CN114759175B - Preparation method and application of polyarylene diamine/metal oxide composite material - Google Patents
Preparation method and application of polyarylene diamine/metal oxide composite material Download PDFInfo
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- CN114759175B CN114759175B CN202210362874.6A CN202210362874A CN114759175B CN 114759175 B CN114759175 B CN 114759175B CN 202210362874 A CN202210362874 A CN 202210362874A CN 114759175 B CN114759175 B CN 114759175B
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- diamine
- component
- metal oxide
- composite material
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- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 50
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 50
- 150000004985 diamines Chemical class 0.000 title claims abstract description 35
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 96
- -1 poly (arylene diamine Chemical class 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 15
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 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 57
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 15
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 15
- 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
- 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
- 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
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 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
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 239000000463 material Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 36
- 239000002585 base Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 22
- 238000005303 weighing Methods 0.000 description 19
- 239000011787 zinc oxide Substances 0.000 description 16
- 239000011149 active material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000002572 peristaltic effect Effects 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 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 7
- 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
- 229920003235 aromatic polyamide Polymers 0.000 description 5
- 239000006260 foam 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
- 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
- 239000011230 binding agent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000203 mixture Substances 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
- 238000005096 rolling process 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
- 229910013684 LiClO 4 Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 230000001351 cycling effect Effects 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
- 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
- 239000007773 negative electrode material Substances 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
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 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
- 235000012431 wafers Nutrition 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
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 230000002401 inhibitory effect Effects 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 238000012827 research and development Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention relates to the technical field of battery materials, and discloses a preparation method and application of a polyarylene 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 A component solution or the B component solution to prepare a mixed solution; (4) Mixing the mixed solution with another component solution to perform an oxidative polymerization reaction; (5) And (3) carrying out solid-liquid separation on the reacted product, and washing and drying a solid phase to obtain the polyarylene diamine/metal oxide composite material. The invention can solve the problems of non-conductive metal oxide and easy dissolution in strong alkali by compounding conductive poly (arylene diamine), and the preparation process has the advantages of simple operation, convenience, 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 polyarylene diamine/metal oxide composite material.
Background
Zinc-based batteries are an important branch of chemical storage batteries, and are a research and development hotspot for chemical power sources. The zinc storage is abundant, the price is low, the specific capacity is high, and the production and the use of the zinc-based battery can not pollute the environment, thus being a real green battery cathode material. With these excellent characteristics, zinc-based batteries, such as zinc-nickel secondary batteries, zinc-nickel flow batteries, zinc-bromine batteries, and the like, have been attracting attention of researchers and have become an important 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 the mixture of zinc oxide (ZnO) powder and metal zinc powder is charged, zinc oxide powder particles which are in contact with the metal zinc powder due to poor zinc oxide conductivity are easy to charge, so that the problems of polarization, insufficient charging of a zinc electrode, attenuation and the like are caused. Therefore, zinc oxide is modified to improve conductivity, and is widely studied. For example: literature (Electrochimica Acta (2013) 40-46) explores techniques and battery applications for zinc oxide overcladding with conductive carbon, but the conductive carbon has a low hydrogen evolution potential and requires pyrolysis to affect the electrochemical activity of zinc oxide. The literature (batteries 41 (2011) 101-103) has studied techniques and battery applications in which zinc oxide is coated with indium oxide, but indium oxide improves hydrogen evolution potential and cannot improve conductivity of zinc oxide. There are also some documents that doping and coating oxide and hydroxide such as aluminum, tin, etc. into zinc oxide crystal cannot improve conductivity of zinc oxide. The literature (material guide 30 (2016) 15-20) describes zinc oxide/graphene nanocomposite preparation techniques, but the cost is high, and future industrial preparation and application have no clear prospect.
Therefore, the method for improving the conductivity of the zinc oxide, which has the advantages of simple and convenient operation, easy industrialization, low production cost and less pollution, is developed and has important significance.
