CN114759175A - Preparation method and application of polyaryl diamine/metal oxide composite material - Google Patents
Preparation method and application of polyaryl diamine/metal oxide composite material Download PDFInfo
- Publication number
- CN114759175A CN114759175A CN202210362874.6A CN202210362874A CN114759175A CN 114759175 A CN114759175 A CN 114759175A CN 202210362874 A CN202210362874 A CN 202210362874A CN 114759175 A CN114759175 A CN 114759175A
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- China
- Prior art keywords
- solution
- component
- composite material
- metal oxide
- diamine
- Prior art date
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- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 150000004985 diamines Chemical class 0.000 title claims abstract description 52
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 49
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 96
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000007790 solid phase Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- 239000011701 zinc Substances 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 14
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- -1 fluoroborate Chemical compound 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 6
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 6
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 6
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- NDMVXIYCFFFPLE-UHFFFAOYSA-N anthracene-9,10-diamine Chemical compound C1=CC=C2C(N)=C(C=CC=C3)C3=C(N)C2=C1 NDMVXIYCFFFPLE-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- KBKZYWOOZPIUJT-UHFFFAOYSA-N azane;hypochlorous acid Chemical compound N.ClO KBKZYWOOZPIUJT-UHFFFAOYSA-N 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 3
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229940001468 citrate Drugs 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- IYQHCPGJNZBANF-UHFFFAOYSA-N phenazine-1,2-diamine Chemical compound C1=CC=CC2=NC3=C(N)C(N)=CC=C3N=C21 IYQHCPGJNZBANF-UHFFFAOYSA-N 0.000 claims description 3
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 37
- 239000002585 base Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 19
- 238000005303 weighing Methods 0.000 description 18
- 239000011787 zinc oxide Substances 0.000 description 16
- 230000002572 peristaltic effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 239000011149 active material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000001351 cycling effect Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 5
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VZPGINJWPPHRLS-UHFFFAOYSA-N phenazine-2,3-diamine Chemical compound C1=CC=C2N=C(C=C(C(N)=C3)N)C3=NC2=C1 VZPGINJWPPHRLS-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
Abstract
The invention relates to the technical field of battery materials, and discloses a preparation method and application of a polyaryl diamine/metal oxide composite material, wherein the preparation method comprises the following steps: (1) adding aromatic diamine into a solvent to prepare a component A solution; (2) adding an oxidant into a solvent to prepare a component B solution; (3) adding soluble metal salt into the component A solution or the component B solution to prepare a mixed solution; (4) mixing the mixed solution with another component solution to carry out oxidative polymerization reaction; (5) and carrying out solid-liquid separation on the product after the reaction, and cleaning and drying the solid phase to obtain the polyaryl diamine/metal oxide composite material. The invention can solve the problems that metal oxide does not conduct electrons and is easy to dissolve in strong alkali by compounding the conductive polyaryl diamine, and the preparation process has simple and convenient operation, easy industrialization, low production cost and less pollution.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a preparation method and application of a polyaryl diamine/metal oxide composite material.
Background
The zinc-based battery is an important branch of a chemical storage battery and is a research and development hotspot of a chemical power supply. The zinc has rich storage capacity, low price and high specific capacity, and the production and the use of the zinc-based battery can not pollute the environment, thereby being a real green battery cathode material. Because of these excellent characteristics, zinc-based batteries, such as zinc-nickel secondary batteries, zinc-nickel flow batteries, zinc-bromine batteries, etc., are receiving attention from researchers, and become an important research and development direction for energy storage batteries.
Secondary zinc electrodes typically employ a mixture of zinc oxide (ZnO) powder and metallic zinc powder as the electrode material. When a mixture of zinc oxide (ZnO) powder and metallic zinc powder is charged, zinc oxide powder particles in contact with the metallic zinc powder are easily charged due to poor conductivity of zinc oxide, thereby causing problems of polarization, insufficient charging of a zinc electrode, attenuation and the like. Therefore, zinc oxide is modified to improve the conductivity thereof, and the research is widely carried out. For example: the literature (Electrochimica Acta 105(2013)40-46) researches the technology and the battery application of coating conductive carbon outside zinc oxide, but the conductive carbon has a lower hydrogen evolution potential and needs high-temperature pyrolysis to influence the electrochemical activity of the zinc oxide. The literature (batteries 41(2011)101-103) researches the technology of coating indium oxide outside zinc oxide and the application of the batteries, but the indium oxide improves the hydrogen evolution potential and cannot improve the conductivity of the zinc oxide. There are also some documents that doping and coating oxides and hydroxides such as aluminum and tin in zinc oxide crystals cannot improve the conductivity of zinc oxide. The literature (material report 30(2016)15-20) introduces the preparation technology of the zinc oxide/graphene nanocomposite, but the cost is high, and the future industrial preparation and application have no clear prospect.
