CN109576454A - Preparation method, metal nano plate, purposes and the negative electrode active material of metal nano plate - Google Patents
Preparation method, metal nano plate, purposes and the negative electrode active material of metal nano plate Download PDFInfo
- Publication number
- CN109576454A CN109576454A CN201811561463.XA CN201811561463A CN109576454A CN 109576454 A CN109576454 A CN 109576454A CN 201811561463 A CN201811561463 A CN 201811561463A CN 109576454 A CN109576454 A CN 109576454A
- Authority
- CN
- China
- Prior art keywords
- metal
- organic
- metal nano
- nano plate
- wax
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 336
- 239000002184 metal Substances 0.000 title claims abstract description 335
- 239000002055 nanoplate Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 127
- 238000000576 coating method Methods 0.000 claims abstract description 127
- 239000000463 material Substances 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 82
- 239000002131 composite material Substances 0.000 claims abstract description 54
- 239000011888 foil Substances 0.000 claims abstract description 44
- 230000008569 process Effects 0.000 claims abstract description 37
- 239000001993 wax Substances 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 41
- 238000011282 treatment Methods 0.000 claims description 30
- 230000032683 aging Effects 0.000 claims description 23
- 229910045601 alloy Inorganic materials 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 21
- -1 lanocerin Substances 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 18
- 238000012805 post-processing Methods 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 17
- 238000010409 ironing Methods 0.000 claims description 16
- 238000005530 etching Methods 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 235000013339 cereals Nutrition 0.000 claims description 11
- 239000002608 ionic liquid Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910052787 antimony Inorganic materials 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 229910052732 germanium Inorganic materials 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- 229910052745 lead Inorganic materials 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 229920002521 macromolecule Polymers 0.000 claims description 8
- 229910052762 osmium Inorganic materials 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 238000005242 forging Methods 0.000 claims description 7
- 239000012188 paraffin wax Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000002482 conductive additive Substances 0.000 claims description 6
- 239000004519 grease Substances 0.000 claims description 6
- 229920006305 unsaturated polyester Polymers 0.000 claims description 6
- 238000010422 painting Methods 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 4
- 229920002907 Guar gum Polymers 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 4
- 230000001680 brushing effect Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000010417 guar gum Nutrition 0.000 claims description 4
- 239000000665 guar gum Substances 0.000 claims description 4
- 229960002154 guar gum Drugs 0.000 claims description 4
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 4
- 229920002530 polyetherether ketone Polymers 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 238000000992 sputter etching Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 claims description 3
- 241000206575 Chondrus crispus Species 0.000 claims description 3
- 241000238631 Hexapoda Species 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- LCJHLOJKAAQLQW-UHFFFAOYSA-N acetic acid;ethane Chemical compound CC.CC(O)=O LCJHLOJKAAQLQW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 239000012164 animal wax Substances 0.000 claims description 3
- 239000012179 bayberry wax Substances 0.000 claims description 3
- 235000013871 bee wax Nutrition 0.000 claims description 3
- 239000012166 beeswax Substances 0.000 claims description 3
- 239000004203 carnauba wax Substances 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 238000001548 drop coating Methods 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 150000002460 imidazoles Chemical group 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 229940119170 jojoba wax Drugs 0.000 claims description 3
- 239000003077 lignite Substances 0.000 claims description 3
- 230000001050 lubricating effect Effects 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 3
- 150000003053 piperidines Chemical group 0.000 claims description 3
- 229920000083 poly(allylamine) Polymers 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000009719 polyimide resin Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 238000007761 roller coating Methods 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000012177 spermaceti Substances 0.000 claims description 3
- 229940084106 spermaceti Drugs 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000003760 tallow Substances 0.000 claims description 3
- 229920001567 vinyl ester resin Polymers 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 235000010493 xanthan gum Nutrition 0.000 claims description 3
- 229920001285 xanthan gum Polymers 0.000 claims description 3
- 239000000230 xanthan gum Substances 0.000 claims description 3
- 229940082509 xanthan gum Drugs 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 2
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004170 rice bran wax Substances 0.000 claims description 2
- 235000019384 rice bran wax Nutrition 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract description 5
- 239000002894 chemical waste Substances 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 38
- 238000005096 rolling process Methods 0.000 description 22
- 150000002736 metal compounds Chemical class 0.000 description 12
- 238000003801 milling Methods 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 11
- 239000011229 interlayer Substances 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000035882 stress Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 239000002356 single layer Substances 0.000 description 9
- 238000010410 dusting Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002905 metal composite material Substances 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000010297 mechanical methods and process Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 150000002738 metalloids Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910018140 Al-Sn Inorganic materials 0.000 description 1
- 229910018564 Al—Sn Inorganic materials 0.000 description 1
- 229910018575 Al—Ti Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910017091 Fe-Sn Inorganic materials 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910017142 Fe—Sn Inorganic materials 0.000 description 1
- 206010057855 Hypotelorism of orbit Diseases 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 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
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003233 pyrroles Chemical group 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000012056 semi-solid material Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention belongs to metal nano plate technical fields, are related to preparation method, metal nano plate, purposes and the negative electrode active material of a kind of metal nano plate.The preparation method of metal nano plate of the present invention a, comprising the following steps: metal foil is provided, coats organic coating on the surface of the metal foil, the multiple doubling of metal foil and repeatedly pressurization of organic coating is then coated with, obtains metal-organic coating composite sheet；By in metal-organic coating composite sheet sheet metal and organic coating separate, obtain metal nano plate.Present invention process is simple, easy to implement, simplifies process flow, the range of choice of two-dimensional nano metal can be widened, material preparation cost is reduced, reduces the generation of chemical waste fluid, environmentally protective, low energy consumption, can obtain purity is high, high-quality two-dimensional metallic nano material.
Description
Technical field
The invention belongs to metal nano plate technical fields, preparation method, gold in particular to a kind of metal nano plate
Belong to nanometer sheet, purposes and negative electrode active material.
Background technique
Nanometer two-dimensional material is widely studied in recent years, and reason is that it mainly has the advantage that 1. due to two dimension
Plane limits the three-dimensional motion of electronics, therefore electronics will do it faster transmission on two-dimensional surface；2. two-dimensional material has
The specific surface area of super large；3. the single film that two-dimensional material can prepare high quality；4. two-dimensional material have outstanding mechanical strength,
Flexible and optical clarity；5. surface atom it is highly exposed provide by surface modification/functionalization, element doping and/
Or the condition that the means such as defect, strain, phase engineering easily regulate and control material property.
And at present for the two-dimensional material of the cheap metal of traditional field and popular domain, the intersection that the two is formed is led
Domain does not occur research hotspot, and even research contents is all more rare.It is primarily due to following problems and limits the direction
Development: 1. part cheap metal such as Al have stronger reproducibility, and the condition for restoring simple substance by chemical synthesis is more severe
It carves；2. there are complex process, purification difficult and environmental pollutions etc. for the synthetic method of part metals nanometer sheet；3. current synthesis
Method yield is lower, can not form the magnanimity preparation of metal nano plate.
The preparation research of metal nano plate is concentrated on substantially in three methods at present, is closed including chemistry from bottom to top
At and sedimentation and top-down Mechanical Method.Wherein, the greatest problem that chemical synthesis is faced is more difficult be applied to
The strong metal of reproducibility, therefore the chemical synthesis of current mainstream is substantially all and is to prepare noble metal nano-plate.This outer chemical
Sedimentation there are also complex process, purification hardly possible, low output, environmental pollution the disadvantages of.Sedimentation mainly includes electrodeposition process and physics
Vapour deposition process (PVD).Although sedimentation can obtain the high-quality nano thin-layer of large area but the less energy consumption of yield is bigger, simultaneously
Equipment used in PVD is generally all more expensive, also harsher to vacuum condition, and the separation in substrate is also one to ask greatly
Topic, these all affect application of the sedimentation in nanometer sheet.Mechanical Method then have in contrast simple process, low energy consumption,
Industrial automation, suitable metal type be wide, super large-tonnage advantage, it is ensured that the following metal nano plate industrialization production is certain
Possibility.As it can be seen that be directed to the preparation of metal nano plate, Mechanical Method is due to some obvious advantages, in recent years
The desk study of researchers is obtained.