Disclosure of Invention
The invention provides a preparation method and application of a poly (arylene diamine)/metal oxide composite material, which are used for solving the problems that metal oxide is not conductive and is easy to dissolve in strong alkali by compounding conductive poly (arylene diamine), and the preparation process is simple and convenient to operate, easy to industrialize, low in production cost and less in pollution, so as to solve the problems that polarization and insufficient charging of a zinc electrode are caused by zinc oxide particles which are in contact with metal zinc powder are easy to charge when a mixture of zinc oxide powder and metal zinc powder of a secondary zinc electrode in the prior art is charged.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing a polyarylene diamine/metal oxide composite material, comprising the steps of:
(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 A component solution or the B component solution to prepare a mixed solution;
(4) Mixing the mixed solution with another component solution to perform an oxidative polymerization reaction;
(5) And (3) carrying out solid-liquid separation on the reacted product, and washing and drying a solid phase to obtain the polyarylene diamine/metal oxide composite material.
The polyarylene diamine/metal oxide composite material of the present invention is prepared by mixing a metal material to be compounded in the form of a soluble metal salt into an oxidative polymerization system of an aromatic diamine and initiating polymerization. During the reaction, the aromatic diamine is polymerized to form aromatic diamine, and metal ion oxide sol gel is precipitated to form metal oxide (or hydroxide), so that the aromatic diamine and the metal oxide (or hydroxide) form micro-nano structure composite. The polyaramid has better conductivity and high stability in the reduced state, can inhibit dissolution and provide a certain electrochemical specific capacity, and improves the conductivity inside the metal oxide (or hydroxide) particles, thereby more effectively solving the problem of poor conductivity of the metal oxide (or hydroxide) itself.
The composite material can solve the problems that metal oxide is not conductive and is easy to dissolve in strong alkali through the composition of conductive polyarylene diamine, and the prepared composite material can be used in zinc-based batteries with alkaline and near-neutral electrolytes, so that the cycle life of zinc cathodes of the batteries and the specific energy of the batteries are prolonged; the material can also be used as a negative electrode material of a lithium ion battery, and the cycling stability of the battery is improved. Meanwhile, the preparation method of the composite material does not need pyrolysis treatment, avoids high-temperature and high-energy consumption such as carbon inclusion, is simple and convenient to operate, is easy to industrialize, has low production cost and less pollution, and has the advantages of economy and environmental protection.
Preferably, the aromatic diamine in the step (1) is selected from one or more of o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminonaphthalene, diaminophenazine, diaminoanthracene and diaminoanthraquinone.
Preferably, the oxidant in the step (2) is selected from one or more of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, ammonium hypochlorite, sodium hypochlorite, potassium hypochlorite and peracetic acid.
Preferably, the solvents in steps (1) and (2) are each independently selected from one or more of deionized water, methanol, ethanol, ethylene glycol, polyethylene glycol, glycerol, polyvinyl alcohol, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide.
Preferably, in the soluble metal salt in 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 step (4) is mixed, the molar ratio of the aromatic diamine, the oxidant and the soluble metal salt is 1:3-5:4-8. With the usage amount, the polyaromatic 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 reaction conditions in step (4) are: the reaction temperature is 0-100 ℃, the pH=8-10, and the reaction time is 1-12 h; the alkali used for adjusting the pH of the reaction to 8-10 is one or more selected from ammonia water, ethylenediamine, potassium hydroxide, sodium hydroxide and lithium hydroxide.
Preferably, the A component solution or the B component solution further comprises a conductive material, wherein the conductive material is one or more selected from graphene, carbon nano tubes, acetylene black and graphite powder; the addition amount of the conductive material is 1-15% of the mass of the poly (arylene diamine)/metal oxide composite material.
Preferably, the addition amount of the conductive material is 3-8% of the mass of the polyarylene diamine/metal oxide composite material.
Preferably, the drying temperature in step (5) is not more than 200 ℃.
The invention also provides an application of the polyaramid/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 polyarylene diamine/metal oxide composite material, the conductive agent and the binder in water or an organic solvent to form slurry; the slurry is coated on a current collector, and the current collector is dried and rolled into an electrode.
Preferably, the mass ratio of the polyarylene diamine/metal oxide composite material, the conductive agent and 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 aluminum foam.
