CN114122414A - Piperidine nitroxide free radical/zinc composite redox flow battery and preparation method thereof - Google Patents
Piperidine nitroxide free radical/zinc composite redox flow battery and preparation method thereof Download PDFInfo
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- CN114122414A CN114122414A CN202111308746.5A CN202111308746A CN114122414A CN 114122414 A CN114122414 A CN 114122414A CN 202111308746 A CN202111308746 A CN 202111308746A CN 114122414 A CN114122414 A CN 114122414A
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- 239000011701 zinc Substances 0.000 title claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- -1 Piperidine nitroxide free radical Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 239000000126 substance Substances 0.000 claims abstract description 51
- 239000000243 solution Substances 0.000 claims description 43
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 239000010439 graphite Substances 0.000 claims description 26
- 229910002804 graphite Inorganic materials 0.000 claims description 26
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 229920000858 Cyclodextrin Polymers 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- ODLHGICHYURWBS-LKONHMLTSA-N trappsol cyclo Chemical group CC(O)COC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)COCC(O)C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1COCC(C)O ODLHGICHYURWBS-LKONHMLTSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 23
- 239000001103 potassium chloride Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000004108 freeze drying Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 235000011164 potassium chloride Nutrition 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
- 229940067157 phenylhydrazine Drugs 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- AKKLAJYCGVIWBS-UHFFFAOYSA-N O=[N].CC1(C)CCCC(C)(C)N1 Chemical compound O=[N].CC1(C)CCCC(C)(C)N1 AKKLAJYCGVIWBS-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- IUKQLMGVFMDQDP-UHFFFAOYSA-N azane;piperidine Chemical compound N.C1CCNCC1 IUKQLMGVFMDQDP-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a piperidine nitroxide free radical/zinc composite redox flow battery and a preparation method thereof, wherein zinc is used as a negative electrode; will contain a poorly soluble substance
The clathrate is used as positive electrode of aqueous aerobic reduction flow battery and is insoluble
The clathrate compound active molecules can perform reversible redox reaction and have good reversibility and excellent kinetic performance. In particular, poor solubility
The inclusion compound can show larger potential than before inclusion, and can be matched with a proper cathodeSo as to match with the high-voltage aqueous organic flow battery.
Description
Technical Field
The invention belongs to the field of large-scale energy storage, and particularly relates to a piperidine nitroxide free radical/zinc composite redox flow battery and a preparation method thereof.
Background
With the continuous development of new energy technologies, the proportion of new energy technologies such as solar energy, hydroelectric power, wind power, tidal power and the like in energy supply is larger and larger, however, most new energy technologies are greatly influenced by the outside world, the risk resistance is poorer, and the new energy technologies are easily influenced in extreme situations. The production fluctuation is large, and the continuous production capacity is poor, so that the development of energy storage materials is an inevitable choice. Electrochemical energy storage has the advantages of high energy efficiency, convenient maintenance, good cycle performance and the like, and compared with a lithium ion battery, a flow battery has the advantages of low cost, strong safety and strong designability, can store wind energy, solar energy and the like when being at peak values, and stabilizes the energy at a trough, thereby providing favorable conditions for the popularization of new energy technology.
The energy of the flow battery is stored in an electrolyte separate from the battery, thereby making the power output of the battery independent of the energy storage. Generally, the structure of a flow battery includes: two liquid storage tanks of positive negative pole, positive negative pole material, diaphragm and battery shell. The positive and negative electrolytes can circularly flow in the liquid storage tank and the battery chamber under the action of the peristaltic pump, and oxidation-reduction reaction is carried out on the electrodes, so that charging and discharging are realized. The flow battery can change the battery capacity by changing the quantity and concentration of the positive and negative electrolytes, and change the battery power by changing the number of batteries connected in series and the effective area in the pile, thereby facilitating the battery design.