Therefore, the development of a method for improving the conductivity of the zinc oxide, which is simple and convenient to operate and easy to industrialize, has low production cost and little pollution, and has important significance.
Disclosure of Invention
The invention provides a preparation method and application of a polyaryl diamine/metal oxide composite material, aiming at overcoming the problem that when a mixture of zinc oxide powder and metal zinc powder of a secondary zinc electrode in the prior art is charged, zinc oxide powder particles contacted with the metal zinc powder are easy to charge due to poor conductivity of the zinc oxide, so that polarization and insufficient charging of the zinc electrode are caused and the zinc electrode is attenuated.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a polyaryl diamine/metal oxide composite material comprises the following steps:
(1) adding aromatic diamine into a solvent to prepare a component A solution;
(2) adding an oxidant into a solvent to prepare a component B solution;
(3) adding soluble metal salt into the component A solution or the component B solution to prepare a mixed solution;
(4) mixing the mixed solution with another component solution to carry out oxidative polymerization reaction;
(5) and (3) carrying out solid-liquid separation on the product after reaction, and cleaning and drying the solid phase to obtain the polyaryl diamine/metal oxide composite material.
The polyaryl diamine/metal oxide composite material is prepared through mixing the metal material to be compounded into the oxidation polymerization system of aromatic diamine in the form of soluble metal salt and initiating polymerization reaction. In the reaction process, aromatic diamine is polymerized to form polyaryl diamine, metal ion oxide sol-gel is precipitated to form metal oxide (or hydroxide), and the polyaryl diamine and the metal oxide (or hydroxide) form micro-nano structure composite. The polyaryl diamine has better conductivity and high stability in a reduction state, can inhibit dissolution, provide certain electrochemical specific capacity, and improve the conductivity inside metal oxide (or hydroxide) particles, thereby more effectively solving the problem of poor conductivity of the metal oxide (or hydroxide) per se.
The composite material can solve the problem that metal oxide is not conductive and is easy to dissolve in strong base through the compounding of the conductive polyaryl diamine, and the prepared composite material can be used in zinc-based batteries of alkaline and near-neutral electrolytes, so that the cycle life of a zinc cathode of the battery and the specific energy of the battery are prolonged; the composite material can also be used as a lithium ion battery cathode material, and the cycling stability of the battery is improved. Meanwhile, the preparation method of the composite material does not need high-temperature pyrolysis treatment, avoids high-temperature and high-energy consumption such as carbon coating and the like, is simple and convenient to operate, is easy to industrialize, has low production cost and little pollution, and has the advantages of economy and environmental protection.
Preferably, the aromatic diamine in step (1) is selected from one or more of o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminonaphthalene, diaminophenazine, diaminoanthracene and diaminoanthraquinone.
Preferably, the oxidant in step (2) is one or more selected from ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, ammonium hypochlorite, sodium hypochlorite, potassium hypochlorite and peroxyacetic acid.
Preferably, the solvent in steps (1) and (2) is selected from one or more of deionized water, methanol, ethanol, ethylene glycol, polyethylene glycol, glycerol, polyvinyl alcohol, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, in the soluble metal salt in the step (3), the metal element is selected from one or more of zinc, copper, tin, titanium, iron, chromium, vanadium, lead, bismuth and indium.
Preferably, the soluble metal salt in step (3) is selected from one or more of nitrate, sulfate, chloride, chlorate, perchlorate, bromide, bromate, formate, acetate, fluoroborate, fluorosulfonate, methylsulfonate, trifluoromethylsulfonate, benzenesulfonate, citrate, tartrate and nitrilotriacetate.
Preferably, after the mixing in the step (4), the molar ratio of the aromatic diamine, the oxidant and the soluble metal salt is 1: 3-5: 4-8. Under the condition of the using amount, the polyaryl diamine in the prepared composite material accounts for 5-35% of the total mass of the composite material, so that the conductivity of the metal oxide can be effectively improved, and the electrochemical activity of the metal oxide can not be influenced.
Preferably, the oxidative polymerization conditions in step (4) are: the reaction temperature is 0-100 ℃, the pH is 8-10, and the reaction time is 1-12 h; and adjusting the pH value of the reaction to be between 8 and 10 by using one or more alkali selected from ammonia water, ethylenediamine, potassium hydroxide, sodium hydroxide and lithium hydroxide.