Therefore, the invention has the following beneficial effects:
(1) The problem that the metal oxide is not conductive and is easy to dissolve in strong alkali can be solved by compounding conductive polyarylene diamine;
(2) The preparation method of the composite material does not need pyrolysis treatment, avoids high-temperature and high-energy consumption such as carbon inclusion, is simple and convenient to operate, is easy to industrialize, has low production cost and less 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 can improve the cycle life of a zinc cathode of the battery and the specific energy of the battery; the material can also be used as a negative electrode material of a lithium ion battery, and the cycling stability of the battery is improved.
Detailed Description
The invention is further described below in connection with the following detailed description.
General examples:
a method for preparing a polyarylene diamine/metal oxide composite material, comprising the steps of:
(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 one or more selected from deionized water, methanol, ethanol, glycol, polyethylene glycol, glycerol, polyvinyl alcohol, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide;
(2) Adding an oxidant into a solvent to prepare a component B solution; the oxidant is one or more selected from ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, ammonium hypochlorite, sodium hypochlorite, potassium hypochlorite and peracetic acid; the solvent is one or more selected from 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 A component solution or the B component 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, chlorate, perchlorate, bromide, bromate, formate, acetate, fluoroborate, fluorosulfonate, methylsulfonate, trifluoromethylsulfonate, benzenesulfonate, citrate, tartrate and nitrilotriacetate;
(4) Mixing the mixed solution with another component solution to perform an 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=8-10, and the reaction time is 1-12 h; the alkali used for adjusting the pH of the reaction to 8-10 is one or more selected from ammonia water, ethylenediamine, potassium hydroxide, sodium hydroxide and lithium hydroxide;
(5) Carrying out solid-liquid separation on the reacted product, and washing and drying a solid phase to obtain the polyarylene diamine/metal oxide composite material; the drying temperature is not more than 200 ℃;
optionally, the solution A or the solution B further comprises a conductive material, wherein the conductive material is one or more selected from graphene, carbon nanotubes, acetylene black and graphite powder; the addition amount of the conductive material is 1-15% of the mass of the poly (arylene diamine)/metal oxide composite material.
Example 1:
4.32g (0.04 mol) of o-phenylenediamine and 35.09g (0.16 mol) of zinc acetate dihydrate are weighed and dissolved in 200mL of deionized water together to prepare a component A solution; 36.53g (0.16 mol) of ammonium persulfate and 40.00g (1.00 mol) of sodium hydroxide are weighed and dissolved together in 200mL of deionized water to prepare a component B solution; and (3) placing the component A solution into a water bath with the temperature of 70 ℃ to serve as a base solution, continuously magnetically stirring, dripping the component B solution into the base solution by using a peristaltic pump, controlling the dripping speed to be about 0.5mL/min, keeping the temperature of the mixed solution after dripping at the temperature of 70 ℃ and continuously stirring for reaction for 12 hours. Cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove liquid phase, washing by using deionized water until filtrate is colorless, and finally drying for 15 hours at a constant temperature of 120 ℃ in vacuum to obtain the dark brown black poly (arylene diamine)/metal oxide composite material. Through testing, the zinc oxide in the dried composite material accounts for 70wt% and the polyaramid accounts for 30wt%.
Example 2:
weighing 0.02mol of o-phenylenediamine, 0.02mol of diaminonaphthalene, 0.15mol of zinc acetate dihydrate and 0.01mol of copper acetate, and dissolving the components together in 200mL of deionized water to prepare a component A solution; weighing 0.16mol of ammonium persulfate and dissolving in 150mL of deionized water to prepare a component B solution; 1mol/L sodium hydroxide aqueous solution is additionally prepared. Placing the A component solution into a water bath with the temperature of 100 ℃ to serve as a base solution and continuously stirring magnetically, dripping the B component solution into the base solution by a peristaltic pump, controlling the dripping speed to be about 0.5mL/min, adding 1mol/L sodium hydroxide aqueous solution into the base solution by another peristaltic pump, setting the pH value to be 8-10, keeping the temperature of the mixed solution after the dripping of the B component solution is finished at the temperature of 100 ℃ and continuously stirring for reacting for 12 hours (adjusting the pH value during the period to be 8-10). Cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove liquid phase, washing by using deionized water until filtrate is colorless, and finally drying for 10 hours at a constant temperature of 200 ℃ in vacuum to obtain the dark brown black poly (arylene diamine)/metal oxide composite material. Through testing, the polyarylene diamine accounts for 32wt% in the dried composite material.