Existing Mechanical Method is prepared there are mainly three types of metal nano plates: 1. pressure sinterings；Hussain et al. uses pressure sintering,
It is pressurizeed by being heated to Bi nano particle, final compacting obtains Bi nanometer sheet (Small 2017,13 (36)).This method is due to being
Metal nanoparticle is directly processed, therefore the metal nano plate being able to produce on unit area is extremely limited.2. liquid phase
Stripping method；Although most metals material is non-layer structure, there are a few metals, such as Sb and As, has in specific environment item
Stable allotrope layered under part.Yang et al. passes through the aqueous isopropanol ultrasound Sb powder containing sodium hydroxide
Obtain Sb nanometer sheet (Adv.EnergyMater.2017,7 (17)).But due to metal allotrope layered
It is as rare, therefore this method use scope is greatly limited.3. roll process；Due to the excellent extension of metal material
Property, the thickness of metal plate can reduce by Repeated Compression at room temperature and folding, and Wu et al. just used this strategy system
Make the metal nano plates such as Au, Ag and Fe (Adv.Mater.2016,28 (37)).Its bimetallic roll process used must be in rolling work
One of metal is etched away after the completion of skill to obtain the nanometer sheet of required metal, after heating rolling 20 times, metal layer
Most thin thickness is reduced to only several nanometers or less.To slow down the breaking and Dusting occurred after multiple rolling, also moved back after rolling
Processing hardening and internal stress have been eliminated in fire post-processing.This method realized metal nano plate magnanimity preparation, use scope also compared with
Extensively.But this method faces a serious problem: since it is desired that etching away sacrificial metal to obtain the nanometer of another metal
Piece, therefore prepare a certain amount of nanometer sheet and need to consume another metal of equivalent.Cheap metal is used for noble metal
Still receive as sacrificial metal, but to prepare cheap metal nanometer sheet, preparation cost can then be significantly improved, this just industry
It the use of for upper is worthless.Roll milling process, surface oxide layer can rupture simultaneously, expose new exposing metal.Due to two kinds
Metal interlevel is difficult to form fine and close lattice, therefore when powder phenomenon-tion occurs, air may be permeated in metal layer itself not
Break in new exposing metal Surface Creation oxidation film.And in etching process, it is also possible to will increase the degree of oxidation of metal surface.
Bimetallic rolling is caused so far, not occur and be correspondingly improved in academia from report just because of disadvantage mentioned above.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of metal nano plate, easy to operate, easy to implement, energy
Enough simplification of flowsheet, widen the range of choice of two-dimensional nano metal, reduce material preparation cost, reduce the production of chemical waste fluid
It is raw, purity is high, high-quality two-dimensional metallic nano material are obtained, the above problem can be overcome or partial solution is above-mentioned asks
Topic.
The second object of the present invention is to provide a kind of metal nano plate that there are with high purity, high-quality, metal species to select
The features such as range is wide, low in cost.
The third object of the present invention is to provide a kind of purposes of metal nano plate as negative electrode active material, is capable of increasing
The specific surface area of negative electrode active material improves active material high rate performance.
The fourth object of the present invention is to provide a kind of negative electrode active material, including metal nano plate, the gold of two-dimensional structure
Belong to nanometer sheet to be easier to be expanded in thickness direction in expansion process, reduces the level of stretch of the binder of surface attachment, change
It is apt to current metal negative electrode dusting, metal active material is easy to the problem of bonding division.
To achieve the above object, the technical solution adopted by the present invention are as follows:
According to an aspect of the present invention, the present invention provides a kind of preparation method of metal nano plate, comprising the following steps:
One metal foil is provided, organic coating is coated on the surface of the metal foil, is then coated with the metal of organic coating
The multiple doubling of foil and repeatedly pressurization, obtain metal-organic coating composite sheet；
By in metal-organic coating composite sheet sheet metal and organic coating separate, obtain metal nano plate.
As further preferred technical solution, the metal foil is malleable/metal, alloy or Metals composite for easily forging
Material；
Preferably, the metal be Al, Sn, Zn, Pd, Sb, Bi, Au, Ag, Pt, Rh, Ir, Ru, Os, Li, Na, K, Mg,
Any one in Ca, Cr, Mn, V, Ti, Fe, Co, Ni, Cu, Ga, Ge, Zr, Nb, Mo, Cd, In, Pb or Pd；
Or, the alloy be including at least Al, Sn, Zn, Pd, Sb, Bi, Au, Ag, Pt, Rh, Ir, Ru, Os, Li, Na, K,
The alloy of any one in Mg, Ca, Cr, Mn, V, Ti, Fe, Co, Ni, Cu, Ga, Ge, Zr, Nb, Mo, Cd, In, Pb or Pd；
Or, the metallic composite be including at least Al, Sn, Zn, Pd, Sb, Bi, Au, Ag, Pt, Rh, Ir, Ru, Os,
Any one in Li, Na, K, Mg, Ca, Cr, Mn, V, Ti, Fe, Co, Ni, Cu, Ga, Ge, Zr, Nb, Mo, Cd, In, Pb or Pd
Composite material.
As further preferred technical solution, the organic-containing materials include ionic liquid, organic gel materials, wax material
At least one of material, resin, siliceous organic matter, gel macromolecule or organic-inorganic multi-component material；
It preferably, further include conductive additive in the organic-containing materials；
Preferably, the ionic liquid includes quaternary ammonium salt, quaternary phosphine salt, imidazoles, piperidines or pyroles ionic liquid
At least one of body；
Preferably, the organic gel materials include at least one of pitch or rubber；
Preferably, the wax material includes haze tallow, bayberry wax, candelila wax, bears wax in ground, Japan smart wax, palm wax, rice
Chaff wax, Jojoba Oil, castor wax, animal wax, beeswax, insect wax, lanocerin, spermaceti, lignite wax, paraffin, pertroleum wax, Fischer-Tropsch
Wax, polyethylene wax, polypropylene wax, ethane-acetic acid ethyenyl are copolymerized at least one of wax or oxidized polyethylene wax；
Preferably, the resin includes unsaturated polyester (UP), vinyl esters, epoxy resin, phenolic resin, bismaleimide
Resin, polyimide resin, polypropylene, polycarbonate, nylon, polyether-ether-ketone, polyether sulfone, polyethylene, polyvinyl chloride, polyphenyl second
At least one of alkene or ABS resin；
Preferably, the siliceous organic matter includes silicone grease and/or silicone oil；
Preferably, the gel macromolecule include guar gum, xanthan gum, carragheen, Sodium Polyacrylate, PAAm, PEG or
At least one of PAA；
Preferably, the organic-inorganic multi-component material is that various ingredients are mixed comprising organic and inorganic solid particles
At least one of waxy solid, semisolid or liquid, including PVA solid gum, conducting resinl or lubricating grease.
It include that pretreated step is carried out to metal foil before coating organic coating as further preferred technical solution
Suddenly；
Preferably, the pretreatment includes cleaning and/or etching, and the preferably described etching is ion etching；
And/or the coating includes at least one in spin coating, blade coating, brushing, drop coating, dip-coating, spraying, roller coating or showering
Kind.
As further preferred technical solution, which comprises
(a) organic coating is coated on the surface of metal foil；(b) metal foil for being coated with organic coating carries out fold handling；
(c) metal foil Jing Guo doubling is subjected to pressurized treatments；Step (a), (b) and (c) is repeated several times, it is organic to obtain metal-
Coating composite sheet；
Preferably, the number of the doubling is >=5 times, and the number of the pressurization is corresponding with the number of the doubling；
Preferably, the number of the doubling is 5~30 times, preferably 10~20 times；
Preferably, the doubling includes folding the metal foil that one has been coated with organic coating；Or, two are had been coated with
The metal foil of organic coating is overlapped according to the one side for being coated with organic coating；
Preferably, the doubling further include will have been coated with organic coating, at least pressurizeed primary metal-organic coating
Composite sheet is overlapped according to the one side for being coated with organic coating；
Preferably, the pressurization includes axial pressure processing and/or roller process；
Preferably, the driving method of pressurized treatments includes manual pressure and/or electric propulsion；
Preferably, pressurized treatments are while being heated and pressurizeed processing, and heating temperature is 60~300 DEG C；Or,
Pressurized treatments are first to carry out pressurized treatments to carry out heating or ironing processing again, and heating or ironing temperature are 60~300
℃。
As further preferred technical solution, after 5~6 doublings and pressurized treatments, to the organic painting of obtained metal-
Layer composite sheet is post-processed；
Preferably, the post-processing includes natrual ageing and/or artificial aging；
Preferably, the natrual ageing is low temperature natrual ageing, and temperature is 20~80 DEG C, and the time is 12~48h；
Preferably, the artificial aging includes heating anneal, and the temperature of heating anneal is 80~300 DEG C, and the time is 1~
12h；
Preferably, further include the steps that post-processing metal nano plate, the post-processing includes that fine grain is annealed；
Preferably, the temperature of fine grain annealing is the recrystallization temperature of metal, and the time is 10~120min.
As further preferred technical solution, the separation includes ultrasound removing or liquid phase removing；
Preferably, first metal-organic coating composite sheet is soaked in organic solvent, is stirred, then carry out ultrasonic removing
Or liquid phase removing；
Preferably, organic solvent is heated, heating temperature is 60~80 DEG C；
Preferably, stirring includes at least one of mechanical stirring, magnetic agitation or artificial stirring；
Preferably, surfactant or coupling agent are added in separation process；
Preferably, cleaning and drying are include thed steps that after separation；
Preferably, the metal-organic coating composite sheet is with a thickness of 0.001~10mm；
And/or the metal nano plate with a thickness of 5~1000nm.
