte layer, contains active material of cathode (for example, being free of lithium at lithium film or foil as anode
V2O5And MnO2) cathode and collector constitute.Either or both of the anode collector and cathode current collector can
To be the collector of the invention based on graphene.
Another example of the invention is a kind of lithium-ion capacitor (or hybrid super capacitor), the capacitor by
Collector, graphite or titanate anode at anode, immersed with the porous septum of liquid or gel electrolyte, living containing cathode
Property material the activated carbon of high-specific surface area (for example, with) cathode and collector constitute.Once again, the anode collector
It can be the collector of the invention based on graphene with either or both of cathode current collector.
Another example again of the invention is another lithium-ion capacitor or hybrid super capacitor, by anode
The collector at place, graphite anode (and lithium paillon of a part as anode), immersed with liquid electrolyte porous septum, contain
The cathode and collector for having active material of cathode (for example, activated carbon with high-specific surface area) are constituted.Once again, the sun
Either or both of pole collector and cathode current collector can be the collector of the invention based on graphene.
Still another example of the invention is a kind of lithium-graphene battery core, and the battery core is by the collector, more in anode
The anode of hole nanostructure (for example, comprising the graphene film with high surface area, recharges the lithium ion of period return in battery core
It can be deposited thereon, the graphene film is mixed with the lithium powder particle of surface-stable；Or has and be attached in nanostructure
Lithium paillon), immersed with liquid electrolyte porous septum, comprising based on graphene active material of cathode (for example, have height
Specific surface area with during battery core is discharged capture lithium ion graphene, graphene oxide or graphene fluoride piece) yin
Pole and cathode current collector are constituted.Once again, either or both of the anode collector and cathode current collector can be this
The collector based on graphene of invention.
Example 1: the preparation of discrete graphene film (NGP) and exfoliated graphite sheet
By with 12 μm of average diameter chopped graphite fibre and natural graphite particles alone serve as starting material, will
To prepare graphite intercalation in its mixture (as chemical graft object and oxidant) for immersing the concentrated sulfuric acid, nitric acid and potassium permanganate
It closes object (GIC).Starting material is dried for 24 hours at 80 DEG C in vacuum drying oven first.Then, in cooling appropriate and stirring
Under, the mixture (weight ratio in 4:1:0.05) of the concentrated sulfuric acid, fuming nitric aicd and potassium permanganate is added slowly to containing fibre
In the three-neck flask for tieing up segment.After reaction in 16 hours, the processed graphite fibre of acid or natural graphite particles are filtered
And it is sufficiently washed with deionized water until the pH level of solution reaches 6.After being dried overnight at 100 DEG C, insert gained graphite
Layer compound (GIC) through heat-shock continues 45 seconds at 1050 DEG C in tube furnace, and to form expanded graphite, (or graphite is compacted
Worm).
The alcohol that 5 grams of gained expanded graphites (graphite worm) and 2,000ml are made of pure and mild distilled water with the ratio of 65:35
Solution mixes 12 hours to obtain suspension.Then, the ultrasonic radiation for making mixture or suspension be subjected to power 200W continues
The different time.After sonication in two hours, EG particle is by effectively fragment at thin NGP.Then, by the suspension mistake
It filters and dries at 80 DEG C to remove residual solvent.The NGP for preparing original sample has the average thickness of about 9.7nm.
Make other 5 grams of gained expanded graphites (EG) be subjected to the injection of low-intensity air to mill to decompose graphite worm, be formed swollen
Swollen graphite flake (average thickness with 139nm).By the sample of exfoliated graphite sheet and graphene film all with adhesive resin
(PVDF) it mixes and is then applied in the main surface of Cu foil and Al foil with the collector for forming expanded graphite coating and oxidation
The collector of graphene coating.In addition, Al paillon is cleaned with acetone and then with the spraying of both GO and RGO pieces.In lithium electricity
Gained collector is evaluated in pond and supercapacitor the two.
Example 2: graphene is prepared by carbonaceous mesophase spherules (MCMB)
Carbonaceous mesophase spherules (MCMB) are by China Steel chemical inc (China Steel Chemical
Co. it) supplies.This material has about 2.24g/cm3Density and about 16 μm of median particle diameter.With acid solution (be in 4:1:
Sulfuric acid, nitric acid and the potassium permanganate of 0.05 ratio) 72 hours are continued to (10 grams) progress intercalations of MCMB.After completion of the reaction, will
Mixture is poured into deionized water and is filtered.MCMB through intercalation is repeatedly washed in 5% solution of HCl big to remove
Part of sulfuric acid radical ion.Then sample is repeatedly washed with deionized water until the pH of filtrate is neutral.Slurry is dry simultaneously
And continue 24 hours in the vacuum drying oven being stored at 60 DEG C.Dry powder sample is placed in quartz ampoule, and is inserted into
Continue 45 seconds in the horizontal pipe furnace being preset at desired 1,080 DEG C of temperature to obtain grapheme material.TEM and atomic force are aobvious
Micro mirror is studies have shown that most of NGP are single-layer graphenes.Free-standing graphene paper or deposition is made (even in these graphene films
Same resin binder) on thin metal foil.In the case where Al foil, it is also prepared for Al foil (adhesive-free) sample of graphene coating
Product.
Example 3: raw graphite alkene piece/platelet preparation
In typical program, about 20 μm are milled to by 5 grams or smaller size of graphite flake is scattered in 1,000mL and goes
Ionized water (containing by weight 0.1% dispersing agent, from E.I.Du Pont Company (DuPont)FSO to be hanged in)
Supernatant liquid.Extruding, separation and the ruler of graphene film are used for using the ultrasound energy level (Branson S450 ultrasonic generator) of 85W
Very little reduction continues 15 minutes to 2 hours periods.
Example 4: the preparation of graphene oxide (GO) gel
Graphene oxide gel be by 30 DEG C with by be in 4:1:0.05 ratio sulfuric acid, sodium nitrate and permanganic acid
It is prepared by the oxidant liquid graphite oxide thin slice of potassium composition.When by natural graphite flake (14 μm of partial sizes) submerge and point
When being dispersed in oxidant mixture liquid, suspension or slurry seem optically opaque and dark.The suspension is initial 52
It keeps being opaque in the reaction process of hour.However, between when reacted more than 52 hours when, the suspension gradually becomes
Optical translucent (a little muddy), and the color of the suspension becomes dark-brown from black.It is described after 96 hours
Suspension suddenly becomes the optical clear solution with light brown color.The solution seems very in color and transparency
It is even, show the discrete object there is no any dispersion.Entire solution behaves like gel, with typical polymer gel very phase
Seemingly.
Unexpectedly, by by this gel curtain coating on metal foil surface (Cu, Al, Ni, Ti or stainless steel) and from
Liquid medium is removed in the film of curtain coating, we obtain optically transparent graphene oxide films.This film is looked like, has been touched
Come as and behaves like general polymer film.However, being heat-treated typically under certain temperature (from 80 DEG C to 1,500 DEG C)
After 1-3 hours, this GO film is changed into the monolithic thin-film entity comprising big size graphene farmland.This GO film is integrated to down well
In the metal foil in face.