There are many different systems of inorganic redox flow batteries today, such as all vanadium flow batteries, Fe/V flow batteries (IVB), polysulfide/bromide flow batteries (PSB), Zn/polyiodide flow batteries (ZIB), Zn/Ce flow batteries, soluble lead acid flow batteries (SLFB), H2/Br2Flow batteries, polysulfide/ferricyanide flow batteries, all-iron flow batteries, and the like. However, these inorganic flow batteries have various disadvantages, such as the presence of Br in PSB flow batteries2Cross contamination, sulfur precipitation and slow kinetics during film penetration, while Zn/Ce will produce zinc dendrite during charging and discharging, resulting in high cost and short service life. Meanwhile, the problems of gas influence, requirement of expensive catalyst, high requirement of a diaphragm and the like are the problems which the development of the battery has to face. Therefore, the theoretical cost is low and the modification is easyThe water system organic oxidation flow battery with the characteristic becomes a new direction, wherein the chemical performance of 2,2,6,6-tetramethyl piperidine-nitrogen-oxide (2,2,6,6-tetramethyl piperidine-1-oxyl, TEMPO) is stable, and the adjacent methyl group forms steric hindrance to inhibit the chemical reaction of generating the dimer. The free radical can generate oxidation-reduction reaction with single electron participation and has good reversibility, so the free radical has better prospect in the field of flow batteries, but the development of the insoluble TEMPO substance is restricted by the problems of poor solubility, low electrochemical stability and easy occurrence of permeation phenomenon.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a piperidine nitroxide radical/zinc composite redox flow battery and a preparation method thereof, so as to solve the problems of poor solubility, low electrochemical stability and easy permeation of insoluble TEMPO substances in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a piperidine nitroxide radical/zinc composite redox flow battery comprises a positive electrode and a negative electrode; the positive electrode is a subject-guest inclusion compound, the subject-guest inclusion compound is a substance formed by bonding a host substance and a guest substance, the host substance is TEMPO or a TEMPO derivative, and the guest substance is a cyclodextrin substance or a cyclodextrin substance derivative; the TEMPO has a structural formula as follows:
the TEMPO derivative has a structural formula:
r is-OCH3Or OC7H7。
The invention is further improved in that:
preferably, the solubility of the host-guest inclusion compound in an electrolyte is 0.01-10 mol/L.
Preferably, the electrolyte is one or more of an acid solution, an alkali solution or an aqueous solution.
Preferably, the cyclodextrin species include α -CD, β -CD and γ -CD; the cyclodextrin derivative is HP-beta-CD.
A preparation method of a piperidine nitroxide free radical/zinc composite redox flow battery takes Zn as a negative electrode and a host-guest inclusion compound as a positive electrode, the guest substance is TEMPO or TEMP derivative, and the host substance is cyclodextrin substance or cyclodextrin derivative; sequentially assembling the battery according to the sequence of a copper current collector, a graphite plate flow channel, a carbon paper/graphite felt electrode, a perfluorinated sulfonic acid-polytetrafluoroethylene copolymer film, an electrode, a graphite plate flow channel and a copper current collector;
the preparation method of the host-guest inclusion compound comprises the following steps: mixing a host substance and a guest substance in a KCl solution, stirring or ultrasonically treating, confirming to form a host-guest inclusion compound when the solution becomes turbid, and cooling and drying the host-guest inclusion compound to obtain a final host-guest inclusion compound; the guest substance is TEMPO or a TEMPO derivative, and the host substance is a cyclodextrin substance or a cyclodextrin derivative.
Preferably, the molar ratio of the host substance to the guest substance is (0.1-1): (1-3).
Preferably, the stirring time is more than 24h, and the ultrasonic time is more than 40 min.
Preferably, the electrode is a graphite felt, a carbon paper or a metal electrode; the metal electrode is one or more of a combination of a gold electrode, a platinum electrode and a silver electrode.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a piperidine nitroxide free radical/zinc composite redox flow battery, which takes zinc as a negative electrode; will contain a poorly soluble substance
Clathrate compound as positive electrode of aqueous aerobic reduction flow batteryVery much, use is made of the insolubility
The clathrate compound active molecules can perform reversible redox reaction and have good reversibility and excellent kinetic performance. In particular, poor solubility
The inclusion compound can show a larger potential than that before inclusion, and can be matched with a proper negative electrode to form a high-voltage aqueous organic flow battery. Furthermore, poor solubility
The solubility of the inclusion compound is greatly improved compared with that before inclusion, the osmosis is well avoided, and simultaneously, the indissolvability is caused
The clathrate is mainly composed of carbon, hydrogen, nitrogen and oxygen, and has low cost and abundant sources, so it is insoluble after mass production and manufacture
The cost of the clathrate compound/Zn water system organic redox flow battery is greatly reduced compared with the cost of the existing heavy metal ion flow battery such as vanadium, and the method can be used for large-scale energy storage technology.