According to another aspect of the present invention, the present invention provides a kind of preparation method by above-described metal nano plate
The metal nano plate being prepared.
According to another aspect of the present invention, the preparation method that the present invention provides the metal nano plate described in more than one obtains
Purposes of the metal nano plate or the metal nano plate arrived as negative electrode active material.
According to another aspect of the present invention, the present invention provides a kind of negative electrode active material, including above-described metal
The metal nano plate or the metal nano plate that the preparation method of nanometer sheet obtains.
Compared with prior art, the beneficial effects of the present invention are:
(1), the preparation method of metal nano plate provided by the invention covers one layer of organic coating on the surface of sheet metal,
And extended through multiple doubling and pressurization, so that sheet thicknesses are gradually thinning and are finally reached nanoscale, coating can then be made
Each sheet metal is separated for interlayer, the stacking again of sheet metal is avoided to be bonded, and by sheet metal and organic by way of separation
Coating segregation is opened, and then obtains metal nano plate.This method overall process only has a kind of metal to participate in, by coating organic coating generation
Sacrificial metal is replaced, and organic coating obtained after separation can also realize that repetitive cycling uses, and then greatly reduce
Cost；The process material therefor is common materials simultaneously, simple, cheap and easy to get, environmentally friendly and at low cost；Without strong acid and strong base
Etching reduces the generation of chemical waste, environmentally protective, it can be achieved that magnanimity preparation, is more suitable for industrializing, in automated production
Application.
(2), the present invention has widened the range of choice of two-dimensional nano metal, can not be by metal material chemical activity, valence
The limitation of lattice etc., flexibility is good, strong applicability.
(3), this invention simplifies preparation processes, and preparation method is simple, facilitate control, and process safety is efficiently controllable,
It is environmental-friendly, it is low in cost, it is easier to realize large-scale industrial production.
(4), present invention reduces the degree of oxidation of two-dimensional metallic nano material, obtained two-dimensional metallic nano material is pure
Degree is high, high-quality, and available lamella is bigger, thinner two-dimensional metallic nano material.
(5), metal nano plate of the invention has wide range of applications, such as can apply in negative electrode active material, can
Increase the specific surface area of negative electrode active material, improves active material high rate performance, and the metal nano plate of two-dimensional structure is swollen
It is easier to be expanded in thickness direction during swollen, reduces the level of stretch of the binder of surface attachment, it is negative to improve current metal
Pole dusting, metal active material are easy to the problems such as bonding division, realize the developing and expansion of the high-valued application of metal nano plate
Exhibition.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the preparation method flow diagram for the metal nano plate that one embodiment of the present invention provides；
Fig. 2 is the monometallic rolling schematic diagram that one embodiment of the present invention provides；
Fig. 3 (a) is the schematic cross-section of Al- paraffin composite sheet before the removing that the embodiment of the present invention 3 provides；Fig. 3 (b) is
The monolithic Al piece schematic diagram that the embodiment of the present invention 3 provides；
Fig. 4 (a) is the schematic cross-section of Sn- paraffin composite sheet before the removing that the embodiment of the present invention 5 provides；Fig. 4 (b) is
Sn piece schematic diagram after the removing that the embodiment of the present invention 5 provides；
Fig. 5 (a) is the schematic cross-section of Al-PVA composite sheet before the removing that the embodiment of the present invention 16 provides；Fig. 5 (b) is
The monolithic Al piece partial enlargement diagram that the embodiment of the present invention 16 provides；
The Al nanometer sheet schematic diagram being coated on after the removing that Fig. 6 (a) provides for the embodiment of the present invention 4 in organic group bottom；Figure
6 (b) the single layer Al nanometer sheet schematic diagrames provided for the embodiment of the present invention 4.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiments and examples, but this field skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and are not construed as limiting model of the invention
It encloses.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.The person that is not specified actual conditions, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
It should be understood that
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and preferred implementation method
It can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can be with
Intercombination forms new technical solution.
In the present invention, unless otherwise indicated, numberical range " a~b " indicates the contracting of any real combinings between a to b
Sketch form shows that wherein a and b is real number.
" range " disclosed in this invention can be respectively one or more lower limits and one in the form of lower and upper limit
A or multiple upper limits.
In the present invention, unless otherwise indicated, each reaction or operating procedure can be carried out sequentially, can not also be in sequence
It carries out.Preferably, method herein is that sequence carries out.
Unless otherwise indicated, profession used herein and meaning phase known to scientific term and one skilled in the art
Together.In addition, any method similar to or equal to what is recorded or material can also be applied in the present invention.
In a first aspect, providing a kind of preparation method of metal nano plate at least one embodiment, comprising the following steps:
One metal foil is provided, organic coating is coated on the surface of the metal foil, is then coated with the metal of organic coating
The multiple doubling of foil and repeatedly pressurization, obtain metal-organic coating composite sheet；
By in metal-organic coating composite sheet sheet metal and organic coating separate, obtain metal nano plate.
The present invention coats organic coating, multiple doubling and pressurization on a kind of surface of metal foil, obtains the organic painting of metal-
Layer composite sheet；By in metal-organic coating composite sheet sheet metal and organic coating separate, obtain metal nano plate.
Preparing metal nano plate in view of roll process is method most suitably used in current numerous methods, since metal itself can
The characteristic of extension to reach nanoscale under mechanical deformation, and crystal grain can occur in metal during concurrent deformation
The features such as refinement, deformation texture, so that have a fine grain metal nano plate of unique texture is prepared into possibility, and this is also to remove
The not getable unique texture of other materials institute outside metal.And current roll process prepares used by metal nano plate and is all
Bimetallic roll process, there are at high cost, metals to be easy cracking dusting, part metals are easily oxidized, trivial operations, it is not easy to control,
The problems such as energy consumption is high, seriously polluted.The present invention is off the beaten track, provides a kind of monometallic roll pressing creatively for cheap metal
The method of nanometer sheet, to overcome the problems, such as at least one in the above problem.
It further says, the present invention prepares metal nano plate by the efficient magnanimity of physical compression, has what is cut
The surface of ductile metal covers one layer of organic coating, and carries out multiple doubling pressurization by pressuring machine and extend, so that sheet metal
Thickness is gradually thinning and is finally reached nanoscale, and coating is then used as interlayer to separate each sheet metal, avoids sheet metal again
Bonding is stacked, is finally purified by organic coating and sheet metal separation or by metal nano plate, obtains metal nano plate.Above-mentioned Dan Jin
Belonging to roll process overall process only has a kind of metal to participate in, by coating organic coating instead of sacrificial metal, since organic coating exists
There is solubility in corresponding organic solvent, interlayer only can be removed by the method for dissolution, and can be by the modes such as distilling, extracting
The organic matter of dissolution is purified into recycling again.Thus, this method greatly reduces cost, while stock utilization pole
Height, environmentally protective, the application being extremely suitable in industrial production.
It should be noted that sheet metal used in the present invention is malleable/easy forging with ductility or potential ductility
Sheet metal.Wherein " ductility ", " malleable ", " easily forging " are term well known to those skilled in the art, and it is special that the present invention does not make
Limitation, according to the common understanding of those skilled in the art.
It is understood that " multiple doubling and repeatedly pressurization " refers to, fold handling at least twice, Yi Jizhi have been carried out
Few pressurized treatments twice, and the number of doubling and pressurization is corresponding.It is not special for the specific number of doubling and pressurization
Limitation, as long as not generating limitation to the purpose of the present invention；Such as can for 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times,
9 times, 10 times, 11 times, 12 times, 13 times, 14 times, 15 times, 16 times, 17 times, 18 times, 19 times, 20 times, 21 times, 22 times, 23 times, 24
Secondary, 25 inferior, preferably 5 times or more, more preferably 10 times or more, more preferably 10~25 times.
It is understood that the present invention is not particularly limited the concrete type of metal foil, as long as not to of the invention
Purpose generates limitation.
In a preferred embodiment, the metal foil is malleable/metal, alloy or Metals composite for easily forging
Material.
It should be understood that above-mentioned " a kind of sheet metal " or " monometallic " refer to, in whole preparation process only with
A kind of metal, a kind of alloy or a kind of metallic composite.The type of metal is not done it is specifically limited, likewise, for
Metallic element included in alloy or metallic composite does not do specifically limited yet.
Preferably, metal include but is not limited to Al, Sn, Zn, Pd, Sb, Bi, Au, Ag, Pt, Rh, Ir, Ru, Os, Li, Na,
K, any one in Mg, Ca, Cr, Mn, V, Ti, Fe, Co, Ni, Cu, Ga, Ge, Zr, Nb, Mo, Cd, In, Pb or Pd.
Preferably, alloy include but is not limited to include at least Al, Sn, Zn, Pd, Sb, Bi, Au, Ag, Pt, Rh, Ir, Ru,
It is any one in Os, Li, Na, K, Mg, Ca, Cr, Mn, V, Ti, Fe, Co, Ni, Cu, Ga, Ge, Zr, Nb, Mo, Cd, In, Pb or Pd
The alloy of kind.It is understood that alloy refer to by two or more metal and metal or it is nonmetallic by certain methods
Synthesized substance with metallic character；It is typical but unrestricted, alloy be, for example, Al-Sn alloy, Fe-Sn alloy,
Al-Ti alloy, Ti-Mg alloy etc..