GO film (the painting of removal liquid medium before the heat treatment is respectively illustrated in Fig. 5 (A), Fig. 5 (B) and Fig. 5 (C)
Cover GO gel on the glass surface), heat-treat at 150 DEG C GO film and height reduction and graphited again in one hour
The X-ray diffraction curve of GO film (integral piece graphene layer).The peak (Fig. 5 (A)) at about 2 θ=12 ° of dry GO film is right
Spacing (d between the graphene of Ying Yu about 0.7nm002).By some heat treatments at 150 DEG C, GO film show to be formed with
Hump (Fig. 5 (B)) centered on 22 ° shows to have begun the process of spacing between reducing graphene, shows to be connected chemically and orderly
The beginning of process.Heat treatment temperature by 1,250 DEG C continues 3 hours, d002Spacing has been reduced to about 0.34nm, close to stone
The 0.3354nm of black monocrystalline.
Heat treatment temperature by 1,500 DEG C continues 3 hours, d002Spacing is reduced to about 0.3354nm, is equal to graphite list
Brilliant d002Spacing.In addition, having the second high-intensitive diffraction maximum to occur at 2 θ=55 °, correspond to from (004) plane
X-ray diffraction (Fig. 5 (D)).(004) peak intensity on same diffraction curve is relative to (002) intensity or I (004)/I
(002) ratio is the crystal perfection degree of graphene planes and the good instruction of preferred orientation degree.For being lower than 2,800 DEG C
At a temperature of heat treated all graphite materials, (004) peak be not present or it is relatively weak, I (004)/I (002) ratio <
0.1.The I of heat treated graphite material (for example, height-oriented pyrolytic graphite, HOPG) at 3,000 DEG C -3,250 DEG C
(004)/I (002) ratio is in the range of 0.2-0.5.It is presented in Fig. 5 (E) and continues two hours poly- with 3,000 DEG C of HTT
An example of PG derived from acid imide shows about 0.41 I (004)/I (002) ratio.In contrast, with 1,500 DEG C
HTT continue preparation in 4 hours combination GO film on metal foil show 0.78 I (004)/I (002) ratio and 0.21
Inlay latitude of emulsion value, show the actually perfect graphene monocrystalline with superior preferred orientation degree.It is prepared by GO gel
Thin GO layers (< 1 μm) and following metal foil (Cu, Ni, Ti and steel) between there are synergistic effects.
" inlaying the latitude of emulsion " value is obtained by the full width at half maximum (FWHM) of (002) reflection in x-ray diffraction intensity curve.It is this orderly
The index characterization graphite or graphene crystalline size (or crystallite dimension) of degree, the amount of crystal boundary and other defect and preferred crystalline substance
The grain degree of orientation.The almost ideal monocrystalline of graphite is characterized by having that 0.2-0.4's inlays latitude of emulsion value.Our integral piece stone
(wherein heat treatment temperature is not less than 1,500 to most of latitude of emulsion values of inlaying having in the range of this 0.2-0.4 of black alkene material
℃)。
It is noted that the I (004) for the whole dozens of soft graphite samples studied/I (002) ratio be entirely <
< 0.05, in most cases not actually exist.Even if 3, after being heat-treated 2 hours at 000 DEG C, all graphene papers/
The I (004) of film sample/I (002) ratio < 0.1.Graphitization passes through the CVD that Cu the is catalyzed ultrathin membrane (thickness < 2nm) prepared
Trial has instead resulted in the rupture of film and the formation of graphite particle.These observation results are further confirmed or have been affirmed below
The viewpoint of foundation: the metal foil of combination GO film of the invention is any pyrolytic graphite with freestanding or coating on metal foil
(PG), soft graphite (FG) and ordinary graphite alkene/GO/RGO piece/platelet (NGP) paper/film/film fundamentally different one kind
New and distinguishing material.
Between the graphene of GO by being heat-treated acquisition under the different temperatures in wide temperature range gel derived GO film
Distance values are summarized in Fig. 6 (A).The corresponding oxygen content value in the gel derived GO film of the GO is shown in Fig. 6 (B).For
Correlation between graphene between spacing and oxygen content is shown, the data in Fig. 6 (A) and Fig. 6 (B) are repainted in Fig. 6
(C) in.There are 4 (80 DEG C -200 DEG C of HTT range to be shown to examining for Fig. 6 (A) to Fig. 6 (C)；200℃-500℃；
500℃-1,250℃；With 1,250 DEG C -1,500 DEG C), generate 4 corresponding spacing ranges between oxygen content range and graphene.
The thermal conductivity of GO gel derived GO film and corresponding soft graphite (FG) foil (is also used as identical final heat treatment temperature range
Function draw) be summarized in Fig. 6 (D).
It is important to note that, is enough to make spacing between the average graphite alkene in GO to be lower than down to 500 DEG C of heat treatment temperatures
0.4nm becomes closer to spacing between the average graphite alkene of natural graphite or graphite monocrystalline.The pleasant place of this method is following sight
Point: this GO gel strategy allows us to will be from the plane oxidation graphite of initially different graphite particle or graphene film
Alkene molecular recombination, reorientation and chemistry are merged into graphene monolithic, wherein all graphene planes are at this moment in lateral dimension
It upper larger (the noticeably greater than length and width of original graphite alkene plane) and is substantially parallel to each other.This generated >
The thermal conductivity of 420W/mK (HTT is 500 DEG C) and > 950W/mk (HTT is 700 DEG C), this value than corresponding soft graphite foil
(200W/mK) is big more than 2 to 4 times.These planes GO molecule is derived from graphene planes, and the graphene planes constitute starting day
The prototype structure of right graphite particle (for graphite oxidation to be formed in the program of GO gel).Original natural graphite particles, when with
When machine is piled into aggregation or " graphite green compact ", there will be it to constitute graphene planes random orientation, and show relatively low heat
Conductance simultaneously has the intensity (no structural intergrity) being substantially zero.In contrast, the intensity of integral piece graphene layer is not (even if having
Have the reinforcer of addition) typically in the range of 40-140MPa.
In the case where HTT is down to 800 DEG C, gained integral piece graphene layer shows the thermal conductivity of 1,148W/mK, with
The 244W/mK of the soft graphite foil of identical heat treatment temperature observed is contrasted.In fact, no matter how high (the example of HTT
Such as, even as high as 2,800 DEG C), soft graphite foil only shows the thermal conductivity lower than 600W/mK.At 2,800 DEG C of HTT, this hair
Bright integral piece graphene layer provides the thermal conductivity (Fig. 4 (A) and Fig. 6 (D)) of 1,807W/mK, even if metal foil is such high
At a temperature of melted.
Scanning electron microscope (SEM), the transmission electron microscope (TEM) of the lattice imaging of graphene layer are also carried out
Figure and selective electron diffraction (SAD), light field (BF) and dark field (DF) image are to characterize the structure of integral piece grapheme material.
In order to measure the section view of film, sample is buried in the polymer matrix, is sliced using ultramicrotome, and with Ar plasma
Body etching.
The graphene layer shown in one chip GO film is examined and compared to Fig. 2 (A), Fig. 3 (A) and Fig. 3 (B)
It is essentially parallel from one to another orientation；But for soft graphite foil and graphene oxide paper, situation is not in this way.Two in GO film entity
Inclination angle between a identifiable layer is in most cases less than 5 degree.In contrast, there are so many in soft graphite
Graphite flake, kink and misorientation are folded so that many in angle between two graphite flakes is greater than 10 degree, one
A little up to 45 degree (Fig. 2 (B)).Although misorientation (Fig. 3 between graphene platelet without so bad, in NGP paper
It (B)) is also that there are many gaps between high and platelet.The integral piece graphene entity is substantially gapless.