Example 3:
weighing 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, and dissolving the materials 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 sodium hydroxide together in 200mL of deionized water to prepare a component B solution; and (3) placing the component A solution into a water bath at 0 ℃ to serve as a base solution, continuously magnetically stirring, dripping the component B solution into the base solution by using a peristaltic pump, controlling the dripping speed to be about 0.5mL/min, keeping the temperature of the mixed solution at 0 ℃ after dripping, and continuously stirring for reaction for 5 hours. Filtering by adopting a sand core funnel after the reaction is finished to remove a liquid phase, washing by using deionized water until filtrate is colorless, and finally drying for 10 hours at a constant temperature of 110 ℃ in vacuum to obtain the dark brown black poly (arylene diamine)/metal oxide composite material. Through testing, the polyarylene diamine accounts for 35wt% in 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 materials in 200mL of deionized water together to prepare a component A solution; weighing 0.06mol of sodium hypochlorite and 1.00mol of sodium hydroxide, and dissolving the sodium hypochlorite and the sodium hydroxide together in 200mL of deionized water to prepare a component B solution; and (3) placing the component A solution into a water bath at 80 ℃ to serve as a base solution, continuously magnetically stirring, dripping the component B solution into the base solution by using a peristaltic pump, controlling the dripping speed to be about 0.2mL/min, keeping the temperature of the mixed solution at 80 ℃ after dripping, and continuously stirring for reaction for 1h. Cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove liquid phase, washing by using deionized water until filtrate is colorless, and finally drying for 24 hours at a constant temperature of 60 ℃ in vacuum to obtain the dark brown black poly (arylene diamine)/metal oxide composite material. Through testing, the polyarylene diamine in the dried composite material accounts for 10 weight percent.
Example 5:
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 are weighed and dissolved in 200mL of deionized water together to prepare a component A solution, and 0.7g of water-dispersible graphene is added into the component A solution; weighing 0.06mol of sodium hypochlorite and 1.00mol of sodium hydroxide, dissolving the sodium hypochlorite and the sodium hydroxide together in 200mL of deionized water to prepare a B component solution, and adding 0.7g of water-based dispersed graphene into the B component solution; and (3) placing the component A solution into a water bath at 80 ℃ to serve as a base solution, continuously magnetically stirring, dripping the component B solution into the base solution by using a peristaltic pump, controlling the dripping speed to be about 0.2mL/min, keeping the temperature of the mixed solution at 80 ℃ after dripping, and continuously stirring for reaction for 1h. Cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove liquid phase, washing by using deionized water until filtrate is colorless, and finally drying for 24 hours at a constant temperature of 60 ℃ in vacuum to obtain the dark brown black poly (arylene diamine)/metal oxide composite material. Through testing, the dried composite material contains 10wt% of polyaramid, and the conductive material graphene contains 10wt% of polyaramid/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 0.16mol of titanyl sulfate in 200mL of deionized water together 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 sodium hydroxide together in 200mL of deionized water to prepare a component B solution; and (3) placing the component A solution into a water bath at 50 ℃ to serve as a base solution, continuously magnetically stirring, dripping the component B solution into the base solution by using a peristaltic pump, controlling the dripping speed to be about 0.1mL/min, keeping the temperature of the mixed solution at 50 ℃ after dripping, and continuously stirring for reaction for 12 hours. Cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove liquid phase, washing by using deionized water until filtrate is colorless, and finally drying for 24 hours at a constant temperature of 60 ℃ in vacuum to obtain the dark brown black poly (arylene diamine)/metal oxide composite material. Through testing, the polyarylene diamine in the dried composite material accounts for 12 weight percent.