Preferably, the component A solution or the component B solution further comprises a conductive material, and the conductive material is selected from one or more of graphene, carbon nanotubes, acetylene black and graphite powder; the addition amount of the conductive material is 1-15% of the mass of the polyaryl diamine/metal oxide composite material.
Preferably, the addition amount of the conductive material is 3 to 8% by mass of the polyaryl diamine/metal oxide composite material.
Preferably, the drying temperature in step (5) is not more than 200 ℃.
The invention also provides application of the polyaryl diamine/metal oxide composite material prepared by the method in an electrode.
Preferably, the preparation method of the electrode comprises the following steps: dispersing and mixing the polyaryl diamine/metal oxide composite material, the conductive agent and the binder in water or an organic solvent to form slurry; and coating the slurry on a current collector, drying and rolling to form the electrode.
Preferably, the mass ratio of the polyaryl diamine/metal oxide composite material to the conductive agent to the binder is 85-95: 10: 1-5.
Preferably, the current collector is selected from one or more of copper foam, nickel foam, copper mesh, copper foil, stainless steel mesh, stainless steel foil, titanium mesh, titanium foil, nickel-molybdenum alloy mesh, nickel-molybdenum alloy foil, copper-nickel alloy mesh, copper-nickel alloy foil, copper-zinc alloy mesh, copper-zinc alloy foil, aluminum mesh and foamed aluminum.
Therefore, the invention has the following beneficial effects:
(1) the problem that metal oxide does not conduct electrons and is easy to dissolve in strong base can be solved through the compounding of the conductive polyaryl diamine;
(2) the preparation method of the composite material does not need high-temperature pyrolysis treatment, avoids high-temperature and high-energy consumption such as carbon coating and the like, is simple and convenient to operate, is easy to industrialize, has low production cost and little pollution, and has the advantages of economy and environmental protection;
(3) the composite material can be used in zinc-based battery electrodes of alkaline and near-neutral electrolytes, and the cycle life of a battery zinc negative electrode and the specific energy of the battery are improved; the composite material can also be used as a lithium ion battery cathode material, and the cycling stability of the battery is improved.
Detailed Description
The invention is further described with reference to specific embodiments.
General examples:
a method for preparing a polyaryl diamine/metal oxide composite material comprises the following steps:
(1) adding aromatic diamine into a solvent to prepare a component A solution; the aromatic diamine is selected from one or more of o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminonaphthalene, diaminophenazine, diaminoanthracene and diaminoanthraquinone; the solvent is selected from one or more of deionized water, methanol, ethanol, glycol, polyethylene glycol, glycerol, polyvinyl alcohol, N-methyl pyrrolidone, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide;
(2) adding an oxidant into a solvent to prepare a component B solution; the oxidant is selected from one or more of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, ammonium hypochlorite, sodium hypochlorite, potassium hypochlorite and peroxyacetic acid; the solvent is selected from one or more of deionized water, methanol, ethanol, glycol, polyethylene glycol, glycerol, polyvinyl alcohol, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide;
(3) adding soluble metal salt into the component A solution or the component B solution to prepare a mixed solution; in the soluble metal salt, the metal element is selected from one or more of zinc, copper, tin, titanium, iron, chromium, vanadium, lead, bismuth and indium; the soluble metal salt is selected from one or more of nitrate, sulfate, chloride salt, chlorate, perchlorate, bromide salt, bromate, formate, acetate, fluoroborate, fluorosulfonate, methylsulfonate, trifluoromethylsulfonate, benzenesulfonate, citrate, tartrate and nitrilotriacetate;
(4) mixing the mixed solution with another component solution to carry out oxidative polymerization reaction; the molar ratio of the aromatic diamine to the oxidant to the soluble metal salt is 1: 3-5: 4-8; the oxidation polymerization reaction conditions are as follows: the reaction temperature is 0-100 ℃, the pH is 8-10, and the reaction time is 1-12 h; adjusting the pH value of the reaction to be between 8 and 10, wherein the alkali is selected from one or more of ammonia water, ethylenediamine, potassium hydroxide, sodium hydroxide and lithium hydroxide;
(5) carrying out solid-liquid separation on the product after reaction, and cleaning and drying the solid phase to obtain the polyaryl diamine/metal oxide composite material; the drying temperature is not more than 200 ℃;
optionally, the component a solution or the component B solution further includes a conductive material, and the conductive material is selected from one or more of graphene, carbon nanotubes, acetylene black, and graphite powder; the addition amount of the conductive material is 1-15% of the mass of the polyaryl diamine/metal oxide composite material.