Fig. 4 (A) respectively illustrates the gel derived GO film of GO, by the vacuum assisted filtration RGO GO platelet paper prepared and
The heat conductivity value of FG foil is entirely drawn as the function of final HTT.These data have clearly demonstrated GO film
Superiority under given heat treatment temperature in terms of achievable thermal conductivity.About by raw graphite alkene or graphene oxide
The work that piece/platelet prepares all prior arts of paper or film follows visibly different machining path, generate discrete graphene/
The simple aggregation body or stacked body of GO/RGO platelet.The graphite that these simple aggregation bodies or stacked body show many foldings is thin
Piece, kink, gap and misorientation lead to thermal conductivity, low conductivity and the weak mechanical strength of difference.As shown in Fig. 4 (A),
Even if under 800 DEG C of heat treatment temperature, GO platelet paper also shows the thermal conductivity less than 1,000W/mK up to 2, it is far below
GO gel derived integral piece graphene entity > 1,700W/mK.
In order to compare, polyimide film is also carbonized 1 hour at 500 DEG C under an inert atmosphere and 1,000 by we
Be carbonized 3 hours at DEG C, and then at a temperature in the range of 2,500 DEG C -3,000 DEG C by the film be graphitized 1 to 5 hour with
Form conventional pyrolysis graphite (PG) film.Fig. 4 (B) is shown derived from film derived from thermally treated 3 hours GO and CVD carbon film
The heat conductivity value of PG is entirely drawn as final graphitization or the again function of graphitization temperature.These data are shown, false
If identical HTT continues the heat treatment time of equal length, compared with the gel derived GO film of individual GO, by by polyamides
Imines (PI), which is carbonized and the PI through being carbonized then is graphitized generated routine PG, shows consistently lower thermal conductivity.
For example, the PG from PI shows the thermal conductivity of 820W/mK at 2,000 DEG C after graphitization processing one hour, and 2,000
The thermal conductivity of 1,242W/mK is shown after handling 3 hours at DEG C.These observation results have been proven that raw using GO gel method
It produces and combines GO film on metal foil relative to using the clear and significant excellent of conventional PG method production orientation graphite crystal
Point.In fact, no matter PG graphitization time how long, thermal conductivity is always lower than the thermal conductivity of the gel derived GO film of GO.In other words,
In terms of chemical composition, crystal and defect sturcture, crystal orientation, form, production technology and characteristic, in conjunction with GO on metal foil
Film is fundamentally different from and is clearly distinguishable from soft graphite (FG) foil, graphene/GO/RGO paper/film and pyrolytic graphite
(PG)。
Data in Fig. 4 (C) further support conclusions, the entire model illustrated in the final HTT studied
In enclosing, the conductivity value of GO film derived from GO is far superior to those of GO paper and FG foil from RGO platelet value.
Example 5: conductivity and the thermal conductivity measurement of film derived from different graphene oxide gels
To individual GO layers of film (coated in what is in metal foil surface and be then stripped and be heat-treated), GO/
RGO paper and individually FG foil carry out four-point probe test to measure their face internal conductance rate.Use laser flash method
(Netzsch thermal diffusivity device) measures thermal conductivity in their face.
Have studied thermal conductivity and conductivity and tensile properties in the face of different films.Under about 75 μm of thickness, if FG
Foil is heat-treated not at 700 DEG C or higher than 700 DEG C, then the thermal conductivity of individual soft graphite foil is less than 237W/mK.With
Recompression heat treatment temperature increases to 2,800 DEG C (in each case, one hour graphitization processing) from 700 DEG C afterwards, described
The thermal conductivity of FG foil increases to 582W/mK from 237W/mK, shows that the heat treatment has caused some but limited graphite-structure weights
Group.In contrast, the thermal conductivity of individual GO gel derived thin graphene layer increases to 1,807W/mK from 983W/mK.This is thin
Film obtains in the following manner: shearing on Cu foil surface and deposits one layer of GO gel, in a vacuum from GO layers described
Except liquid continues 1 hour, and it is heat-treated dried solid GO layers.This demonstrate by it is described heat treatment cause it is significant or
Noticeable graphite-structure recombination, wherein all GO molecule edge-to-edges and connecting or being merged into Face to face fully and orderly
The integrated graphene ontology for the graphene planes that ground combines.
It has also obtained corresponding soft graphite foil (by the standby FG of the roll pressing of expanded graphite worm) and expanded graphite is thin
Piece foil or felt (prepare in the following manner: graphite worm being resolved into the graphite flake as described in example 1, the graphite is thin
Piece then be stacked and be rolled into thin foil/felt) thermal conductivity data.It is with the accessible highest heat conductivity value of expanded graphite foil
< 800W/mK, and be < 600W/mK with the accessible value of FG, the two remarkably lower than integral piece graphene base body and
The highest heat conductivity value of both graphene-based composite materials.
Example 6: the tensile strength of the graphene-based composite material of integral piece derived from different graphene oxides
It is prepared for a series of gel derived film graphene layer of GO, GO platelet paper and FG foil.Use universal testing machine
Measure the tensile strength of these materials.Function as graphitization temperature again draws graphene oxide film, GO platelet paper and FG
The tensile strength values of paper, Fig. 7 (A).These data are soft it has been proved that when heat treatment temperature is from when increasing to 2,800 DEG C for 700 DEG C
Property graphite foil tensile strength keep relative constant (whole < 20MPa), and the tensile strength of GO paper is slightly increased (from 22MPa
To 43MPa).In contrast, in identical heat-treatment temperature range, the tensile strength of integral piece graphene layer derived from GO is drawn
People increases to > 100MPa from 32MPa with gazing at.This is the result is that quite surprising and further reflect following viewpoint: GO is solidifying
GO derived from glue layers of and active molecule living containing height during heat treatment, and the graphene platelet in routine GO paper with
Graphite flake in FG foil is substantially dead molecule.Integral piece graphene entity itself derived from GO is a kind of material.
It is carried out using so-called Ford laboratory testing method (Ford Lab Test Method) (FLTM) BN108-13
Scratch test.This equipment is made of the moveable platform for being connected to five beams with 250mm length.Cross out (scratch
Pin it) is attached on one end of each beam.Press polished hardening steel ball (1.0 ± 0.1mm diameter) is placed on the point of each pin
On end.Each pin load has the weight for the power for applying 7N, 6N, 3N, 2N and 0.6N respectively.By compressed air-driven, the beam will
The pin drawing is across specimen surface and generates scratch.Scratch is manufactured under the sliding speed of about 100mm/s.It is all
Test carries out at room temperature.Although test method requires to evaluate granulations, in our current research only to sample
Smooth surface is tested.
After sample board is drawn, they are evaluated with the reflected light petrographic microscope of combination xenon light source.Using having
The image analyzer of image analysis software measures " tonal gradation amount (gray scale mass) ", is total gray scale of object etc.