Example 7:
weighing 0.01mol of m-phenylenediamine, 0.01mol of 2, 3-diaminophenazine and 0.16mol of stannic chloride, and dissolving in 200mL of deionized water together to prepare a component A solution (a small amount of hydrochloric acid is needed to be supplemented to inhibit stannic chloride hydrolysis); weighing 0.08mol of sodium hypochlorite and 1.00mol of sodium hydroxide, and dissolving the sodium hypochlorite and the sodium hydroxide together in 200mL of deionized water to prepare a component B solution; and (3) placing the component A solution into a water bath at 60 ℃ to serve as a base solution, continuously magnetically stirring, dripping the component B solution into the base solution by using a peristaltic pump, controlling the dripping speed to be about 0.1mL/min, keeping the temperature of the mixed solution at 60 ℃ after dripping, and continuously stirring for reaction for 12 hours. Cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove liquid phase, washing by using deionized water until filtrate is colorless, and finally drying for 24 hours at a constant temperature of 60 ℃ in vacuum to obtain the dark brown black poly (arylene diamine)/metal oxide composite material. Through testing, the polyarylene diamine in the dried composite material accounts for 12 weight percent.
Comparative example 1:
weighing 0.14mol of zinc acetate dihydrate, 0.01mol of copper acetate and 0.005mol of indium sulfate, and dissolving in 200mL of deionized water together to prepare a component A solution; weighing 0.4mol of sodium hydroxide and dissolving in 200mL of deionized water to prepare a component B solution; and (3) placing the component A solution into a water bath at 80 ℃ to serve as a base solution, continuously magnetically stirring, dripping the component B solution into the base solution by using a peristaltic pump, controlling the dripping speed to be about 0.2mL/min, keeping the temperature of the mixed solution at 80 ℃ after dripping, and continuously stirring for reaction for 1h. Cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove liquid phase, washing by using deionized water until filtrate is colorless, and finally drying for 24 hours at the constant temperature of 60 ℃ in vacuum 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 together 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 sodium hydroxide together in 200mL of deionized water to prepare a component B solution; and (3) placing the component A solution into a water bath at 0 ℃ to serve as a base solution, continuously magnetically stirring, dripping the component B solution into the base solution by using a peristaltic pump, controlling the dripping speed to be about 0.5mL/min, keeping the temperature of the mixed solution at 0 ℃ after dripping, and continuously stirring for reaction for 5 hours. Filtering by adopting a sand core funnel after the reaction is finished to remove a liquid phase, washing by using deionized water until filtrate is colorless, and finally drying for 10 hours at a constant temperature of 110 ℃ in vacuum to obtain the dark brown black poly (arylene diamine)/metal oxide composite material. Through testing, the polyarylene diamine in the dried composite material accounts for 52wt%.
Comparative example 3:
weighing 0.16mol of titanyl sulfate and jointly dissolving in 200mL of deionized water 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; and (3) placing the component A solution into a water bath at 50 ℃ to serve as a base solution, continuously magnetically stirring, dripping the component B solution into the base solution by using a peristaltic pump, controlling the dripping speed to be about 0.1mL/min, keeping the temperature of the mixed solution at 50 ℃ after dripping, and continuously stirring for reaction for 12 hours. Cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove liquid phase, washing to be neutral by using deionized water, and finally drying for 24 hours at the constant temperature of 60 ℃ in vacuum to obtain the metal oxide composite material.
Comparative example 4:
weighing 0.16mol of stannic chloride, and dissolving in 200mL of deionized water to prepare a component A solution (a small amount of hydrochloric acid is needed to be supplemented to inhibit the hydrolysis of stannic chloride); weighing 0.8mol of sodium hydroxide and dissolving the sodium hydroxide in 200mL of deionized water to prepare a component B solution; and (3) placing the component A solution into a water bath at 60 ℃ to serve as a base solution, continuously magnetically stirring, dripping the component B solution into the base solution by using a peristaltic pump, controlling the dripping speed to be about 0.1mL/min, keeping the temperature of the mixed solution at 60 ℃ after dripping, and continuously stirring for reaction for 12 hours. Cooling to a greenhouse after the reaction is finished, filtering by adopting a sand core funnel to remove liquid phase, washing to be neutral by using deionized water, and finally drying for 24 hours at the constant temperature of 60 ℃ in vacuum to obtain the metal oxide composite material.