The invention also discloses a preparation method of the piperidine nitroxide radical/zinc composite redox flow battery, which simultaneously improves the water solubility, the redox potential and the electrochemical stability of TEMPO substances, has the advantages of flexible power energy design, low cost, simple production process, large-scale assembly and application and the like, and is very suitable for large-scale energy storage application. Compared with other methods for modifying insoluble TEMPO, the method is simpler and more convenient to operate and lower in cost. At the same time, the prior art has not utilized insolubility
Active matter of inclusion compoundAnd assembling the high-water-system organic flow battery.
Drawings
FIG. 1 shows a film obtained in example 1 of the present invention
The nuclear magnetic resonance hydrogen spectrum characterization result of the inclusion compound, TEMPO and gamma-CD takes deuterated water as a solvent and phenylhydrazine as a reducing agent.
FIG. 2 shows a film obtained in example 1 of the present invention
And (3) obtaining a test result of cyclic voltammetry of the clathrate solution, wherein the result is obtained by cyclic voltammetry test at sweep rates of 1225, 625, 100 and 9mV/s by using silver/silver chloride as a reference electrode.
FIG. 3 shows a film obtained in example 1 of the present invention
And linearly fitting the peak current and the square root of the sweep rate of the clathrate solution at different sweep rates in a cyclic voltammetry test.
FIG. 4 shows the cell assembled in example 2 of the present invention at 30mA.cm-2Current density of (a) and (b) are measured and compared to a current density of (a) and (b) to obtain a battery efficiency map for 1000 cycles with different numbers of charge and discharge cycles.
FIG. 5 shows the cell assembled in example 2 of the present invention at 30mA.cm-2Capacity-voltage diagram at different cycle numbers under charging and discharging at current density of (1).
Fig. 6 shows the cell efficiency at different current densities for the assembled cell of example 3 of the present invention.
Fig. 7 is a graph of the charge and discharge capacity of the assembled battery in example 3 of the present invention at different current densities.
Fig. 8 is a graph of capacity versus voltage for different current densities for the assembled cell of example 3 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
the invention discloses piperidine nitrogen oxygenA free radical/zinc composite redox flow battery and a preparation method thereof, wherein the redox flow battery takes Zn as a negative electrode and takes a host-guest inclusion compound
The composite material is used as a positive electrode, the host-guest inclusion compound is a substance formed by bonding a host substance and a guest substance, and particularly the host-guest inclusion compound which is formed by taking insoluble TEMPO and derivatives thereof as a guest and taking cyclodextrin amphiphilic substances as a host through the coordination of the host and the guest through non-covalent actions such as hydrogen bond interaction, Van der Waals bond and hydrophilic and hydrophobic actions is used as the positive electrode; one or more of acid solution, alkali solution and salt water solution are mixed to be used as electrolyte; an anion exchange membrane is taken as an ion exchange membrane diaphragm; two copper plates are used as current collectors of the battery; a graphite plate with a flow channel is used as a flow field plate of the anode and the cathode; carbon paper, graphite felt or metal electrode is used as the electrode of the battery.
In particular, the method comprises the following steps of,
the solubility of the inclusion compound in electrolyte is 0.01-10 mol/L.
The inclusion compound comprises cyclodextrin substances and derivatives thereof, wherein the cyclodextrin substances comprise alpha-CD, beta-CD and gamma-CD; examples of the cyclodextrin derivative include HP-beta-CD.
The inclusion compound guest is TEMPO and derivatives thereof. Wherein the TEMPO structural formula is:
wherein 4 ortho methyl groups can play a role in stabilizing the structure, and nitroxide free radicals can perform redox reaction.