Grade value.Camera lens are located at angle of 90 ° from scratch.Then, the scored portion of object lens record about 1mm long.Then
Integrate and record the electronic signal of every score line.The optical quantities M of object is the grey level of all pixels in the object
The summation of value GL.Individual grey level's value by image analysis program in unitary steps 0-255 in the range of it is specified, wherein
0=black and 255=white.Optical quantities M can be by following calculating: M=∑ GLi(summing from i to n), wherein n is pixel
Number.The brightness B of object is B=M/A, and wherein A indicates the area of the object.The percentage of brightness between scratch and background becomes
Change is scratch visibility Δ B, by Δ B=[(BScratch–BBackground)/(BBackground)] × 100% provide.Use the depth of interferometer measurement scratch
Degree.Magnifying power is arranged in 5X.Depth measurement is carried out by scanning area depth histogram.Scratch test result is shown in Fig. 7 (B)
Out.Also scratch is checked using scanning electron microscope (SEM).
Example 7: contain the Li-S battery core preparation of the metal foil collector in conjunction with graphene oxide at anode and cathode simultaneously
And three kinds of (3) Li-S battery cores of test, each is with lithium foil as active material of positive electrode, sulphur/exfoliated-graphite composite (75/
25 weight ratios) 1M LiN (CF as active material of cathode, in DOL3SO2)2As electrolyte and Celgard 2400
As diaphragm.The first battery core (the baseline battery core for comparing) contains 10 μ m-thick Cu foils as anode collector and 20 μ m-thick Al
Foil is as cathode current collector.Second of battery core (another baseline battery core for comparing) has 10 μ m-thick GO- resin layer conducts
Anode collector and the Al paillon of 14 μm of RGO coating are as cathode current collector.The third battery core is with combination GO's of the invention
Cu foil (12 μ m-thick in total) is as anode collector and the Al paillon of 20 μ m-thick GO coating as cathode current collector.
It periodically measures charge storage capacity and the function as recurring number is recorded.Ratio mentioned by this paper is put
Capacitance is that the total electrical charge/unit mass composite cathode being inserted into cathode during electric discharge (calculates active material of cathode, conduction
The weight of additive or carrier and adhesive, but collector forecloses).The specific energy and specific power presented in this section
Value is based on total battery core weight (including anode and cathode, diaphragm and electrolyte, collector and packaging material).Use transmission
Both electron microscope (TEM) and scanning electron microscope (SEM) observe selected sample in the recharge of desired number and
Form or microstructure change after recharge cycle.
Fig. 9 (A) shows the discharge capacity value of these three battery cores, respectively as the function of charge/discharge cycle number.In order to
Convenient for comparing, each battery core is designed to have the initial battery core capacity of 100mAh.Obviously, with the sheet at anode and cathode two
The Li-S battery core that the collector of the combination GO of invention is characterized shows most stable of circulation behavior, experienced after 50 circulations
6% capacitance loss.The battery core of the Al collector of Cu and GO coating containing the coating of GO/ resin is subject to after 50 circulations
23% capacity attenuation.Battery core containing Cu foil anode collector and Al foil cathode current collector is subject to 26% appearance after 50 circulations
Amount decaying.Check that the Al foil shown in the electrode of all prior arts all suffers from serious corrosion and asks after the circulation of the battery core
Topic.In contrast, the Al collector of combination graphene oxide of the invention keeps complete.
Fig. 9 (B) shows the Ragone curve graph of three kinds of battery cores (gravimetric power density is to gravimetric energy density).Have
Interest is it is noted that the graphene at anode/resin coating collector with the prior art (is wherein that GO is applied at cathode
The Al foil covered) it is compared with Cu/Al collector, the metal foil collector of our combination GO unexpectedly imparts Li-S electricity
Both the higher energy density of core and higher power density.In view of Cu foil is with higher than the conductivity of graphene film more than one
The conductivity of a order of magnitude, this is quite unexpected.The difference of energy density and power density values is greater than by anode
Cu foil and graphene film between the construable difference of phsyical density difference institute.Example 8: contain graphite at anode and cathode
The magnesium ion battery core for the collector that alkene is realized
In order to prepare active material of cathode (manganous silicate magnesium, Mg1.03Mn0.97SiO4), in a vacuum at 150 DEG C after dry 3h
Use SILVER REAGENT KCl (fusing point=780 DEG C) as fluxing agent.Starting material is magnesia (MgO), manganese carbonate (II) (MnCO3)
With silica (SiO2, 15-20nm) and powder.The stoichiometric amount of precursor compound is rubbed with the Mg:Mn:Si of 1.03:0.97:1
You are than control.By mixture (fluxing agent/reactant molar ratio=4) by pestle hand-ground 10 minutes in mortar, and
It is subsequently poured into corundum crucible.Then, will at mixture of powders in a vacuum 120 DEG C dry 5h so that water content in mixture
It minimizes.Then, mixture is immediately transferred in tube furnace and in reducing atmosphere (Ar+5wt%H2) at 350 DEG C
2h is heated to remove carbonate group.After this, 6h is fired finally with the rate of 2 DEG C/min at different temperatures, then certainly
So it is cooled to room temperature.Finally, by product (manganous silicate magnesium, Mg1.03Mn0.97SiO4) be washed with deionized and appointed three times with dissolution
What remaining salt, by centrifuge separation, and dry 2h at 100 DEG C in a vacuum.
Prepare electrode (anode or cathode) typically via following manner: by the electrode active material of 85wt% (for example,
Mg1.03Mn0.97SiO4(PVDF, 5wt% are solid for particle, 7wt% acetylene black (Super-P) and 8wt% polyvinylidene binder
Body content is dissolved in n-methyl-2-pyrrolidone (NMP)) it is mixed to form pulp-like mixture.It is pre- slurry to be coated in
After on the collector of phase, before pressing by 2h dry at the electrode obtained in a vacuum 120 DEG C to remove solvent.Having studied has
Three kinds of battery cores of different collectors: the first battery core has Cu foil and the combination of the combination GO respectively as anode and cathode collector
The Al foil of GO；There is second battery core (battery core of the prior art) the GO/ resin respectively as anode and cathode collector to coat
Cu foil and the Al foil of GO coating (not having pre-etched)；Third battery core (battery core of the prior art) has Cu foil anode collector and Al
Foil cathode current collector.
Then, the electrode is cut into disk (diameter=12mm), is used as cathode.Magnesium tinsel thin slice is attached to anode collector
On surface, and a piece of porous septum (for example, 2400 film of Celgard) is stacked on the top of the magnesium foil in turn.It will apply
The a piece of cathode disc overlayed on cathode current collector is used as cathode and is stacked on membrane layer to form CR2032 coin shape battery core.
Used electrolyte is the 1M Mg (AlCl in THF2EtBu)2.Battery core is assembled in the glove box of argon gas filling and carries out.Make
CV measurement is carried out with the sweep speed of 1mV/s with CHI-6 electrochemical workstation.Also use Arbin and/or LAND electrochemical operation
Stand by under the current density from 50mA/g to 10A/g (for some battery cores, up to 100A/g) carry out constant current charge/
Discharge cycles evaluate the chemical property of the battery core.