Example 1:
weighing 4.32g (0.04mol) of o-phenylenediamine and 35.09g (0.16mol) of zinc acetate dihydrate, and dissolving the o-phenylenediamine and the zinc acetate dihydrate into 200mL of deionized water to prepare a component A solution; weighing 36.53g (0.16mol) of ammonium persulfate and 40.00g (1.00mol) of sodium hydroxide, and dissolving in 200mL of deionized water to prepare a component B solution; placing the component A solution in a 70 ℃ water bath as a base solution, continuously stirring by magnetic force, dropwise adding the component B solution into the base solution by a peristaltic pump, controlling the dropwise adding speed to be about 0.5mL/min, and keeping the temperature of the mixed solution at 70 ℃ after the dropwise adding to be continuously stirred and react for 12 hours. And cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove a liquid phase, washing by using deionized water until filtrate is colorless, and finally drying at constant temperature in vacuum at 120 ℃ for 15 hours to obtain the dark brown-black polyaryl diamine/metal oxide composite material. Tests show that the zinc oxide accounts for 70 wt% and the polyaryl diamine accounts for 30 wt% of the dried composite material.
Example 2:
0.02mol of o-phenylenediamine, 0.02mol of diaminonaphthalene, 0.15mol of zinc acetate dihydrate and 0.01mol of copper acetate are weighed and dissolved in 200mL of deionized water together to prepare a component A solution; weighing 0.16mol of ammonium persulfate to be dissolved in 150mL of deionized water to prepare a component B solution; and 1mol/L sodium hydroxide aqueous solution is additionally prepared. Placing the component A solution in a water bath at 100 ℃ as a base solution, continuously and magnetically stirring, dropwise adding the component B solution into the base solution by using a peristaltic pump, controlling the dropwise adding speed to be about 0.5mL/min, adding 1mol/L of sodium hydroxide aqueous solution into the base solution by using another peristaltic pump, setting the pH value to be between 8 and 10, and keeping the temperature of the mixed solution after the dropwise adding of the component B solution at 100 ℃ and continuously stirring for reacting for 12 hours (adjusting the pH value to be between 8 and 10). And cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove a liquid phase, washing by using deionized water until filtrate is colorless, and finally drying at the constant temperature of 200 ℃ for 10 hours in vacuum to obtain the dark brown-black polyaryl diamine/metal oxide composite material. Tests show that the polyaryl diamine accounts for 32 wt% of the dried composite material.
Example 3:
0.02mol of o-phenylenediamine, 0.02mol of diaminoanthraquinone, 0.14mol of zinc acetate dihydrate, 0.01mol of copper acetate and 0.005mol of indium sulfate are weighed and dissolved in 200mL of deionized water together to prepare a component A solution; weighing 0.20mol of sodium hypochlorite and 1.00mol of sodium hydroxide, and dissolving the sodium hypochlorite and the 1.00mol of sodium hydroxide in 200mL of deionized water to prepare a component B solution; placing the component A solution in a water bath at 0 ℃ as a base solution, continuously stirring by magnetic force, dropwise adding the component B solution into the base solution by a peristaltic pump, controlling the dropwise adding speed to be about 0.5mL/min, and keeping the temperature of the mixed solution at 0 ℃ after the dropwise adding to be continuously stirred and react for 5 hours. And after the reaction is finished, filtering by using a sand core funnel to remove a liquid phase, washing by using deionized water until filtrate is colorless, and finally drying at the constant temperature of 110 ℃ in vacuum for 10 hours to obtain the dark brown black polyaryl diamine/metal oxide composite material. Tests show that the polyaryl diamine accounts for 35 wt% of the dried composite material.
Example 4:
weighing 0.01mol of p-phenylenediamine, 0.01mol of diaminoanthracene, 0.14mol of zinc acetate dihydrate, 0.01mol of copper acetate and 0.005mol of indium sulfate, and dissolving the components in 200mL of deionized water to prepare a component A solution; weighing 0.06mol of sodium hypochlorite and 1.00mol of sodium hydroxide, and dissolving in 200mL of deionized water to prepare a component B solution; placing the component A solution in a water bath at 80 ℃ as a base solution, continuously stirring by magnetic force, dropwise adding the component B solution into the base solution by using a peristaltic pump, controlling the dropwise adding speed to be about 0.2mL/min, and keeping the temperature of the mixed solution at 80 ℃ after the dropwise adding is finished, and continuously stirring for reacting for 1 h. And cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove a liquid phase, washing by using deionized water until filtrate is colorless, and finally drying at the constant temperature of 60 ℃ for 24 hours in vacuum to obtain the dark brown-black polyaryl diamine/metal oxide composite material. Tests show that the polyaryl diamine accounts for 10 wt% of the dried composite material.