Preferably, metallic composite include but is not limited to include at least Al, Sn, Zn, Pd, Sb, Bi, Au, Ag, Pt,
Rh, Ir, Ru, Os, Li, Na, K, Mg, Ca, Cr, Mn, V, Ti, Fe, Co, Ni, Cu, Ga, Ge, Zr, Nb, Mo, Cd, In, Pb or Pd
In any one composite material.It is understood that metallic composite refers to metal institute in conjunction with other nonmetallic materials
The metal-base composites of formation.Typical but non-limiting metallic composite include graphene-metallic composite,
Carbon fiber reinforced metal matrix composite or ceramic-metal composite material etc..
According to the present invention, organic coating is the choosing of the material for separate metal nanometer sheet, for forming organic coating
It selects most important.Reason is: (1) due in roll milling process metal material will be pressurizeed and extended, organic painting
Layer must have good deformation spreading ability to guarantee that being attached to interlayer in roll milling process plays buffer action.(2) due to
The cracking dusting of metal is not can avoid in roll milling process, it is therefore desirable to maintain photomacrograph type complete by the cohesive force of organic coating
The problem of whole, therefore suitable organic coating can alleviate metal dusting.(3) since part metals have greater activity easily by oxygen
Change, needs organic insulating layer to completely cut off water oxygen as far as possible, and reduce the oxidation of two-dimensional metallic nano material using physics removing mode
Therefore suitable organic coating can alleviate the problem of metal oxidation.
Based on this, the present invention passes through a large amount of experimental study, the suitable organic-containing materials found, which rises
To effect include: that (1) coating material and sheet metal surface wettability are good, and sheet metal surface covering plays in pressure process
Separate metal piece avoids surface atom layer hypotelorism between sheet metal from stacking bonding again.(2) coating has certain bonding
Power can guarantee that each sheet metal thin layer will not disperse to slide because internal stress deforms in pressure process, will not because of fragmentation and
It directly falls off, so that whole be able to maintain that lamellar is extended convenient for further pressurization.(3) coating material has good exclusion of water
Oxygen ability, can in roll milling process the stronger metal of preferable protection activity it is not oxidized.(4) coating material can be in toxicity
There is good dissolubility in low, cheap organic solvent, guarantee the removing of sheet metal and low in cost.
In a preferred embodiment, the organic-containing materials include ionic liquid, organic gel materials, wax material
At least one of material, resin, siliceous organic matter, gel macromolecule or organic-inorganic multi-component material and optional conduction
Additive.
It should be noted that " organic-containing materials " refer to, it is used to form the material of organic coating." optional conduction adds
Add agent " refer to, conductive additive can be added in the organic-containing materials, can not also add conductive additive.
According to the present invention, ionic liquid, organogel material can be selected from the organic-containing materials of metal nano plate interlayer
One or more of material, wax material, resin, siliceous organic matter, gel macromolecule or organic-inorganic multi-component material material sheet
Body or solution.That is, organic-containing materials above-mentioned can directly be brought use, or by a certain percentage in coating procedure
It is dissolved in solvent and preparing, or be mixed in solvent with conductive additive be prepared into organic-containing materials by a certain percentage.
Preferably, the ionic liquid includes but is not limited to quaternary ammonium salt, quaternary phosphine salt, imidazoles, piperidines or pyrroles
At least one of class ionic liquid.
Preferably, the organic gel materials include but is not limited at least one of pitch or rubber, preferably pitch.
Preferably, the wax material include but is not limited to haze tallow, bayberry wax, candelila wax, bear wax in ground, the smart wax of Japan,
Palm wax, rice bran wax, Jojoba Oil, castor wax, animal wax, beeswax, insect wax, lanocerin, spermaceti, lignite wax, paraffin, petroleum
Wax, Fischer-Tropsch wax, polyethylene wax (PE wax), polypropylene wax (PP wax), ethane-acetic acid ethyenyl copolymerization wax (EVA wax) or oxidation are poly-
At least one of ethylene waxes.
Preferably, the resin includes but is not limited to unsaturated polyester (UP), vinyl esters, epoxy, phenolic aldehyde, bismaleimide
(BMI), polyimide resin, polypropylene (PP), polycarbonate (PC), nylon (NYLON), polyether-ether-ketone (PEEK), polyether sulfone
(PES), at least one of polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS) or ABS resin.
Preferably, the siliceous organic matter includes but is not limited to silicone grease and/or silicone oil.
Preferably, the gel macromolecule include but is not limited to guar gum, xanthan gum, carragheen, Sodium Polyacrylate,
At least one of PAAm, PEG or PAA, preferably guar gum.
Preferably, the organic-inorganic multi-component material is that various ingredients are mixed comprising organic and inorganic solid particles
Waxy solid, semisolid or liquid, including but not limited at least one of PVA solid gum, conducting resinl or lubricating grease.It needs
Illustrate, organic-inorganic multi-component material is waxy solid, semi-solid material or viscosity of the larger liquid, is contained or not contain
Organic-inorganic solid particle, the material for having features above are regarded as organic-inorganic multi-component material.
According to the present invention, using above-mentioned specific organic-containing materials, during the preparation process by being applied on sheet metal surface
One layer of organic coating is covered, and repeatedly doubling rolled metal foil, organic coating separates each layer metal foil in roll milling process, and rolling is complete
Cheng Houyong solvent dissolves the organic insulating layer of metal interlevel, can then be separated each thin metal layer by way of ultrasound.Entire system
Standby process only has a kind of sheet metal to participate in, used to be etched using being common materials without strong acid and strong base, low in cost,
It is environmentally protective.
Fig. 1 shows the preparation method flow diagram for the metal nano plate that one embodiment of the present invention provides；Fig. 2 is aobvious
The monometallic rolling schematic diagram that one embodiment of the present invention provides is shown；Referring to Figures 1 and 2, preferred in one kind of the invention
In embodiment, this method comprises: cleaning metal foil (sheet metal), coating organic coating, doubling rolling (doubling and pressurization), from
The step of right timeliness, heating immersion, ultrasound removing, cleaning, drying and processing.
It should be noted that natrual ageing therein can use low-temperature heat or other artificial aging processing mode generations
It replaces, it can also be without the step (the step of natrual ageing or artificial aging).
According to the method for the present invention, a kind of malleable easy forging with ductility or potential ductility is used only during the preparation process
Metal or alloy foil, without other metals as sacrificial metal；The organic-containing materials for separate metal nanometer sheet have been used,
And metal surface is applied to before each pressurization；Metal-organic coating composite sheet is obtained by multiple doubling pressurization (doubling rolling)
Material；Sheet metal is separated with organic insulating layer, obtains the metal nano plate of different-thickness.In addition, the present invention also provides specific
Stress release technique, specific heat treatment, post-processing approach.
Present invention optimizes the separating-purifying modes of metal nano plate, are mentioned metal nano plate by the methods of ultrasonic disperse
Pure, i.e., ultrasonic disperse separating-purifying substitutes chemical etching, can reduce impurity introducing, to simplify technique；It is used as dispersion liquid simultaneously
Organic solvent dissolution interlayer after can by separating-purifying realize organic dispersions and separation layer recycling, thus into one
Step reduces cost, reduces discharging of waste liquid and pollutes environment.
Preparation method of the invention can be realized the efficient of metal nano plate, magnanimity preparation, the full mistake of monometallic roll process
Journey only has a kind of metal to participate in, during the preparation process by being coated with one layer of organic coating on sheet metal surface, and repeatedly doubling roller
Sheet metal is rolled, organic coating separates each layer sheet metal in roll milling process, can dissolve metal interlevel with solvent after the completion of rolling
Organic insulating layer, and separated each thin metal layer by way of ultrasound.Common materials, operation letter is used only in entire preparation flow
It is single, easy, it is etched without strong acid and strong base, it is low in cost, it is environmentally protective.
It in a preferred embodiment, include that pretreated step is carried out to metal foil before coating organic coating
Suddenly；
Preferably, the pretreatment includes cleaning and/or etching, and the preferably described etching is ion etching；
And/or the coating includes at least one in spin coating, blade coating, brushing, drop coating, dip-coating, spraying, roller coating or showering
Kind.
Sheet metal is pre-processed before coating, is more conducive to the combination of organic coating and sheet metal, to obtain
The superior metal nano plate of performance.It is understood that present invention spy no for the concrete operations mode for pre-processing, coating
Different limitation, as long as not generating limitation to the purpose of the present invention.