Figure 10 shows the battery core specific discharge capacity value of three kinds of battery cores, individually as charge/discharge cycle number
Function.Obviously, the Mg ion battery core characterized by collector of the invention at anode and cathode two is shown most stable of
Circulation behavior experienced 2.5% capacitance loss after 25 circulations.The Al of Cu foil containing the coating of GO/ resin and GO coating
The battery core of foil collector is subject to 17% capacity attenuation after 25 circulations.Contain Cu foil anode collector and Al foil cathode collector
The battery core of body is subject to 30% capacity attenuation after 25 circulations.It is checked after the circulation of the battery core and shows the coating of GO/ resin
Cu foil and the Al foil collector of GO coating become to be swollen and show some layerings with cathode layer, and Al foil is by serious
Etching problem.In contrast, the metal foil collector of combination GO of the invention keeps complete.
Example 9: the chemistry and mechanical compatibility of the different collectors of the battery or supercapacitor for heterogeneous expectations are surveyed
Examination
As proved in above example 8 and 9, the collector of battery or supercapacitor is relative to the long-term of electrolyte
Stability is to be primarily upon.In order to understand the chemical stability of different collectors, groundwork is carried out: collector has been exposed to
In several representativeness electrolyte.After extended period (for example, 30 days), the collector is removed from electrolyte solution
And it is observed using optics and scanning electron microscope (SEM).As a result it is summarized in the following table 3, the consistent earth's surface of the result
It is bright, the liquid electrolyte of the metal foil collector of combination GO of the invention and all kinds for being usually used in battery and supercapacitor
Highly compatible.Material of the invention is any chemical erosion of tolerance.The collector of these GO protection is relative to Li/Li+'s
It is substantially electrochemicaUy inert in 0-5.5 volts of voltage range, is suitable for and substantially any battery/capacitor electrolyte one
It rises and uses.
It is noted that each collector is necessarily connected on tab, the tab is connected to external circuit electric wire in turn.
The collector must be it is mechanical compatible with tab, be easy to or easily fixed or be bonded thereto.We have found that
CVD graphene film cannot be exactly mechanically secured on tab in the case where not easily damaged or fracture.Even in
Adhesive, the cvd film are also to be easily broken off on being connected to tab or during the program of battery battery core packaging.
Table 3: collector-electrolyte phase capacitive test result.
In short, we have successfully developed a kind of absolutely new, novel, unexpected and have obviously had any different
Highly conductive material: the GO film in conjunction with derived from graphene oxide gel on metal foil.The chemical group of such new material
At, structure (crystal perfection, crystallite dimension, defects count etc.), crystal orientation, form, production technology and characteristic fundamentally not
Be same as and be clearly distinguishable from pyrolytic graphite derived from freestanding or coating soft graphite foil on metal foil, polymer,
PG derived from CVD (including HOPG) and catalysis CVD graphene film.Thermal conductivity, the conductance shown by material of the invention
Rate, scratch resistance, surface hardness and tensile strength are than the flexible graphite platelet of the prior art, discrete graphene/GO/RGO platelet
Paper or other graphite films are in the cards wants much higher.These GO gel derived membrane structure has excellent conductivity, heat
Conductance, mechanical strength, surface scratch resistance, hardness and the optimal combination without peeling tendency.
Claims (60)
1. a kind of metal foil collector of the combination graphene oxide in battery or supercapacitor, the collector includes:
(a) stand alone type, non-loading type thin metal foil, the thin metal foil have thickness from 1 μm to 30 μm and two it is opposite but
Parallel main surface；And
(b) described two opposite main tables of the metal foil are chemically bonded in the case where not using adhesive or adhesive
Graphene oxide sheet film at least one of face, wherein at least one described main surface is free of passive metal oxide
Layer, and wherein the graphene oxide film has the oxygen of thickness from 10nm to 10 μm, by weight from 0.1% to 10%
Content, 0.335nm to 0.50nm graphene planes between spacing, from 1.3g/cm3To 2.2g/cm3Phsyical density, all oxidations
Graphene film, which is oriented to, is substantially parallel to each other and is parallel to the main surface, when in the case where no thin metal foil
When independent measurement, shows the thermal conductivity greater than 500W/mK and/or be greater than the conductivity of 1,500S/cm.
2. collector as described in claim 1, wherein each of described two opposite main surfaces are without using bonding
In the case where agent or adhesive in conjunction with graphene oxide sheet film chemical；Wherein the graphene oxide film has from 10nm
To 10 μm of thickness, by weight from 0.1% to 10% oxygen content, 0.335nm to 0.50nm graphene planes between spacing,
From 1.3g/cm3To 2.2g/cm3Phsyical density, all graphene oxide sheets, which are oriented to, to be substantially parallel to each other and is parallel to
The main surface, when independent measurement in the case where no thin metal foil, show thermal conductivity greater than 500W/mK and
Conductivity greater than 1,500S/cm.
3. collector as described in claim 1, wherein the thin metal foil has the thickness from 4 μm to 10 μm.
4. collector as described in claim 1, wherein the graphene oxide sheet film has the thickness from 20nm to 2 μm.
5. collector as described in claim 1, wherein the metal foil is selected from Cu, Ti, Ni, stainless steel and loses through chemistry
The Al foil at quarter, wherein the surface of the Al foil through chemical etching is not at it before in conjunction with the graphene oxide sheet
The passivation Al of upper formation2O3。
6. collector as described in claim 1, wherein the graphene oxide sheet film has by weight from 1% to 5%
Oxygen content.
7. collector as described in claim 1, wherein the graphene oxide film has oxygen content less than 1%, is less than
Spacing and the conductivity not less than 3,000S/cm between the graphene of 0.345nm.
8. collector as described in claim 1, wherein the graphene oxide film has less than 0.1% oxygen content, small
Spacing and the conductivity not less than 5,000S/cm between the graphene of 0.337nm.
9. collector as described in claim 1, wherein there is the graphene oxide film oxygen no more than 0.05% to contain
Amount, spacing between the graphene less than 0.336nm inlay latitude of emulsion value and the conductance not less than 8,000S/cm no more than 0.7
Rate.
10. collector as described in claim 1, wherein the graphene oxide film has the graphene less than 0.336nm
Between spacing, no more than 0.4 inlay latitude of emulsion value and the conductivity greater than 10,000S/cm.
11. collector as described in claim 1, wherein the graphene oxide film shows the graphite less than 0.337nm
Between alkene spacing and latitude of emulsion value is inlayed less than 1.0.
12. collector as described in claim 1, wherein the graphene oxide film shows the graphite not less than 80%
Change degree and/or latitude of emulsion value is inlayed no more than 0.4.
13. collector as described in claim 1, wherein the graphene oxide sheet film obtains in the following manner: taking
To under the influence of proof stress, deposit to graphene oxide gel at least one described main surface, and then from 80
DEG C to being heat-treated the graphene oxide gel under 1,500 DEG C of heat treatment temperature.
14. collector as claimed in claim 13, wherein the heat treatment temperature is from 80 DEG C to 500 DEG C.
15. collector as claimed in claim 13, wherein the heat treatment temperature is from 80 DEG C to 200 DEG C.
16. collector as described in claim 1, wherein the graphene oxide film contains chemical bonding parallel to each other
Graphene molecules or chemistry merge graphene planes.
17. collector as claimed in claim 13, wherein the graphene oxide gel is by having maximum original graphite crystal grain
The graphite material of size obtains, and the graphene oxide film has the crystal grain bigger than the maximum initial grain size
Size.