Example 5:
weighing 0.01mol of p-phenylenediamine, 0.01mol of diaminoanthracene, 0.14mol of zinc acetate dihydrate, 0.01mol of copper acetate and 0.005mol of indium sulfate, dissolving the materials in 200mL of deionized water together to prepare a component A solution, and adding 0.7g of water-dispersible graphene into the component A solution; weighing 0.06mol of sodium hypochlorite and 1.00mol of sodium hydroxide, dissolving the sodium hypochlorite and the 1.00mol of sodium hydroxide in 200mL of deionized water to prepare a component B solution, and adding 0.7g of aqueous dispersed graphene into the component B solution; placing the component A solution in a water bath at 80 ℃ as a base solution, continuously stirring by magnetic force, dropwise adding the component B solution into the base solution by using a peristaltic pump, controlling the dropwise adding speed to be about 0.2mL/min, and keeping the temperature of the mixed solution at 80 ℃ after the dropwise adding is finished, and continuously stirring for reacting for 1 h. And cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove a liquid phase, washing by using deionized water until filtrate is colorless, and finally drying at the constant temperature of 60 ℃ for 24 hours in vacuum to obtain the dark brown-black polyaryl diamine/metal oxide composite material. Tests show that the polyaryl diamine accounts for 10 wt% of the dried composite material, and the conductive material graphene accounts for 10 wt% of the polyaryl diamine/metal oxide composite material.
Example 6:
weighing 0.02mol of m-phenylenediamine and 0.16mol of titanyl sulfate, and dissolving the m-phenylenediamine and the titanyl sulfate in 200mL of deionized water to prepare a component A solution; weighing 0.08mol of sodium hypochlorite and 1.00mol of sodium hydroxide, and dissolving the sodium hypochlorite and the 1.00mol of sodium hydroxide in 200mL of deionized water to prepare a component B solution; placing the component A solution in a water bath at 50 ℃ as a base solution, continuously stirring by magnetic force, dropwise adding the component B solution into the base solution by using a peristaltic pump, controlling the dropwise adding speed to be about 0.1mL/min, and keeping the temperature of the mixed solution at 50 ℃ after the dropwise adding to react for 12 hours by stirring continuously. And cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove a liquid phase, washing by using deionized water until the filtrate is colorless, and finally drying at the constant temperature of 60 ℃ in vacuum for 24 hours to obtain the dark brown-black polyaryl diamine/metal oxide composite material. Tests show that the polyaryl diamine accounts for 12 wt% of the dried composite material.
Example 7:
weighing 0.01mol of m-phenylenediamine, 0.01mol of 2, 3-diaminophenazine and 0.16mol of stannic chloride, and dissolving the components in 200mL of deionized water to prepare a component A solution (a small amount of hydrochloric acid needs to be supplemented to inhibit hydrolysis of stannic chloride); weighing 0.08mol of sodium hypochlorite and 1.00mol of sodium hydroxide, and dissolving the sodium hypochlorite and the 1.08 mol of sodium hydroxide into 200mL of deionized water to prepare a component B solution; placing the component A solution in a water bath at 60 ℃ as a base solution, continuously stirring by magnetic force, dropwise adding the component B solution into the base solution by using a peristaltic pump, controlling the dropwise adding speed to be about 0.1mL/min, and keeping the temperature of the mixed solution at 60 ℃ after the dropwise adding to react for 12 hours by stirring continuously. And cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove a liquid phase, washing by using deionized water until filtrate is colorless, and finally drying at the constant temperature of 60 ℃ for 24 hours in vacuum to obtain the dark brown-black polyaryl diamine/metal oxide composite material. Tests show that the polyaryl diamine accounts for 12 wt% of the dried composite material.
Comparative example 1:
0.14mol of zinc acetate dihydrate, 0.01mol of copper acetate and 0.005mol of indium sulfate are weighed and dissolved in 200mL of deionized water together to prepare a component A solution; weighing 0.4mol of sodium hydroxide, and dissolving the sodium hydroxide in 200mL of deionized water to prepare a component B solution; placing the component A solution in a water bath at 80 ℃ as a base solution, continuously stirring by magnetic force, dropwise adding the component B solution into the base solution by using a peristaltic pump, controlling the dropwise adding speed to be about 0.2mL/min, and keeping the temperature of the mixed solution at 80 ℃ after the dropwise adding is finished, and continuously stirring for reacting for 1 h. And cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove a liquid phase, washing by using deionized water until filtrate is colorless, and finally drying at constant temperature in vacuum at 60 ℃ for 24 hours to obtain the metal oxide composite material.