In a preferred embodiment, which comprises
(a) organic coating is coated on the surface of metal foil；(b) metal foil for being coated with organic coating carries out fold handling；
(c) metal foil Jing Guo doubling is subjected to pressurized treatments；Step (a), (b) and (c) is repeated several times, it is organic to obtain metal-
Coating composite sheet；
Preferably, the number of the doubling is >=5 times, and the number of the pressurization is corresponding with the number of the doubling；
Preferably, the number of the doubling is 5~30 times, preferably 10~20 times；
Preferably, the doubling includes folding the metal foil that one has been coated with organic coating；Or, two are had been coated with
The metal foil of organic coating is overlapped according to the one side for being coated with organic coating；
Preferably, the doubling further include will have been coated with organic coating, at least pressurizeed primary metal-organic coating
Composite sheet is overlapped according to the one side for being coated with organic coating；
Preferably, the pressurization includes axial pressure processing and/or roller process；
Preferably, the driving method of pressurized treatments includes manual pressure and/or electric propulsion；
Preferably, pressurized treatments are while being heated and pressurizeed processing, and heating temperature is 60~300 DEG C；Or,
Pressurized treatments are first to carry out pressurized treatments to carry out heating or ironing processing again, and heating or ironing temperature are 60~300
℃。
According to the present invention, organic coating is coated with before each pressurization；Doubling includes will have been coated with organic coating a piece of
Sheet metal folds；Or, by a face relative superposition of the same or similar sheet metal coating organic coating of two parts of sizes；Or, by two
Part is identical to have been coated with the metal-organic coating composite sheet overlapping of organic coating, pressurization several times.
It should be noted that doubling includes a variety of implementations, such as can will have been coated with the sheet metal doubling of coating,
Or the sheet metal is cut into after two panels overlapping up and down, or by two parts of identical gold for having been coated with the certain number of coating, rolling
Belong to piece to be overlapped up and down.Pressurization includes axial pressure processing or roller process.The driving method of pressurized treatments can add to be manual
Pressure, or electric propulsion.
Further, above-mentioned pressurized treatments be heating pressurized treatments, it is described heating pressurized treatments heating temperature be 60~
300℃.If being unable to reach while heating the condition of pressurization, the heating means replaced can be used, specifically: to the metal after pressurization
Piece carries out ironing processing, according to an embodiment of the invention, heating temperature is 60~300 DEG C, the selection of actual temp need to be according to institute
With the plastic deformation ability of metal and fusing point burning point of layers of material etc..Ironing concrete mode is to answer the metal after pressurization
It closes piece to be put on the heating plate of surfacing, is slowly pressed on metal composite on piece with another plate and imitates ironing to peripheral direction
The mode of clothes, which pushes away, to be pressed, or by the metal compound sheet roll-in after heating.Example according to the present invention, pressuring method are roll-in, are arrived 5
METAL HEATING PROCESS bating effect is obvious after 6 times, and smooth metal is returned in the metal compound sheet ironing that this ironing mode can deform roll-in
Composite sheet, to a certain degree release internal stress, reduce cracking crushing phenomenon.
Further, multiple doubling and pressurized treatments include: (1) in metallic upper surface one layer of coating of coating；(2) institute is folded
It states metal compound sheet, or metal compound sheet is cut into size is approximate and to be overlapped by two parts, or by two parts of identical metals
Composite sheet overlapping；(3) pressurized treatments are carried out to the sheet metal of at least two panels applying coating, to obtain metal compound sheet；
(4) step (1) (2) (3) are repeated several times, to obtain the multiple layer metal nanometer sheet.
In a preferred embodiment, after 5~6 doublings and pressurized treatments, to the organic painting of obtained metal-
Layer composite sheet is post-processed；
Preferably, the post-processing includes natrual ageing and/or artificial aging；
Preferably, the natrual ageing is low temperature natrual ageing, and temperature is 20~80 DEG C, and the time is 12~48h；
Preferably, the artificial aging includes heating anneal, and the temperature of heating anneal is 80~300 DEG C, and the time is 1~
12h；
Preferably, further include the steps that post-processing metal nano plate, the post-processing includes that fine grain is annealed；
Preferably, the temperature of fine grain annealing is the recrystallization temperature of metal, and the time is 10~120min
It should be noted that post-processing of the invention includes post-processing and doubling pressurization whole process in doubling pressure process
Post-processing after the completion.Post-processing in the process is believed that after 5 times or so doublings and carries out, and is included at room temperature~80 DEG C and places
12~48 hours low temperature natrual ageing and 80~300 1~12 hour low-temperature annealing of degrees Centigrade.After the completion of doubling pressurization
Post-processing be heated to the metal or alloy recrystallization temperature keep the temperature progress fine grain annealing in 10~120 minutes.
It further says, above-mentioned post-processing mainly includes low temperature natrual ageing, heating anneal and fine grain annealing.Wherein, low
Warm natrual ageing for having easy forging metal such as aluminium, tin of high ductibility etc. at room temperature, this metalloid is in roll milling process medium temperature
Degree is maintained at room temperature to 80 DEG C, and releases in a manner of through natrual ageing at doubling 5 times or so rear placements naturally 12~48 hours
Put internal stress.Heating anneal is poor for ductility at room temperature but the wrought metal such as iron of preferable ductility can be obtained after heating
Deng this metalloid temperature in roll milling process is maintained at 80 DEG C to 300 DEG C, and moves back after doubling 5 times or so at 80 DEG C to 300 DEG C
Fiery 2 to 8 hours release internal stress.Fine grain is annealed then mainly for the subsequent reinforced technique after the completion of metal nano plate preparation, if
It needs to carry out refined crystalline strengthening to the metal nano plate for having prepared completion, then it can be by the way that metal nano plate be heated to the metal or conjunction
The recrystallization temperature of gold keeps the temperature progress fine grain annealing in 10 to 120 minutes.Need to indicate, this method for easily forge metal can without
Continue rolling in the case where release stress measures, completes the preparation of nanometer sheet, therefore processing method above-mentioned whether or not using
It can be assumed that within the scope of the present invention.
In a preferred embodiment, the separation includes ultrasound removing or liquid phase removing；
Preferably, first metal-organic coating composite sheet is soaked in organic solvent, is stirred, then carry out ultrasonic removing
Or liquid phase removing；
Preferably, organic solvent is heated, heating temperature is 60~80 DEG C；
Preferably, stirring includes at least one of mechanical stirring, magnetic agitation or artificial stirring；
Preferably, surfactant or coupling agent are added in separation process；
Preferably, cleaning and drying are include thed steps that after separation.
According to the present invention, mode metal nano plate and organic coating separated includes: by the metal-after the completion of rolling
Organic insulating layer composite sheet is soaked in organic solution, and slightly stirring dissolves part organic insulating layer material, then carries out ultrasonic stripping
From or liquid phase removing.Ultrasound removing is ultrasonically treated solution, disperses metal plate layer.Liquid phase removing applies solution
Ultrahigh speed rotation, removes metal plate layer by tangential force.It should be noted that be wax-like material for part room temperature,
The fusing point or softening point of material are heated to when need to impregnate organic solvent before separation, so that material fusing accelerates dissolution.
Preferably, the metal-organic coating composite sheet is with a thickness of 0.001~10mm；
Preferably, metal nano plate described in single layer with a thickness of 5~1000nm.
According to the present invention, metal nano plate is two-dimensional sheet structure, and thickness belongs to nano-grade size, such as can be several
Nanometer is to tens nanometers, and on two-dimensional surface, size is not limited specifically.In the present invention, the thickness of single-layer metal nanometer sheet
Degree it is typical but unrestricted for example can for 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 50nm, 60nm, 80nm, 100nm,
200nm, 500nm, 600nm, 800nm or 1000nm.Intermediate product metal-organic coating composite sheet thickness typical case but non-limit
System for example can for 0.001mm, 0.01mm, 0.1mm, 0.5mm, 0.8mm, 1mm, 2mm, 3mm, 5mm, 6mm, 8mm or
10mm。
According to some embodiments of the present invention, the method specifically includes the following steps:
S1, the sheet metal (negative electrode metallic foil/collector) for cutting required size, sheet metal is cleaned up；Or it is logical
Cross ion etching processing sheet metal surface；
S2, by organic-containing materials above-mentioned (ionic liquid, organic gel materials, wax material, resin, siliceous organic matter,
At least one of gel macromolecule or organic-inorganic multi-component material) use is directly brought, or be dissolved in by a certain percentage molten
It is prepared in agent, or is mixed in solvent with conductive additive is prepared into coating by a certain percentage；
S3, one of table that organic coating slurry is coated on to sheet metal uniformly through modes such as spin coating, blade coating, brushings
Face；
S4, sheet metal is cut into the identical two halves of size, together by one face relative superposition of coating sizing-agent；
S5, pressurized treatments are carried out to sheet metal, to obtain metal-organic coating composite sheet.It should be noted that
In the step, the concrete mode of pressurized treatments is not particularly limited, and those skilled in the art can select according to the actual situation
It selects.According to an embodiment of the invention, the pressurized treatments can be axial pressure processing or roller process.The driving of pressurized treatments
Mode can be manual pressure, or electric propulsion.Thus, it is possible to guarantee to be applied to the pressure of metal composite on piece more
It is evenly dispersed in full wafer metal composite on piece, it is more uniform thick to thereby may be ensured that the multiple layer metal nanometer sheet of acquisition has
Degree.For example, roll squeezer can be used, roller process is carried out to metal compound sheet.Two metal compound sheets become after pressurized treatments
Thin and fit closely in together, interlayer is equally distributed coating material；
S6: carrying out simple heating anneal to the sheet metal after pressurization or ironing handled, according to an embodiment of the invention, heating
Temperature is 60~300 DEG C, and the selection of actual temp need to be according to the plastic deformation ability of metal used and the fusing point of layers of material
Burning point etc..Ironing concrete mode is that the metal compound sheet after pressurization is put on the heating plate of surfacing, with another plate
It is slowly pressed on metal composite on piece to push away and press to the mode that peripheral direction imitates ironing clothes, or by the metal compound sheet roller after heating
Pressure.Example according to the present invention, pressuring method are roll-in, and METAL HEATING PROCESS bating effect is obvious after 5 to 6 times, this ironing mode can
Smooth metal compound sheet is returned into the metal compound sheet ironing of roll-in deformation, to a certain degree release internal stress, reduces cracking and crush
Phenomenon.It should be noted that step 6 can be carried out, it can also be without step 6.