Application examples 1 to 4:
the polyarylene diamine/metal oxide composites prepared in examples 1 to 4 were pulverized to 400 mesh or more as an active material for an electrode, respectively, according to the active material: acetylene black: mixing the binder (60 wt% polytetrafluoroethylene emulsion) at a mass ratio of 87:10:3 (based on solid mass ratio), adding a small amount of deionized water and absolute ethyl alcohol, fully grinding, rolling into tablets, drying in an oven at 120 ℃ for 12 hours, and cutting into 2X 2cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The active material loading is 5.0mg/cm 2 And pressing the electrode on a 100-mesh tinned copper wire by using a pressure of 4MPa on an oil press to prepare the electrode.
7mol/L potassium hydroxide aqueous solution is used as electrolyte, 2X 2cm 2 The specific discharge capacities (charge-discharge cycle conditions: 50mA/g or 500mA/g charged to 1.1 times the theoretical capacity and the same current density discharged to a cut-off voltage of 1.2V) of the above electrodes were respectively measured as counter electrodes, and the results are shown in Table 1.
Application example 5:
the polyarylene diamine/metal oxide composite material prepared in example 5 was pulverized to 400 mesh or more as an active material for an electrode, respectively, according to the active material: the binder (60 wt% polytetrafluoroethylene emulsion) was mixed at a mass ratio of 97:3 (as a solid mass ratio), and a small amount of deionized water was added and no water was addedGrinding with water and ethanol, rolling into tablet, drying in oven at 120deg.C for 12 hr, and cutting into 2×2cm pieces 2 The method comprises the steps of carrying out a first treatment on the surface of the The active material loading is 5.0mg/cm 2 And pressing the electrode on a 100-mesh tinned copper wire by using a pressure of 4MPa on an oil press to prepare the electrode.
7mol/L potassium hydroxide aqueous solution is used as electrolyte, 2X 2cm 2 The specific discharge capacities (charge-discharge cycle conditions: 50mA/g or 500mA/g charged to 1.1 times the theoretical capacity and the same current density discharged to a cut-off voltage of 1.2V) of the above electrodes were respectively measured as counter electrodes, and the results are shown in Table 1.
Comparative application examples 1-2:
the zinc oxide prepared in comparative example 1 and the polyarylene diamine/metal oxide composite prepared in comparative example 2 were each pulverized to 400 mesh or more as an active material of an electrode, and the rest was the same as in application example 1.
7mol/L potassium hydroxide aqueous solution is used as electrolyte, 2X 2cm 2 The specific discharge capacities (charge-discharge cycle conditions: 50mA/g or 500mA/g charged to 1.1 times the theoretical capacity and the same current density discharged to a cut-off voltage of 1.2V) of the above electrodes were respectively measured as counter electrodes, and the results are shown in Table 1.
Application example 6:
the polyarylene diamine/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 active material: acetylene black: mixing adhesive (60 wt% 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 tablets, drying in an oven at 120 ℃ for 12 hours, cutting into wafers with the diameter of 14mm, and loading 5.0mg/cm according to active substance 2 The electrode was made by pressing on aluminum foam with a pressure of 4MPa on an oil press.
With 1mol/L LiClO 4 The discharge specific capacity and cycle performance of the above electrodes were tested (charge-discharge cycle conditions: 50mA/g or 500mA/g discharge 1.0V, same current density charged to cut-off) using (EC+DMC) (EC to DMC volume ratio 1:1) as electrolyte, 14mm round lithium sheet as counter electrode, celgard2500 separatorPressure 2.5V) and the results are shown in table 2.
Application example 7:
the polyarylene diamine/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% 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 tablets, drying in an oven at 120 ℃ for 12 hours, cutting into wafers with the diameter of 14mm, and loading 5.0mg/cm according to active substance 2 The electrode was made by pressing on aluminum foam with a pressure of 4MPa on an oil press.