Comparative example 2:
weighing 0.04mol of o-phenylenediamine, 0.04mol of diaminoanthraquinone, 0.14mol of zinc acetate dihydrate, 0.01mol of copper acetate and 0.005mol of indium sulfate, and dissolving the materials in 200mL of deionized water to prepare a component A solution; weighing 0.40mol of sodium hypochlorite and 1.50mol of sodium hydroxide, and dissolving the sodium hypochlorite and the 1.50mol of sodium hydroxide into 200mL of deionized water to prepare a component B solution; placing the component A solution in a water bath at 0 ℃ as a base solution, continuously stirring by magnetic force, dropwise adding the component B solution into the base solution by a peristaltic pump, controlling the dropwise adding speed to be about 0.5mL/min, and keeping the temperature of the mixed solution at 0 ℃ after the dropwise adding to be continuously stirred and react for 5 hours. And after the reaction is finished, filtering by using a sand core funnel to remove a liquid phase, washing by using deionized water until filtrate is colorless, and finally drying at the constant temperature of 110 ℃ in vacuum for 10 hours to obtain the dark brown black polyaryl diamine/metal oxide composite material. Tests show that the polyaryl diamine accounts for 52 wt% of the dried composite material.
Comparative example 3:
weighing 0.16mol of titanyl sulfate, and dissolving the titanyl sulfate and the titanyl sulfate in 200mL of deionized water to prepare a component A solution; weighing 0.4mol of sodium hydroxide, and dissolving the sodium hydroxide together in 200mL of deionized water to prepare a component B solution; placing the component A solution in a water bath at 50 ℃ as a base solution, continuously stirring by magnetic force, dropwise adding the component B solution into the base solution by using a peristaltic pump, controlling the dropwise adding speed to be about 0.1mL/min, and keeping the temperature of the mixed solution at 50 ℃ after the dropwise adding to react for 12 hours by stirring continuously. And cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove a liquid phase, washing to be neutral by using deionized water, and finally drying at a constant temperature in vacuum at 60 ℃ for 24 hours to obtain the metal oxide composite material.
Comparative example 4:
0.16mol of stannic chloride is weighed and dissolved in 200mL of deionized water together to prepare a component A solution (a small amount of hydrochloric acid needs to be supplemented to inhibit hydrolysis of stannic chloride); weighing 0.8mol of sodium hydroxide, and dissolving the sodium hydroxide together in 200mL of deionized water to prepare a component B solution; placing the component A solution in a water bath at 60 ℃ as a base solution, continuously stirring by magnetic force, dropwise adding the component B solution into the base solution by using a peristaltic pump, controlling the dropwise adding speed to be about 0.1mL/min, and keeping the temperature of the mixed solution at 60 ℃ after the dropwise adding to react for 12 hours by stirring continuously. And cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove a liquid phase, washing to be neutral by using deionized water, and finally drying for 24 hours at a constant temperature in vacuum at 60 ℃ to obtain the metal oxide composite material.
Application examples 1 to 4:
the polyaryl diamine/metal oxide composite materials prepared in examples 1 to 4 were respectively pulverized to 400 mesh or more as active materials for electrodes, and the ratio of the active materials: acetylene black: mixing adhesive (60 wt% of polytetrafluoroethylene emulsion) at a mass ratio of 87:10:3 (based on solid mass ratio), adding small amount of deionized water and anhydrous ethanol, grinding, rolling into sheet, drying in oven at 120 deg.C for 12 hr, and cuttingAt a height of 2X 2cm2(ii) a The loading of active substances is 5.0mg/cm2The electrodes were formed by pressing a 100 mesh tin-plated copper mesh on an oil press at a pressure of 4 MPa.
Using 7mol/L potassium hydroxide aqueous solution as electrolyte, 2X 2cm2The sintered nickel electrode of (1) was used as a counter electrode, and the discharge specific capacity of the above electrode was measured (charge-discharge cycle condition: 50mA/g or 500mA/g charged to 1.1 times the theoretical capacity of electricity, and discharge at the same current density to 1.2V cut-off voltage), respectively, and the results are shown in Table 1.