S7, step 3 is repeated to step 6.Specifically, the plate shears after pressurization are cut into roughly the same two parts, up and down
Overlapping continues pressurized operation after placing and pushes back original thickness, so that the number of plies doubles thickness and halves, it, can by multiple roll-in
So that in final metal compound sheet single-layer metal piece thickness reach tens nanometers it is even following；
S8, metal-organic coating composite sheet is placed in the organic solvent of heating and is stirred, heating temperature according to it is organic every
Layer material difference can be set between 60~80 DEG C, and agitating mode can be a variety of agitating modes such as magnetic stirring, mechanical stirring, stirring
Time is 1~2 hour.
S9, the stirring of ultrasonic or high speed rotation is carried out to solution, metal plate layer is separated from each other.It should be noted that improve
A small amount of surfactant or coupling agent can be added in peeling effect.
It should be noted that if there is heat simultaneously the conditions of pressurized treatments then allow step 5 and step 6 simultaneously into
Row.
It should be understood that unspecified content in above-mentioned preparation method, such as the concrete operations condition of coating etc.
Be this field routine, can be regulated and controled according to the actual situation by those skilled in the art, thus can be omitted to its
It is described in detail.
It can be seen from the above preparation method of the invention mainly has the advantage that (1) is single compared with prior art
Metallic rolled method is due to being used only a kind of metal, because of the problem of sacrificial metal may be not present, simultaneously because the removal of organic insulating layer
It is to be realized by being scattered in organic solvent, belongs to physical method, therefore the organic liquid waste after separation can pass through distillation, liquid separation etc.
Mode carries out separating-purifying to internal composition to realize recycling.Whole process can reach the superelevation material close to 95% or more
Utilization rate.(2) monometallic rolling reduces the temperature and time of annealing compared to current bimetallic roll process, or even without
Stress release processing, although not can avoid the Fragmentation Phenomena of sheet metal in roll milling process, since organic insulating layer has bonding
Property, therefore broken sheet metal still can be bonded mutually, maintain integral sheet shape, so that powder phenomenon-tion does not interfere with roller
Roll the progress of process.(3) organic insulating layer can prevent the water oxygen in air from contacting with new exposing metal in roll milling process, You Jicai
Material can form protective layer in metal surface, reduce metal oxidation.In addition, this method replaces etching using dissolution, further avoid
The oxidation of metal.(4) due to the high volatile of organic solvent, high purity metal nanometer sheet can be obtained by volatilization.This
Outside, monometallic roll process of the invention remains original advantage such as while solving existing issue: magnanimity preparation, not by
Metal species limitation, achievable industrial automation production etc..
Second aspect provides a kind of preparation method system by above-described metal nano plate at least one embodiment
Standby obtained metal nano plate.
Has the whole of the preparation method of above-mentioned metal nano plate using the metal nano plate that preparation method of the present invention obtains
Advantage, details are not described herein.
The third aspect, the preparation method for providing a kind of metal nano plate as described above at least one embodiment obtain
Purposes of the metal nano plate or the metal nano plate arrived as negative electrode active material.
Fourth aspect, at least one embodiment a kind of negative electrode active material, including above-described metal nano plate
Preparation method obtained metal nano plate or the metal nano plate.
It should be understood that the third aspect of the present invention and fourth aspect and the preparation method of metal nano plate above-mentioned are
Based on the same inventive concept, thus at least have the institute of the preparation method of metal nano plate above-mentioned effective, herein no longer
It repeats.
In addition, applying metal nano plate of the invention as negative electrode active material in all kinds of ion-conductances, Dual-ion cell
Or in capacitor, it is capable of increasing the specific surface area of negative electrode active material, improvement active material high rate performance, and two-dimensional structure
Metal nano plate is easier to be expanded in thickness direction in expansion process, reduces the level of stretch of the binder of surface attachment,
Improve current metal negative electrode dusting, metal active material is easy to the problems such as bonding division, realize the high-valued of metal nano plate
The developing and extension of application.
Combined with specific embodiments below, comparative example and attached drawing, the invention will be further described.
Embodiment 1-4
A kind of preparation method of metal nano plate, comprising the following steps:
One metal foil is provided, coats organic coating on the surface of metal foil, the metal foil for being then coated with organic coating is more
Secondary doubling and repeatedly pressurization, obtain metal-organic coating composite sheet；
By in metal-organic coating composite sheet sheet metal and organic coating separate, obtain metal nano plate.
Metal species used by embodiment 1-4 and organic-containing materials are all the same, and difference essentially consists in rolling
(doubling) number, the prevailing operating conditions of embodiment 1-4 and obtained metal nano chip size are as shown in table 1.
The operating condition of 1 embodiment 1-4 of table and obtained metal nano chip size
Embodiment 5-10
Compared with Example 4, used organic-containing materials are all the same, and difference essentially consists in by embodiment 5-10
The prevailing operating conditions of metal species and rolling (doubling) number, embodiment 4 and embodiment 5-10 and obtained metal nano
Chip size is as shown in table 2.
The operating condition of 2 embodiment 4-10 of table and obtained metal nano chip size
Embodiment 11-23
Compared with Example 4, used metal species are all the same, and difference essentially consists in organic by embodiment 11-23
The prevailing operating conditions of coating material and rolling (doubling) number, embodiment 4 and embodiment 11-23 and obtained sheet metal ruler
It is very little as shown in table 3.
3 embodiment 4 of table, the operating condition of 11-23 and obtained metal nano chip size
In addition, Fig. 3 shows the SEM shape appearance figure of 3 gained roll-in sheet material of the embodiment of the present invention, can be seen that from Fig. 3 (a)
Obvious lamination is can be seen that after multiple roll-in, at section；Fig. 3 (b) is single-layer metal piece partial enlarged view, from Fig. 3 (b)
It can be seen that single-layer metal piece thickness is reduced to 100nm or less.
Fig. 4 shows the SEM shape appearance figure of 5 gained composite sheet of the embodiment of the present invention, from Fig. 4 (a) as can be seen that paraffin
(black) is good to be distributed between Sn sheet metal (white)；And in Fig. 4 (b), by separating-purifying, paraffin has been completely removed,
Obtain high-purity tin nanometer sheet.
Fig. 5 shows the SEM shape appearance figure of 16 gained composite sheet of the embodiment of the present invention, from Fig. 5 it will be evident that through multiple
After roll-in, PVA plays the role of good isolating metal piece and contacts with each other, well-separated between metal plate layer, while single
Layer has reached nanometer grade thickness.
Fig. 6 shows that the SEM shape appearance figure for the Al nanometer sheet that the embodiment of the present invention 4 obtains, Fig. 6 (a) are to remove by ultrasound
And it is coated on the Al nanometer sheet in organic group bottom, average thickness is 50nm or less；Fig. 6 (b) is obtained by adhesive tape stripping method
Translucent phenomenon is presented under SEM observation since the thickness of Al nanometer sheet is very thin in large area Al nanometer sheet.
As can be seen that metal nano plate produced by the present invention purity is high, high-quality from the figures above.
Application Example and comparative example
Application Example 1: corresponding obtained cathode is filtered with the material mixed oxidization graphene of embodiment 5, with ferric phosphate
Lithium is anode, with LiPF6/ EC-DEC is electrolyte, and wherein EC:DEC is 4:6, is assembled into battery, is carried out to the secondary cell
Electrochemical property test, test result are as shown in table 4.
Comparison study example 1: slurry is mixed with simultaneously with 8:1:1 ratio in NMP with natural graphite, conductive black, PVDF
It is coated on copper foil and obtains cathode, with the identical anode of Application Example 1 and electrolyte assembled battery, the comparative example that is applied 1,
And electrochemical property test is carried out to the secondary cell, test result is as shown in table 4.