With 1mol/L LiClO 4 The specific discharge capacity and cycle performance (charge-discharge cycle conditions: 50mA/g or 500mA/g discharge 1.0V, the same current density charged to a cut-off voltage of 2.5V) of the above electrode were tested as an electrolyte, a 14mm round lithium sheet as a counter electrode, and Celgard2500 separator, and 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 each pulverized to 400 mesh or more as an active material of an electrode, and the rest was the same as in application example 6.
With 1mol/L LiClO 4 The specific discharge capacity and cycle performance (charge-discharge cycle conditions: 50mA/g or 500mA/g discharge 1.0V, the same current density charged to a cut-off voltage of 2.5V) of the above electrode were tested as an electrolyte, a 14mm round lithium sheet as a counter electrode, and Celgard2500 separator, and the results are shown in Table 2.
Table 1: and (5) testing the application performance of the zinc-based battery.
Table 2: and (5) testing the application performance of the lithium ion battery.
It can be seen from tables 1 and 2 that the polyarylene diamine/metal oxide composite materials 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 comparative application example 1, zinc oxide was not compounded with polyarylene diamine, and thus the conductivity of zinc oxide was poor, and the initial specific capacity for zinc-based batteries was high, but the cycle specific capacity was significantly lower than in examples; the material after the poly (arylene diamine) is compounded has high multiplying power performance and circulation specific capacity, and the poly (arylene diamine) is beneficial to improving the electronic conduction of oxides and inhibiting the dissolution and migration of zinc oxide; as can be seen from the data of application examples 1 to 4 and comparative application example 2, when the content of the polyarylene diamine is high, the specific capacity of the composite material is also significantly reduced due to the low specific capacity and low density of the polyarylene diamine itself. Similarly, as can be seen from table 2, the metal oxide composite polyarylene diamine improves the electron conductivity of the oxide, improves the rate performance, and also improves the specific capacity as a negative electrode of a lithium ion battery.
Claims (8)
1. A method for preparing a polyarylene diamine/metal oxide composite material, comprising the steps of:
(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; the oxidant is one or more selected from ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, ammonium hypochlorite, sodium hypochlorite, potassium hypochlorite and peracetic acid;
(3) Adding soluble metal salt into the A component solution or the B component solution to prepare a mixed solution;
(4) Mixing the mixed solution with another component solution to perform an oxidative polymerization reaction; after mixing, the molar ratio of the aromatic diamine, the oxidant and the soluble metal salt is 1:3-5:4-8;
(5) And (3) carrying out solid-liquid separation on the reacted product, and washing and drying a solid phase to obtain the polyarylene diamine/metal oxide composite material.
2. The process according to claim 1, wherein the aromatic diamine in the 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 process of claim 1, wherein the solvents in steps (1) and (2) are each independently selected from one or more of deionized water, methanol, ethanol, ethylene glycol, polyethylene glycol, glycerol, polyvinyl alcohol, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide.
4. The method according to claim 1, wherein the soluble metal salt in the step (3) contains one or more metal elements selected from zinc, copper, tin, titanium, iron, chromium, vanadium, lead, bismuth, and indium.
5. The process according to claim 1 or 4, 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.
6. The process according to claim 1, wherein the oxidative polymerization conditions in step (4) are: the reaction temperature is 0-100 ℃, the pH=8-10, and the reaction time is 1-12 h; the alkali used for adjusting the pH of the reaction to 8-10 is one or more selected from ammonia water, ethylenediamine, potassium hydroxide, sodium hydroxide and lithium hydroxide.
7. The preparation method of claim 1, wherein the solution of component a or the solution of component B further comprises a conductive material, and the conductive material is one or more selected from graphene, carbon nanotubes, acetylene black and graphite powder; the addition amount of the conductive material is 1-15% of the mass of the poly (arylene diamine)/metal oxide composite material.
8. Use of a polyarylene diamine/metal oxide composite material prepared using the method of any one of claims 1 to 7 in an electrode.
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| 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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| 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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