Application example 5:
the polyaryldiamide/metal oxide composite material prepared in example 5 was pulverized to 400 mesh or more, respectively, as an active material for an electrode, according to the active material: mixing binder (60 wt% polytetrafluoroethylene emulsion) at a mass ratio of 97:3 (based on solid mass ratio), adding small amount of deionized water and anhydrous ethanol, grinding, rolling into sheet, drying in oven at 120 deg.C for 12 hr, and cutting into 2 × 2cm pieces2(ii) a The loading amount of active substances is 5.0mg/cm2The electrodes were formed by pressing a 100 mesh tin-plated copper mesh on an oil press at a pressure of 4 MPa.
Using 7mol/L potassium hydroxide aqueous solution as electrolyte, 2X 2cm2The sintered nickel electrode of (1) was used as a counter electrode, and the discharge specific capacity of the above electrode was measured (charge-discharge cycle condition: 50mA/g or 500mA/g charged to 1.1 times the theoretical capacity of electricity, and discharge at the same current density to 1.2V cut-off voltage), respectively, and the results are shown in Table 1.
Comparative application examples 1 to 2:
the zinc oxide prepared in comparative example 1 and the polyaryldiamide/metal oxide composite prepared in comparative example 2 were pulverized to 400 mesh or more, respectively, as active materials for electrodes, and the rest was the same as in application example 1.
2X 2cm using 7mol/L potassium hydroxide aqueous solution as electrolyte2The sintered nickel electrode of (1) was used as a counter electrode, and the discharge specific capacity of the above electrode was measured (charge-discharge cycle condition: 50mA/g or 500mA/g charged to 1.1 times the theoretical capacity of electricity, and discharge at the same current density to 1.2V cut-off voltage), respectively, and the results are shown in Table 1.
Application example 6:
the polyaryldiamide/metal oxide composite material prepared in example 6 was pulverized to 400 mesh or more as an active material for an electrode, according to the following ratio of active material: acetylene black: mixing adhesive (60 wt% of polytetrafluoroethylene emulsion) at a mass ratio of 87:10:3 (according to solid mass ratio), adding a small amount of deionized water and absolute ethyl alcohol, fully grinding, rolling into sheets, drying in a 120 ℃ oven for 12 hours, cutting into disks with the diameter of 14mm, and loading 5.0mg/cm of active substances2The electrodes were made by pressing on foamed aluminum with a pressure of 4MPa on an oil press.
At 1mol/L LiClO4(EC + DMC) (EC to DMC volume ratio 1:1) as electrolyte, 14mm round lithium plate as counter electrode, Celgard2500 diaphragm, the above electrodes were tested for specific discharge capacity and cycling performance (charge-discharge cycling conditions: 50mA/g or 500mA/g discharge 1.0V, same current density charge to cut-off voltage 2.5V), the results are shown in Table 2.
Application example 7:
the polyaryldiamide/metal oxide composite material prepared in example 7 was pulverized to 400 mesh or more as an active material for an electrode, according to the active material: acetylene black: mixing adhesive (60 wt% of polytetrafluoroethylene emulsion) at a mass ratio of 87:10:3 (according to solid mass ratio), adding a small amount of deionized water and absolute ethyl alcohol, fully grinding, rolling into sheets, drying in a 120 ℃ oven for 12 hours, cutting into 14 mm-diameter round pieces, and loading 5.0mg/cm of active substance2The electrode was formed by pressing on foamed aluminum with a pressure of 4MPa on an oil press.
At 1mol/L LiClO4(EC + DMC) (EC to DMC volume ratio 1:1) as electrolyte, 14mm round lithium plate as counter electrode, Celgard2500 diaphragm, the above electrodes were tested for specific discharge capacity and cycling performance (charge-discharge cycling conditions: 50mA/g or 500mA/g discharge 1.0V, same current density charge to cut-off voltage 2.5V), the results are shown in Table 2.
Comparative application examples 3 to 4:
the titanium oxide composite material prepared in comparative example 3 and the tin oxide composite material prepared in comparative example 4 were respectively pulverized to 400 mesh or more as an active material of an electrode, and the rest was the same as in application example 6.
At 1mol/L LiClO4/(EC + DMC) (volume ratio of EC to DMC 1:1) as electrolyte, 14mm round lithium sheet as counter electrode, Celgard2500 separator, the above electrodes were tested for specific discharge capacity and cycling performance (charge-discharge cycling conditions: 1.0V for 50mA/g or 500mA/g discharge, also current density charge to 2.5V cut-off voltage), with the results as shown in Table 2.
Table 1: and testing the application performance of the zinc-based battery.
Table 2: and testing the application performance of the lithium ion battery.