18. collector as claimed in claim 13, wherein the graphene oxide gel is by natural or artificial graphite
Grain production, the particle is by with the initial length L in crystallography a- axis directiona, original width L in b- axis directionbAnd
Thickness L in c- axis directioncGraphite microcrystal constitute, and the graphene oxide film has greater than the graphite microcrystal
Initial LaAnd LbGraphene farmland or crystal length or width.
19. collector as described in claim 1, wherein the graphene oxide film contains with sp2And sp3Electron configuration
Combined graphene planes.
20. collector as described in claim 1, wherein the graphene oxide film be with not less than 5cm length and
The continuous length film of width not less than 1cm.
21. collector as described in claim 1, wherein when independent measurement, the graphene oxide film, which has, to be greater than
The phsyical density of 1.8g/cm3 and/or tensile strength greater than 40MPa.
22. collector as described in claim 1, wherein when independent measurement, the graphene oxide film, which has, to be greater than
The phsyical density of 1.9g/cm3 and/or tensile strength greater than 60MPa.
23. collector as described in claim 1, wherein when independent measurement, the graphene oxide film, which has, to be greater than
2.0g/cm3Phsyical density and/or tensile strength greater than 80MPa.
24. a kind of lithium rechargeable battery or lithium ion battery contain collector as described in claim 1 as anode collection
Fluid and/or cathode current collector.
25. a kind of lithium rechargeable battery contains collector as described in claim 1 as anode collector or cathode collection
Fluid, the lithium battery be lithium-sulphur battery core, lithium-selenium battery core, lithium sulphur/selenium battery core, lithium-air battery core, lithium-graphene battery core or
Lithium-carbon battery core.
26. a kind of capacitor contains collector as described in claim 1 as anode collector or cathode current collector, institute
State capacitor be symmetrical supercapacitor, asymmetric super capacitor electric core, hybrid super capacitor-battery battery core,
Or lithium-ion capacitor battery core.
27. a kind of for producing the side for being used for the metal foil collector of combination film graphene oxide of battery or supercapacitor
Method, which comprises (a) preparation has the graphene oxide gel for the graphene oxide molecule being dissolved in fluid media (medium),
Wherein the graphene oxide molecule contains by weight of from more than 20% oxygen content；(b) in two main surfaces of metal foil
At least one on distribute and deposit one layer of graphene oxide gel, to form the wet oxidation graphene that is deposited thereon
Gel layer, wherein the distribution and deposition procedure include the shear-induced desaturation of the graphene oxide gel；(c) from being deposited
Graphene oxide gel wet layer in remove the fluid media (medium) partially or even wholly to form graphene oxide dry film, it is described
Dry film has the interplanar spacing d of the 0.4nm to 1.2nm such as measured by X-ray diffraction002It is not less than 20% by weight
Oxygen content；And the graphene oxide dry film (d) is heat-treated to be formed under the heat treatment temperature from 80 DEG C to 2,500 DEG C
The metal foil collector of the combination film graphene oxide, degree are so that interplanar spacing d002It is reduced to from 0.335nm
To 0.5nm value and oxygen content be reduced to by weight less than 10% and the graphene oxide film have from 10nm to
10 μm of thickness, from 1.3g/cm3To 2.2g/cm3Phsyical density, and all graphene oxide sheets be oriented to substantially mutually
In parallel and it is parallel at least one described main surface.
28. method as claimed in claim 27, wherein step (b) includes: in described two main surfaces of the metal foil
Each on distribute and deposit one layer of graphene oxide gel, with formed be deposited on it is every in described two main surfaces
Wet oxidation Graphene gel layer on one, wherein the metal foil has the thickness from 1 μm to 30 μm.
29. method as claimed in claim 27, wherein the metal foil is selected from Cu, Ti, Ni, stainless steel and loses through chemistry
The Al foil at quarter, wherein the surface of the Al foil through chemical etching is without on it before in conjunction with the graphene oxide
The passivation Al of formation2O3。
30. method as claimed in claim 27, wherein step (c) includes being formed between the interplanar with 0.4nm to 0.7nm
Away from d002The graphene oxide layer of oxygen content by weight not less than 20%；And step (d) includes being heat-treated the oxidation
Graphene layer, degree are so that interplanar spacing d002It is reduced to the value from 0.3354nm to 0.36nm and the oxygen content
It is reduced to by weight less than 2%.
31. method as claimed in claim 27, wherein when being measured at 20 DEG C before the shear-induced desaturation, institute
Stating graphene oxide gel has the viscosity for being greater than 2,000 centipoise, and during or after shear-induced desaturation, the viscosity
It is decreased to less than 2,000 centipoises.
32. method as claimed in claim 27, wherein when being measured at 20 DEG C before the shear-induced desaturation, institute
Stating graphene oxide gel has from 500 centipoises to the viscosity of 500,000 centipoises.
33. method as claimed in claim 27, wherein when being measured at 20 DEG C before the shear-induced desaturation, institute
Stating graphene oxide gel has the viscosity for being not less than 5,000 centipoise, and during or after shear-induced desaturation, described viscous
Degree is decreased to less than 2,000 centipoises.
34. method as claimed in claim 27, wherein when increasing shear rate at 20 DEG C, the graphene oxide is solidifying
Glue has the viscosity for reducing at least 10 times.
35. method as claimed in claim 27, wherein the graphene oxide gel has the pH value less than 5.0.
36. method as claimed in claim 27, wherein the graphene oxide gel has the pH value less than 3.0.
37. method as claimed in claim 27, wherein shear-induced desaturation is carried out by the program selected from following item: coating,
Curtain coating, printing, the spraying of air auxiliary, ultrasound spraying squeeze out.
38. method as claimed in claim 27, wherein the step (d) includes being heat-treated the oxidation under compressive stress
Graphene layer.
39. method as claimed in claim 27, wherein the graphene oxide gel is prepared in the following manner: reacting
It is initially optically opaque and dark to be formed in oxidation liquid by being immersed in the graphite material of powder or fibers form in container
Suspension, impregnate enough a period of times at the reaction temperatures with obtain homogeneous solution and or it is optically transparent, half
Transparent or brown graphene oxide gel, wherein the graphene oxide gel is by being dissolved in the pH having not higher than 5
Graphene oxide molecule in the acid medium of value is constituted, and the graphene oxide molecule has and is not less than by weight
20% oxygen content.
40. method as claimed in claim 27, wherein the graphene oxide gel is prepared in the following manner: by graphite
Material is immersed to form initially optically opaque and dark suspension in oxidant, and allow to carry out oxidation reaction until
Uniform and optically transparent, translucent or brown solution is formed, and wherein the graphite material is selected from natural stone
Ink, artificial graphite, mesocarbon, mesophase pitch, carbonaceous mesophase spherules, soft carbon, hard carbon, coke, carbon fiber, carbon Nanowire
Dimension, carbon nanotube, or combinations thereof.
41. method as claimed in claim 27, the method is reel-to-reel method, wherein the step (b) and (c) include:
The metal foil is fed into crystallizing field from roller, one layer of oxidation is deposited at least one main surface described in the metal foil
Graphene gel is to be formed on graphene oxide gel wet layer, and the dry graphene oxide gel wet layer is to form deposition
Drying graphene oxide layer on said principal surface, and the gold that the dry graphene oxide layer of collection deposits on collector roller
Belong to foil.