The structure of the insoluble TEMPO derivative is as follows:
wherein R is-OCH3、-OC7H7More specifically, the insoluble TEMPO derivative is 4-OBn-TEMPO or 4-OMe-TEMPO. The insolubility
The inclusion compound is obtained by directly using TEMPO or modifying 4-OH-TEMPO, and the inclusion compound is obtained by an ultrasonic or stirring method.
In the electrolyte, the acidic aqueous solution is sulfuric acid, nitric acid, phosphoric acid or hydrochloric acid. The neutral aqueous solution is sodium chloride, potassium nitrate, potassium phosphate, potassium sulfate, sodium nitrate, sodium sulfate or sodium phosphate. The alkaline aqueous solution is potassium hydroxide, sodium hydroxide, lithium hydroxide or barium hydroxide.
The method for assembling the organic redox flow battery comprises the following steps:
zn is used as a negative electrode; by insolubility in water
The inclusion compound is used as a positive electrode; one or more of acid solution, alkali solution and salt water solution are mixed to be used as electrolyte; the battery is sequentially assembled by a copper current collector, a graphite plate flow channel, an electrode, a perfluorinated sulfonic acid-polytetrafluoroethylene copolymer film, a carbon paper/graphite felt electrode, a graphite plate flow channel and a copper current collector.
Wherein it is poorly soluble
The preparation process of the inclusion compound comprises the following steps:
taking 1mol L-1And (3) 20mL of KCl solution, weighing and preparing a mixed solution of 1-3 mmol of cyclodextrin substances or cyclodextrin derivatives and 0.1-1 mmol of TEMPO or derivatives thereof in a round-bottom flask, and violently stirring at room temperature for more than 24h or ultrasonically treating for more than 40 min. When the solution became turbid, the formation of inclusion compound was confirmed. The inclusion compound solid can be obtained by freeze drying.
The invention provides a slightly soluble
clathrate/Zn-based aqueous organic redox flow battery, and insoluble matter of redox flow battery
The clathrate compound derivative is used as a positive electrode active material to perform oxidation-reduction reaction for charging and discharging.
The electrode material is graphite felt, carbon paper or metal electrode which is subjected to high-temperature heat-preservation annealing treatment or acidification pretreatment; the metal electrode is one or more of a gold electrode, a platinum electrode and a silver electrode.
For aqueous organic redox flow batteries, the following advantages exist: 1. the energy density and the output power of the battery can be separately designed, and the designability and the flexibility of the battery are increased. The energy density of the flow battery depends on the amount of the electrolyte and the concentration of the redox substances, the amount of the electrolyte is increased by changing the liquid storage tank, the power density of the flow battery is related to the galvanic pile, the larger the area of the galvanic pile is, the larger the accessible current is, the voltage is unchanged, the output power is increased, and the design between the liquid storage tank and the galvanic pile is not influenced mutually, so that the battery structure of the flow battery can be designed according to the actual situation, and various requirements are met. 2. Compared with the traditional inorganic flow batteries such as all-vanadium flow batteries and iron-chromium flow batteries, the organic active material mainly comprises the following components: C. h, O, N, which are quite common in nature, with relatively little contamination after leakage. Therefore, the economy and the environmental protection are better in theory. 3. The solvent of the water-based flow battery is water, and compared with organic solvents such as methanol and the like, the water-based flow battery has less environmental pollution and is difficult to burn when colliding or in a high-temperature environment, so that the safety coefficient is higher, and the water-based flow battery is more suitable for large-scale popularization. 4. Compared with inorganic matters, the organic matters have the advantages that the structure is easier to adjust, the modification difficulty is lower, and the electrochemical performance of the active substances can be changed by adding or modifying functional groups, so that the working voltage and the energy density of the battery are changed.
Compared with other redox active substance modification methods, the method has the following advantages for host-guest coordination: 1. the main body can be designed according to the properties of the guest body such as molecular size, structure, water solubility, electrical property and the like, and the design is simpler compared with methods for modifying functional groups and the like. 2. The solubility and the electrochemical stability of the object can be greatly improved, and the oxidation-reduction potential can be changed, so that the working performance of the flow battery is improved, and the service life of the flow battery is prolonged. 3. The volume of the redox substance can be increased by forming the inclusion compound, so that the permeation phenomenon of the small-molecule redox substance is reduced 4. compared with the addition or modification of functional groups, the host-guest coordination operation is simpler and more convenient, and the required energy is less. Is easier for large-scale production.