As can be seen from tables 1 and 2, the polyaryl diamine/metal oxide composite material prepared by the method of the present invention in examples 1 to 7 can effectively improve the cycle life and specific capacity of the battery when applied to zinc-based batteries and lithium ion batteries. In contrast, in application example 1, when zinc oxide and polyaryl diamine are not compounded, the initial specific capacity of the zinc-based battery is high due to poor conductivity of the zinc oxide, but the cyclic specific capacity is remarkably reduced compared with that in the examples; the material rate performance and the cyclic ratio capacity of the compounded polyaryl diamine are high, and the polyaryl diamine improves the electronic conductivity of oxides and inhibits the dissolution and migration of zinc oxide; it can be seen from the data of application examples 1 to 4 and comparative application example 2 that when the content of the polyaryl diamine is higher, the specific capacity of the composite material is obviously reduced due to low specific capacity and low density of the polyaryl diamine. Similarly, it can be seen from table 2 that the electron conductivity of the oxide is improved by the metal oxide composite polyaryl diamine, the rate capability is improved, and the specific capacity of the lithium ion battery cathode is also improved.
Claims (10)
1. A preparation method of a polyaryl diamine/metal oxide composite material is characterized by comprising the following steps:
(1) adding aromatic diamine into a solvent to prepare a component A solution;
(2) adding an oxidant into a solvent to prepare a component B solution;
(3) adding soluble metal salt into the component A solution or the component B solution to prepare a mixed solution;
(4) mixing the mixed solution with another component solution to carry out oxidative polymerization reaction;
(5) and (3) carrying out solid-liquid separation on the product after reaction, and cleaning and drying the solid phase to obtain the polyaryl diamine/metal oxide composite material.
2. The method according to claim 1, wherein the aromatic diamine in step (1) is one or more selected from the group consisting of o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminonaphthalene, diaminophenazine, diaminoanthracene, and diaminoanthraquinone.
3. The preparation method according to claim 1, wherein the oxidant in step (2) is one or more selected from ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, ammonium hypochlorite, sodium hypochlorite, potassium hypochlorite and peroxyacetic acid.
4. The method according to claim 1, wherein the solvent in steps (1) and (2) is selected from one or more of deionized water, methanol, ethanol, ethylene glycol, polyethylene glycol, glycerol, polyvinyl alcohol, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.
5. The method according to claim 1, wherein the soluble metal salt in step (3) contains one or more metal elements selected from zinc, copper, tin, titanium, iron, chromium, vanadium, lead, bismuth and indium.
6. The method according to claim 1 or 5, wherein the soluble metal salt in step (3) is selected from one or more of nitrate, sulfate, chloride, chlorate, perchlorate, bromide, bromate, formate, acetate, fluoroborate, fluorosulfonate, methylsulfonate, trifluoromethylsulfonate, benzenesulfonate, citrate, tartrate, and nitrilotriacetate.
7. The method according to claim 1, wherein the molar ratio of the aromatic diamine, the oxidizing agent and the soluble metal salt after the mixing in the step (4) is 1:3 to 5:4 to 8.
8. The production process according to claim 1 or 7, wherein the oxidative polymerization conditions in the step (4) are: the reaction temperature is 0-100 ℃, the pH = 8-10, and the reaction time is 1-12 h; and adjusting the pH value of the reaction to be between 8 and 10 by using one or more alkali selected from ammonia water, ethylenediamine, potassium hydroxide, sodium hydroxide and lithium hydroxide.
9. The preparation method of claim 1, wherein the A component solution or the B component solution further comprises a conductive material, and the conductive material is selected from one or more of graphene, carbon nanotubes, acetylene black and graphite powder; the addition amount of the conductive material is 1-15% of the mass of the polyaryl diamine/metal oxide composite material.
10. Use of a polyaryldiamide/metal oxide composite material prepared by the method of any one of claims 1 to 9 in an electrode.
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| CN114122394A (en) * | 2020-08-31 | 2022-03-01 | 浙江裕源储能科技有限公司 | Polyoxazine material and preparation method and application thereof |
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| US20140302407A1 (en) * | 2013-04-03 | 2014-10-09 | Panisolar Inc | Air Electrode Catalyst |
| CN103441253A (en) * | 2013-08-15 | 2013-12-11 | 陕西科技大学 | Graphene/ZnO/polyaniline composite material and preparation method and application thereof |
| CN108538620A (en) * | 2018-03-19 | 2018-09-14 | 江苏大学 | Mn (manganese) 3 O 4 -Fe 3 O 4 Preparation method and application of @ POPD bimetal oxide @ conductive polymer |
| CN114122394A (en) * | 2020-08-31 | 2022-03-01 | 浙江裕源储能科技有限公司 | Polyoxazine material and preparation method and application thereof |
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