42. method as claimed in claim 27, wherein the heat treatment temperature includes the thermal reduction scheme at 80 DEG C -500 DEG C
Interior temperature, and the graphene oxide membrane have the oxygen content less than 5%, between the graphene less than 0.4nm spacing and/or
At least thermal conductivity of 100W/mK.
43. method as claimed in claim 27, wherein the heat treatment temperature is included in 500 DEG C -1, within the scope of 000 DEG C
Temperature, and integral piece grapheme material has the oxygen content less than 1%, spacing, at least 1 between the graphene less than 0.345nm,
The thermal conductivity of 300W/mK and/or conductivity not less than 3,000S/cm.
44. method as claimed in claim 27, wherein the heat treatment temperature is included within the scope of 1,000 DEG C -1,500 DEG C
Temperature, and the graphene oxide membrane have the oxygen content less than 0.01%, spacing between the graphene less than 0.337nm,
At least thermal conductivity of 1,500W/mK and/or the conductivity not less than 5,000S/cm.
45. method as claimed in claim 27, wherein the graphene oxide membrane shows the graphene less than 0.337nm
Between spacing and inlay latitude of emulsion value less than 1.0.
46. method as claimed in claim 27, wherein the graphene oxide membrane shows the degree of graphitization not less than 40%
And/or latitude of emulsion value is inlayed less than 0.7.
47. method as claimed in claim 27, wherein the graphene oxide membrane shows the degree of graphitization not less than 80%
And/or latitude of emulsion value is inlayed no more than 0.4.
48. method as claimed in claim 27, wherein the graphene oxide membrane contains chemically combined stone parallel to each other
The graphene planes that black alkene molecule or chemistry merge.
49. method as claimed in claim 27, wherein the graphene oxide gel is by the graphite with multiple graphite microcrystals
Material obtains, and the graphite microcrystal does not show preferred crystal orientation, is such as surveyed by X-ray diffraction or electron diffraction
Fixed, and wherein the graphene oxide membrane has preferred crystal orientation, is such as spread out by the X-ray diffraction or electronics
Shooting method measurement.
50. method as claimed in claim 27, wherein the graphene oxide gel obtains in the following manner: reacting
In container, it will be immersed in the graphite material of powder or fibers form continue enough one in oxidation liquid medium at the reaction temperatures
Section the time to obtain the homogeneous solution being made of the graphene oxide molecule being dissolved in the liquid medium, wherein it is described uniformly
Solution is optically transparent, translucent or brown, and when being in gel state, the graphene oxide molecule
Molecular weight with the oxygen content for being not less than 20% by weight and less than 43,000 grams/mol.
51. method as claimed in claim 50, wherein when being in gel state, the graphene oxide molecule has small
In 4,000 grams/mol of molecular weight.
52. method as claimed in claim 50, wherein when being in gel state, the graphene oxide molecule has
Molecular weight between 200 grams/mol and 4,000 grams/mol.
53. method as claimed in claim 27, wherein the heat treatment step causes the chemistry of graphene oxide molecule even
It connects, merge or is chemically combined and/or graphite-structure is graphitized again or recombinates.
54. method as claimed in claim 27, wherein the graphene oxide membrane have greater than 3,000S/cm conductivity,
Thermal conductivity greater than 600W/mK, the phsyical density greater than 1.8g/cm3 and/or the tensile strength greater than 40MPa.
55. method as claimed in claim 27, wherein the graphene oxide membrane have greater than 5,000S/cm conductivity,
Thermal conductivity greater than 1,000W/mK, the phsyical density greater than 1.9g/cm3 and/or the tensile strength greater than 60MPa.
56. method as claimed in claim 27, wherein the graphene oxide membrane has the conductance greater than 15,000S/cm
Rate, is greater than 2.0g/cm at the thermal conductivity greater than 1,500W/mK3Phsyical density, and/or tensile strength greater than 80MPa.
57. method as claimed in claim 27, wherein the metal foil has the thickness from 4 μm to 10 μm.
58. method as claimed in claim 27, wherein the graphene oxide membrane has the thickness from 20nm to 2 μm.
59. a kind of for producing the side for being used for the metal foil collector of combination film graphene oxide of battery or supercapacitor
Method, which comprises (a) preparation has the graphene oxide gel for the graphene oxide molecule being dissolved in fluid media (medium)
Bath, wherein the graphene oxide molecule contains by weight of from more than 20% oxygen content and the graphene oxide gel has
There is the pH value less than 5.0；(b) metal foil is fed in the bath and the metal foil is removed into the bath, so that
It can be in the upper deposited oxide Graphene gel wet layer of each of two main surfaces of the metal foil；(c) from being deposited
The fluid media (medium) is removed in graphene oxide gel wet layer partially or even wholly to form graphene oxide dry film, it is described dry
Film has the interplanar spacing d of the 0.4nm to 1.2nm such as measured by X-ray diffraction002；And (d) from 80 DEG C to 2,
The graphene oxide dry film is heat-treated under 500 DEG C of heat treatment temperature to form the metal of the combination film graphene oxide
Foil collector, degree are so that interplanar spacing d002It is reduced to value and oxygen content from 0.335nm to 0.5nm to be reduced to
By weight less than 10% and the graphene oxide film has thickness from 10nm to 10 μm, from 1.3g/cm3Extremely
2.2g/cm3Phsyical density, and all graphene oxide sheets be oriented to be substantially parallel to each other and be parallel to it is described at least
One main surface.