Comparison study example 2: it using Al foil as cathode, with the identical anode of Application Example 1 and electrolyte assembled battery, obtains
Comparison study example 2, and electrochemical property test is carried out to the secondary cell, test result is as shown in table 4.
4 secondary cell the performance test results of table
| Serial number | Cycle-index | Capacity retention ratio | Coulombic efficiency |
| Application Example 1 | 500 | 88% | 93.20% |
| Comparison study example 1 | 500 | 75% | 86.10% |
| Comparison study example 2 | 500 | 72% | 85.50% |
As can be seen that in the secondary battery by metal nano plate application of the invention, the cycle performance of battery can be improved,
Hoist capacity conservation rate and coulombic efficiency.
Comparative example 1
A kind of preparation method of metal nano plate in the prior art, the patent disclosure of Publication No. CN105774120A
Prepare the method or document 2D Metals by Repeated Size Reduction of metal nano plate
(Adv.Mater.2016,28 (37)
Disclosed method.
The pressurization that overlaps using two different metal or alloy sheet materials is emphasized in preparation method in the prior art,
And doubling rolling repeatedly, so that metal or alloy sheet material is constantly extended thinning, be finally reached thickness in monolayer be nanoscale metal or
Alloy stratiform composite sheet (obtains the straticulate structure that thickness in monolayer is 0.9~21nm), and rotten by chemical attack, electrochemistry
Erosion or the modes such as heat erosion eliminate a kind of metal to obtain the nanometer chip architecture of another metal.The metal nano plate of comparative example
Preparation method distinguished compared with mainly with the method for the embodiment of the present invention are as follows:
(1) existing method is repeatedly emphasized to carry out rolling using two kinds or more of metal, and one kind is used only in the present invention
Metal simultaneously uses the organic-containing materials of high ductibility as interlayer, for cheap metal cost considerable decrease.In addition, sacrificing gold
The metal species of the selection of category preparation nanometer sheet needed for limiting to a certain degree, since it is desired that etching away sacrificial metal to obtain
Another nanometer sheet of metal, therefore prepare a certain amount of nanometer sheet and need to consume another metal of equivalent.For noble metal
For use cheap metal still to receive as sacrificial metal, but to prepare cheap metal nanometer sheet, preparation cost then can
It significantly improves, this is worthless on industrial application.
(2) existing method eliminates processing hardening and the internal stress of metal using the mode of heating anneal to avoid metal
Dusting cracking influence rolling, that is, used long-time high annealing to restore the ductility of metal as far as possible；And present invention benefit
So that sheet metal is cracked with the caking property of organic insulating layer and do not fall off, eliminate the influence to roll milling process of cracking, so as to only into
Row low-temperature heat does not even heat direct rolling.
(3) existing method eliminates interlayer using chemical modes such as chemical attack, electrochemical corrosion or heat erosions, this
Invention eliminates interlayer, more safety and environmental protection, low energy consumption by fusing, dissolution, the physics modes such as vaporization.In addition, existing method
Purification difficult carries out that multiple ultracentrifugation is needed to clean due to needing to remove metal salt impurity in solution after etching,
Improve cost for purification.
(4) existing method may result in metal in chemically etching process and cross polyoxy for high activity metal
Change, such as Al, Sn metal nano plate preparation stronger for activity forms challenge, and the course of dissolution of the method for the present invention can pole
Big degree avoids the oxidation of metal.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of metal nano plate, which comprises the following steps:
One metal foil is provided, coats organic coating on the surface of the metal foil, the metal foil for being then coated with organic coating is more
Secondary doubling and repeatedly pressurization, obtain metal-organic coating composite sheet；
By in metal-organic coating composite sheet sheet metal and organic coating separate, obtain metal nano plate.
2. the preparation method of metal nano plate according to claim 1, which is characterized in that the metal foil is malleable/easy
Metal, alloy or the metallic composite of forging；
Preferably, the metal be Al, Sn, Zn, Pd, Sb, Bi, Au, Ag, Pt, Rh, Ir, Ru, Os, Li, Na, K, Mg, Ca, Cr,
Any one in Mn, V, Ti, Fe, Co, Ni, Cu, Ga, Ge, Zr, Nb, Mo, Cd, In, Pb or Pd；
Or, the alloy be including at least Al, Sn, Zn, Pd, Sb, Bi, Au, Ag, Pt, Rh, Ir, Ru, Os, Li, Na, K, Mg,
The alloy of any one in Ca, Cr, Mn, V, Ti, Fe, Co, Ni, Cu, Ga, Ge, Zr, Nb, Mo, Cd, In, Pb or Pd；
Or, the metallic composite be including at least Al, Sn, Zn, Pd, Sb, Bi, Au, Ag, Pt, Rh, Ir, Ru, Os, Li,
Any one in Na, K, Mg, Ca, Cr, Mn, V, Ti, Fe, Co, Ni, Cu, Ga, Ge, Zr, Nb, Mo, Cd, In, Pb or Pd it is compound
Material.
3. the preparation method of metal nano plate according to claim 1, which is characterized in that the organic-containing materials include
In ionic liquid, organic gel materials, wax material, resin, siliceous organic matter, gel macromolecule or organic-inorganic multi-component material
At least one；
It preferably, further include conductive additive in the organic-containing materials；
Preferably, the ionic liquid includes in quaternary ammonium salt, quaternary phosphine salt, imidazoles, piperidines or pyrrole ionic liquid
At least one；
Preferably, the organic gel materials include at least one of pitch or rubber；
Preferably, the wax material includes haze tallow, bayberry wax, candelila wax, bears wax in ground, Japan smart wax, palm wax, rice bran
Wax, Jojoba Oil, castor wax, animal wax, beeswax, insect wax, lanocerin, spermaceti, lignite wax, paraffin, pertroleum wax, Fischer-Tropsch wax,
Polyethylene wax, polypropylene wax, ethane-acetic acid ethyenyl are copolymerized at least one of wax or oxidized polyethylene wax；
Preferably, the resin includes unsaturated polyester (UP), vinyl esters, epoxy resin, phenolic resin, bismaleimide tree
Rouge, polyimide resin, polypropylene, polycarbonate, nylon, polyether-ether-ketone, polyether sulfone, polyethylene, polyvinyl chloride, polystyrene
Or at least one of ABS resin；
Preferably, the siliceous organic matter includes silicone grease and/or silicone oil；
Preferably, the gel macromolecule includes guar gum, xanthan gum, carragheen, Sodium Polyacrylate, PAAm, PEG or PAA
At least one of；
Preferably, the organic-inorganic multi-component material is that various ingredients are mixed comprising organic and inorganic solid particles waxes
At least one of shape solid, semisolid or liquid, including PVA solid gum, conducting resinl or lubricating grease.
4. the preparation method of metal nano plate according to claim 1, which is characterized in that wrapped before coating organic coating
It includes and pretreated step is carried out to metal foil；
Preferably, the pretreatment includes cleaning and/or etching, and the preferably described etching is ion etching；
And/or the coating includes at least one of spin coating, blade coating, brushing, drop coating, dip-coating, spraying, roller coating or showering.
5. the preparation method of metal nano plate according to claim 1, which is characterized in that the described method includes:
(a) organic coating is coated on the surface of metal foil；(b) metal foil for being coated with organic coating carries out fold handling；(c) will
The metal foil by doubling carries out pressurized treatments；Step (a), (b) and (c) is repeated several times, obtains metal-organic coating
Composite sheet；
Preferably, the number of the doubling is >=5 times, and the number of the pressurization is corresponding with the number of the doubling；
Preferably, the number of the doubling is 5~30 times, preferably 10~20 times；
Preferably, the doubling includes folding the metal foil that one has been coated with organic coating；Or, having been coated with organic painting for two
The metal foil of layer is overlapped according to the one side for being coated with organic coating；
Preferably, the doubling further includes that will to have been coated with organic coating, the primary metal-organic coating that at least pressurizeed compound
Piece is overlapped according to the one side for being coated with organic coating；
Preferably, the pressurization includes axial pressure processing and/or roller process；
Preferably, the driving method of pressurized treatments includes manual pressure and/or electric propulsion；
Preferably, pressurized treatments are while being heated and pressurizeed processing, and heating temperature is 60~300 DEG C；Or,
Pressurized treatments are first to carry out pressurized treatments to carry out heating or ironing processing again, and heating or ironing temperature are 60~300 DEG C.
6. the preparation method of metal nano plate according to claim 1, which is characterized in that at 5~6 doublings and pressurization
After reason, obtained metal-organic coating composite sheet is post-processed；
Preferably, the post-processing includes natrual ageing and/or artificial aging；
Preferably, the natrual ageing is low temperature natrual ageing, and temperature is 20~80 DEG C, and the time is 12~48h；
Preferably, the artificial aging includes heating anneal, and the temperature of heating anneal is 80~300 DEG C, and the time is 1~12h；
Preferably, further include the steps that post-processing metal nano plate, the post-processing includes that fine grain is annealed；
Preferably, the temperature of fine grain annealing is the recrystallization temperature of metal, and the time is 10~120min.