The following is further described with reference to the examples:
example 1
Taking 1mol L-1KCl solution is 20mL, a mixed solution of 3mmol of gamma-CD and 1mmol of TEMPO is weighed in a round-bottom flask, and is stirred vigorously for more than 24 hours at room temperature, and the solution is found to become turbid, so that the clathrate compound is formed. The inclusion compound solid can be obtained by freeze drying. Deuterium-substituted water is used as a solvent, phenylhydrazine is used as a reducing agent to respectively react on gamma-CD, TEMPO,
And performing a nuclear magnetic resonance hydrogen spectrum test.
From the chemical shift data of fig. 1, the positions of the characteristic peaks of the nmr hydrogen spectra before and after inclusion are substantially the same, but the positions of the characteristic peaks of the nmr hydrogen spectra after inclusion are shifted from those before inclusion. The host-guest complex is generated, and the host gamma-CD and the guest TEMPO form a host-guest inclusion compound through non-covalent interactions such as hydrogen bond interaction, Van der Waals bond, hydrophilic and hydrophobic interactions and the like
Wherein, the inclusion compound
A new peak is generated at 4.89ppm, the absorption peak positions at 4.70ppm, 2.67ppm and 2.79ppm are shifted forward compared with TEMPO, and the absorption peaks in the range of 0.5-1.5ppm are reduced to two and the peak values are greatly reduced, which proves that the hydrogen atom position of TEMPO in the inclusion compound is changed by the action of the host and the guestInstead, the generation of inclusion compounds was demonstrated.
Example 2
Weighing
Dissolving in 30 ml of 1mol/L potassium chloride solution, shaking and stirring, and preparing into 0.05mol/L potassium chloride solution
And (3) solution. And (3) performing cyclic voltammetry test on the prepared electrolyte by using a three-electrode system, wherein silver/silver chloride is used as a reference electrode, a platinum electrode is used as a counter electrode, and a glassy carbon electrode is used as a working electrode. The sweep rates were 0.009V/s, 0.100mV/s, 0.625V/s, and 1.225V/s.
From the CV data in fig. 2, under neutral conditions, there are a pair of significantly reversible redox peaks with good electrochemical reversibility, and when silver/silver chloride is used as a reference electrode,
the average potential of (2) is about 0.5795V, and a positive potential is exhibited as a positive electrode material.
The linear fit of the square root of its redox peak potential to sweep rate, with slopes on the same order of magnitude, in FIG. 3, demonstrates
Has reversible electrochemical performance, and the diffusion coefficients of the oxidation reaction and the reduction reaction are approximately the same and are in the same order of magnitude.
Example 3
Weighing
Dissolving in 7.5 ml of 1mol/L potassium chloride solution, stirring with shaking, and making into 0.1 mol/L solution
The solution served as the positive electrode. Taking a zinc sheet as a negativeA1 mol/L potassium chloride solution is used as a negative electrode electrolyte. And introducing nitrogen into the electrolyte to remove oxygen, and then introducing the electrolyte into a flow battery device as a positive electrode and a negative electrode. The graphite felt or the carbon paper is subjected to heat treatment, and the specific operation is that the graphite felt is placed in a muffle furnace, heated for ten hours at five hundred ℃, cooled to room temperature, taken out and then directly used. Using copper current collector-graphite plate flow channel-carbon paper/graphite felt electrode (5 cm)2) -perfluorosulfonic acid-polytetrafluoroethylene copolymer membrane-carbon paper/graphite felt electrode-graphite plate flow channel-copper current collector in sequence and position to assemble the cell, with liquid drive charging and discharging with peristaltic pump.
The battery is subjected to long-cycle performance test at 30mA.cm-2The current density of (a) was measured for a long cycle.