60. method as claimed in claim 59, wherein the metal foil includes aluminium foil.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15/231,498 | 2016-08-08 | ||
| US15/231,486 | 2016-08-08 | ||
| US15/231,498 US10158122B2 (en) | 2016-08-08 | 2016-08-08 | Graphene oxide-bonded metal foil thin film current collector and battery and supercapacitor containing same |
| US15/231,486 US10586661B2 (en) | 2016-08-08 | 2016-08-08 | Process for producing graphene oxide-bonded metal foil thin film current collector for a battery or supercapacitor |
| PCT/US2017/018707 WO2018031064A1 (en) | 2016-08-08 | 2017-02-21 | Graphene oxide-bonded metal foil thin film current collector |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109565053A true CN109565053A (en) | 2019-04-02 |
Family
ID=61163274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780047369.XA Pending CN109565053A (en) | 2016-08-08 | 2017-02-21 | In conjunction with the metal foil film current collector of graphene oxide |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7126492B2 (en) |
| KR (1) | KR20190039536A (en) |
| CN (1) | CN109565053A (en) |
| WO (1) | WO2018031064A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110049661A (en) * | 2019-05-17 | 2019-07-23 | 台州思碳科技有限公司 | A kind of graphite multicellular metal foil heat dissipation film and preparation method thereof |
| CN110212153A (en) * | 2019-06-24 | 2019-09-06 | 珠海格力电器股份有限公司 | A kind of collector and preparation method thereof |
| CN110265666A (en) * | 2019-06-11 | 2019-09-20 | 东旭光电科技股份有限公司 | Composite microporous copper foil of graphene and preparation method thereof, lithium ion battery |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7463874B2 (en) | 2019-06-27 | 2024-04-09 | 東レ株式会社 | Laminate |
| CN110350201B (en) * | 2019-06-29 | 2022-07-26 | 华南理工大学 | Light high-conductivity graphene current collector for water-based battery and preparation method thereof |
| CN111661838A (en) * | 2020-04-03 | 2020-09-15 | 武汉汉烯科技有限公司 | Light high-conductivity flexible lithium battery current collector material and preparation method and application thereof |
| CN114730888A (en) * | 2020-05-08 | 2022-07-08 | 株式会社Lg新能源 | Negative electrode current collector for lithium-free battery, electrode assembly comprising same, and lithium-free battery |
| WO2023056591A1 (en) * | 2021-10-08 | 2023-04-13 | 宁德时代新能源科技股份有限公司 | Composite positive electrode current collector, pole piece, and secondary battery |
| CN114957897B (en) * | 2022-06-27 | 2022-12-13 | 苏福（深圳）科技有限公司 | High-performance graphene film and preparation method thereof |
| CN117023569A (en) * | 2023-08-17 | 2023-11-10 | 小米汽车科技有限公司 | Graphene electrothermal film and preparation method thereof, negative electrode, lithium metal battery and dendrite removing method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102047488A (en) * | 2008-03-07 | 2011-05-04 | 莱登能源公司 | Electrochemical cells with tabs |
| CN103187576A (en) * | 2011-12-28 | 2013-07-03 | 清华大学 | Current collector, electrochemical battery electrode and electrochemical battery |
| CN103426941A (en) * | 2012-05-15 | 2013-12-04 | 三星电机株式会社 | Transparent electrode and electronic material comprising the same |
| US20140030590A1 (en) * | 2012-07-25 | 2014-01-30 | Mingchao Wang | Solvent-free process based graphene electrode for energy storage devices |
| US20140127488A1 (en) * | 2012-11-02 | 2014-05-08 | Aruna Zhamu | Graphene oxide-coated graphitic foil and processes for producing same |
| CN103839694A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene/metal current collector preparing method |
| US20150086881A1 (en) * | 2013-09-23 | 2015-03-26 | Aruna Zhamu | Large-grain graphene thin film current collector and secondary batteries containing same |
| WO2015061327A1 (en) * | 2013-10-21 | 2015-04-30 | The Penn State Research Foundation | Method for preparing graphene oxide films and fibers |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11283104B2 (en) * | 2012-06-01 | 2022-03-22 | Global Graphene Group, Inc. | Rechargeable dual electroplating cell |
-
2017
- 2017-02-21 JP JP2019506509A patent/JP7126492B2/en active Active
- 2017-02-21 WO PCT/US2017/018707 patent/WO2018031064A1/en active Application Filing
- 2017-02-21 CN CN201780047369.XA patent/CN109565053A/en active Pending
- 2017-02-21 KR KR1020197005445A patent/KR20190039536A/en unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102047488A (en) * | 2008-03-07 | 2011-05-04 | 莱登能源公司 | Electrochemical cells with tabs |
| CN103187576A (en) * | 2011-12-28 | 2013-07-03 | 清华大学 | Current collector, electrochemical battery electrode and electrochemical battery |
| CN103426941A (en) * | 2012-05-15 | 2013-12-04 | 三星电机株式会社 | Transparent electrode and electronic material comprising the same |
| US20140030590A1 (en) * | 2012-07-25 | 2014-01-30 | Mingchao Wang | Solvent-free process based graphene electrode for energy storage devices |
| US20140127488A1 (en) * | 2012-11-02 | 2014-05-08 | Aruna Zhamu | Graphene oxide-coated graphitic foil and processes for producing same |
| CN103839694A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene/metal current collector preparing method |
| US20150086881A1 (en) * | 2013-09-23 | 2015-03-26 | Aruna Zhamu | Large-grain graphene thin film current collector and secondary batteries containing same |
| WO2015061327A1 (en) * | 2013-10-21 | 2015-04-30 | The Penn State Research Foundation | Method for preparing graphene oxide films and fibers |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110049661A (en) * | 2019-05-17 | 2019-07-23 | 台州思碳科技有限公司 | A kind of graphite multicellular metal foil heat dissipation film and preparation method thereof |
| CN110265666A (en) * | 2019-06-11 | 2019-09-20 | 东旭光电科技股份有限公司 | Composite microporous copper foil of graphene and preparation method thereof, lithium ion battery |
| CN110212153A (en) * | 2019-06-24 | 2019-09-06 | 珠海格力电器股份有限公司 | A kind of collector and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2019525420A (en) | 2019-09-05 |
| KR20190039536A (en) | 2019-04-12 |
| JP7126492B2 (en) | 2022-08-26 |
| WO2018031064A1 (en) | 2018-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109565053A (en) | In conjunction with the metal foil film current collector of graphene oxide | |
| US10158122B2 (en) | Graphene oxide-bonded metal foil thin film current collector and battery and supercapacitor containing same | |
| US9484160B2 (en) | Large-grain graphene thin film current collector and secondary batteries containing same | |
| CN109314225B (en) | Alkali metal battery with electrodes based on monolithic 3D graphene-carbon-metal hybrid foam | |
| JP6968074B2 (en) | How to Make Alkali Metal or Alkaline Ion Batteries with High Volume and Weight Energy Density | |
| US20190363394A1 (en) | Process for producing lithium batteries having an ultra-high energy density | |
| JP7075338B2 (en) | Alkali metal or alkali ion batteries with high volume and weight energy density | |
| US10586661B2 (en) | Process for producing graphene oxide-bonded metal foil thin film current collector for a battery or supercapacitor | |
| US11631893B2 (en) | Artificial solid electrolyte interface cap layer for an anode in a Li S battery system | |
| CN109311053A (en) | For alkali metal battery based on graphene-metal hybrid foam electrode | |
| US11735740B2 (en) | Protective carbon layer for lithium (Li) metal anodes | |
| US11539074B2 (en) | Artificial solid electrolyte interface (A-SEI) cap layer including graphene layers with flexible wrinkle areas | |
| KR102565802B1 (en) | Shape adaptable cable type flexible alkali metal battery | |
| KR20180101474A (en) | Alkali metal-sulfur batteries with high volume and weight energy densities | |
| KR20220105658A (en) | Bonded Graphene Balls and Metal Particles for Anodes in Alkali Metal Batteries | |
| Liu et al. | Microstructure and superior electrochemical activity of Cu3P/reduced graphene oxide composite for an anode in lithium-ion batteries | |
| CN110063004A (en) | Battery with low output voltage | |
| WO2019199770A1 (en) | Graphene-enabled selenium cathode active material for an alkali metal-selenium secondary battery | |
| WO2022056008A1 (en) | Artificial solid electrolyte interface cap layer for an anode in a li s battery system | |
| US20190312267A1 (en) | Production process for graphene-enabled selenium cathode active material for an alkali metal-selenium secondary battery | |
| CN109792055B (en) | Metal foil film current collector combined with humic acid and battery and super capacitor containing metal foil film current collector | |
| Qi et al. | Hollow nickel microtube/carbon nanospheres Core–Shell arrays as electrode material for rechargeable Li-ion batteries | |
| Hossain et al. | Advances on synthesis and performance of Li-Ion anode batteries-a review | |
| Yu et al. | Compositing SrLi2Ti6O14 with chemical deposited silver for enhancing lithium ion storage | |
| Chao et al. | Vanadium pentoxide for Li-ion storage |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190402 |
|
| RJ01 | Rejection of invention patent application after publication |