7. the preparation method of described in any item metal nano plates according to claim 1~6, which is characterized in that the separation packet
Include ultrasound removing or liquid phase removing；
Preferably, first metal-organic coating composite sheet is soaked in organic solvent, is stirred, then carry out ultrasonic removing or liquid
Mutually remove；
Preferably, organic solvent is heated, heating temperature is 60~80 DEG C；
Preferably, surfactant is added in separation process；
Preferably, cleaning and drying are include thed steps that after separation；
Preferably, the metal-organic coating composite sheet is with a thickness of 0.001~10mm；
And/or the metal nano plate with a thickness of 5~1000nm.
8. the metal nano plate being prepared by the preparation method of the described in any item metal nano plates of claim 1~7；
Preferably, the metal nano plate with a thickness of 5~1000nm.
9. metal nano plate or claim 8 that the preparation method of the described in any item metal nano plates of claim 1~7 obtains
Purposes of the metal nano plate as negative electrode active material.
10. a kind of negative electrode active material, which is characterized in that the system including the described in any item metal nano plates of claim 1~7
The metal nano plate or metal nano plate according to any one of claims 8 that Preparation Method obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811561463.XA CN109576454A (en) | 2018-12-19 | 2018-12-19 | Preparation method, metal nano plate, purposes and the negative electrode active material of metal nano plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811561463.XA CN109576454A (en) | 2018-12-19 | 2018-12-19 | Preparation method, metal nano plate, purposes and the negative electrode active material of metal nano plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109576454A true CN109576454A (en) | 2019-04-05 |
Family
ID=65931162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811561463.XA Pending CN109576454A (en) | 2018-12-19 | 2018-12-19 | Preparation method, metal nano plate, purposes and the negative electrode active material of metal nano plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109576454A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020125561A1 (en) * | 2018-12-19 | 2020-06-25 | 深圳先进技术研究院 | Negative electrode material, negative electrode and preparation method therefor, negative electrode slurry, secondary battery and electric appliance |
| CN111653760A (en) * | 2020-04-30 | 2020-09-11 | 中南大学 | Two-dimensional metal sheet and preparation method and application thereof |
| CN112359176A (en) * | 2020-11-02 | 2021-02-12 | 江苏苏讯新材料科技有限公司 | Continuous annealing process for special steel strip |
| CN114147211A (en) * | 2021-12-07 | 2022-03-08 | 合肥工业大学 | Copper-tin bimetallic alkene nanosheet and preparation method thereof |
| WO2024174133A1 (en) * | 2023-02-22 | 2024-08-29 | 宁波杭州湾新材料研究院 | Two-dimensional metal nanosheets, preparation method therefor, and thermal interface material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328606A (en) * | 1998-10-23 | 2001-12-26 | 艾弗里·丹尼森公司 | Process for making metal flakes |
| JP2005052862A (en) * | 2003-08-04 | 2005-03-03 | Toyo Kohan Co Ltd | Method for manufacturing ultrathin metallic sheet and ultrathin metallic sheet manufactured by using the same |
| CN1596322A (en) * | 2001-11-29 | 2005-03-16 | 艾弗里·丹尼森公司 | Process for making angstrom scale and high aspect functional platelets |
| CN102649124A (en) * | 2012-03-09 | 2012-08-29 | 山西银光华盛镁业股份有限公司 | Rolling method of magnesium or magnesium alloy foils |
| CN105774120A (en) * | 2016-03-31 | 2016-07-20 | 清华大学 | Metal nanosheet and manufacture method thereof |
| CN106654232A (en) * | 2017-01-20 | 2017-05-10 | 北京航空航天大学 | Preparation method of laminar composite for negative electrode of secondary metal lithium battery |
| CN108714626A (en) * | 2018-05-02 | 2018-10-30 | 中南大学 | A kind of deep cooling asynchronous rolling method preparing noble metal nano-plate |
-
2018
- 2018-12-19 CN CN201811561463.XA patent/CN109576454A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328606A (en) * | 1998-10-23 | 2001-12-26 | 艾弗里·丹尼森公司 | Process for making metal flakes |
| CN1596322A (en) * | 2001-11-29 | 2005-03-16 | 艾弗里·丹尼森公司 | Process for making angstrom scale and high aspect functional platelets |
| JP2005052862A (en) * | 2003-08-04 | 2005-03-03 | Toyo Kohan Co Ltd | Method for manufacturing ultrathin metallic sheet and ultrathin metallic sheet manufactured by using the same |
| CN102649124A (en) * | 2012-03-09 | 2012-08-29 | 山西银光华盛镁业股份有限公司 | Rolling method of magnesium or magnesium alloy foils |
| CN105774120A (en) * | 2016-03-31 | 2016-07-20 | 清华大学 | Metal nanosheet and manufacture method thereof |
| CN106654232A (en) * | 2017-01-20 | 2017-05-10 | 北京航空航天大学 | Preparation method of laminar composite for negative electrode of secondary metal lithium battery |
| CN108714626A (en) * | 2018-05-02 | 2018-10-30 | 中南大学 | A kind of deep cooling asynchronous rolling method preparing noble metal nano-plate |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020125561A1 (en) * | 2018-12-19 | 2020-06-25 | 深圳先进技术研究院 | Negative electrode material, negative electrode and preparation method therefor, negative electrode slurry, secondary battery and electric appliance |
| CN111653760A (en) * | 2020-04-30 | 2020-09-11 | 中南大学 | Two-dimensional metal sheet and preparation method and application thereof |
| CN111653760B (en) * | 2020-04-30 | 2021-11-05 | 中南大学 | Two-dimensional metal sheet and preparation method and application thereof |
| CN112359176A (en) * | 2020-11-02 | 2021-02-12 | 江苏苏讯新材料科技有限公司 | Continuous annealing process for special steel strip |
| CN114147211A (en) * | 2021-12-07 | 2022-03-08 | 合肥工业大学 | Copper-tin bimetallic alkene nanosheet and preparation method thereof |
| CN114147211B (en) * | 2021-12-07 | 2024-01-30 | 合肥工业大学 | Copper-tin bimetal alkene nanosheet and preparation method thereof |
| WO2024174133A1 (en) * | 2023-02-22 | 2024-08-29 | 宁波杭州湾新材料研究院 | Two-dimensional metal nanosheets, preparation method therefor, and thermal interface material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109576454A (en) | Preparation method, metal nano plate, purposes and the negative electrode active material of metal nano plate | |
| CN106219608B (en) | A kind of preparation method of two-dimensional material | |
| CN108033487A (en) | A kind of method that two-dimensional nano sheet material is prepared using liquid phase stripping method | |
| CN103891013B (en) | The manufacture method of electrode material | |
| CN106548875A (en) | A kind of transparent ultracapacitor of all-solid-state flexible and its prepare and apply | |
| US20190023577A1 (en) | Industrial method for preparing large-sized graphene | |
| CN105439133B (en) | A kind of preparation method of elecrtonegativity single-layer graphene | |
| CN108237063B (en) | Preparation method of metal anticorrosion graphene composite coating | |
| CN106520079A (en) | Graphene heat conductive film and preparation method thereof | |
| CN103482614B (en) | A kind of preparation method of graphene-ZnO nanoparticle composite material | |
| CN106099053A (en) | A kind of molybdenum sulfide/selenizing molybdenum composite material and preparation thereof and application | |
| CN109286009A (en) | A kind of preparation method of nanometer sheet self assembled three-dimensional nano flower artificial gold/graphitization carbonitride lithium ion battery negative material | |
| CN103641172A (en) | Method for preparing nanometer layered molybdenum disulfide | |
| CN103112848B (en) | Method for preparing graphene | |
| CN106587155A (en) | High-concentration molybdenum disulfide nanometer sheet dispersion liquid, and preparation method and application thereof | |
| CN110386597A (en) | Large-scale production thin graphene equipment and large-scale production thin graphene method | |
| CN106185884B (en) | A kind of method of rapid, high volume production graphene | |
| CN107749479A (en) | A kind of painting carbon copper foil negative plate and the electrokinetic cell containing the negative plate | |
| CN108545784A (en) | A kind of small sized metallic oxide nano-slice and preparation method thereof | |
| CN110255546B (en) | Method for preparing graphene by peeling crystalline flake graphite from liquid rubber | |
| CN106571444A (en) | Method for manufacturing negative electrode plate of secondary battery | |
| CN105551818B (en) | β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material and its preparation method and application | |
| CN103101905A (en) | Nanopore grapheme, its preparation method and application | |
| CN111653760B (en) | Two-dimensional metal sheet and preparation method and application thereof | |
| WO2020124452A1 (en) | Method for preparing metal nanosheet, metal nanosheet, use, and negative electrode active material |
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: 20190405 |
|
| RJ01 | Rejection of invention patent application after publication |