As shown in fig. 4, fig. 5,
the Zn full cell shows better coulombic efficiency (above 99.844%) in 1000 cycles, and the energy efficiency can be stably kept at about 73.0%. As can be seen from the graph, the charge-discharge efficiency was attenuated in 1000 cycles, and the capacity retention rate was 99.986%/cycle. Visible battery has better long cycle performance
Example 4
Weighing
Dissolving in 7.5 ml of 1mol/L potassium chloride solution, stirring with shaking, and making into 0.1 mol/L solution
The solution served as the positive electrode. Taking a zinc sheet as a positive electrode, and using 1mol/L potassium chloride solution as a negative electrode electrolyte. And introducing nitrogen into the electrolyte to remove oxygen, and then introducing the electrolyte into a flow battery device as a positive electrode and a negative electrode. The method comprises the following steps of acidizing the graphite felt or the carbon paper, specifically putting the graphite felt into 300ml of 1mol/L dilute salt, stirring for 3-5 hours, taking out, washing with deionized water, and drying for use. Using copper current collector-graphite plate flow channel-carbon paper/graphite felt electrode (5cm2) -perfluorosulfonic acidThe battery is assembled by the sequence and the position of acid-polytetrafluoroethylene copolymer film-carbon paper/graphite felt electrode-graphite plate flow channel-copper current collector, and the liquid is driven by a peristaltic pump to charge and discharge.
The battery is subjected to charge and discharge performance test, and is charged by adopting the current of 100mA at the current of 20mA-2、30mA.cm-2、40mA.cm-2、50mA.cm-2、70mA.cm-2The current magnitude of the battery is discharged, and the battery efficiency, the charge and discharge capacity and the capacity-voltage diagram under different current densities can be obtained.
As shown in fig. 6, the coulombic efficiency of the battery is kept above 99.9%, and the energy efficiency is reduced with the increase of the current density, but still kept above 52.19% at the high current density of 70ma.cm-2, which proves that the battery can work and output higher energy.
As shown in fig. 7, the charge-discharge capacity of the battery decreases as the current density increases due to the presence of internal resistance.
Fig. 8 shows a charge/discharge capacity-voltage curve of the battery at different current densities, which shows that the battery can work normally and stably at different current densities and has higher coulombic efficiency.
Example 5
Taking 1mol L-1KCl solution 20mL, weighing 2.5mmol alpha-CD and 0.8mmol TEMPO mixed solution in a round bottom flask, and vigorously stirring at room temperature for more than 24h to find the solution turns turbid, thereby proving that the inclusion compound is formed. Freeze drying to obtain
And (4) inclusion compound solid.
The procedure for preparing a battery by using the inclusion compound was the same as in example 3.
Example 6
Taking 1mol L-1KCl solution 20mL, weighing a mixed solution of 2.0mmol of beta-CD and 0.6mmol of TEMPO in a round-bottom flask, and vigorously stirring at room temperature for more than 24h to find that the solution becomes turbid, thereby proving that an inclusion compound is formed. Freeze drying to obtain
And (4) inclusion compound solid.
The procedure for preparing a battery by using the inclusion compound was the same as in example 3.
Example 7
Taking 1mol L-1KCl solution 20mL, weighing and preparing a mixed solution of 1.5mmol of beta-CD and 0.5mmol of TEMPO in a round-bottom flask, and vigorously stirring at room temperature for more than 24 hours to find that the solution becomes turbid, thereby proving that an inclusion compound is formed. Freeze drying to obtain
And (4) inclusion compound solid.
The procedure for preparing a battery by using the inclusion compound was the same as in example 3.
Example 8
Taking 1mol L-1KCl solution 20mL, weighing a mixed solution of 1.2mmol HP-beta-CD and 0.3mmol TEMPO in a round-bottomed flask, and vigorously stirring at room temperature for more than 24 hours to find that the solution becomes turbid, thereby proving that an inclusion compound is formed. Freeze drying to obtain
And (4) inclusion compound solid.
The procedure for preparing a battery by using the inclusion compound was the same as in example 3.
Example 9
Taking 1mol L-1KCl solution 20mL, a mixed solution of 1mmol of beta-CD and 0.1mmol of 4-OBn-TEMPO is weighed in a round-bottom flask, and stirred vigorously at room temperature for more than 24 hours, and the solution turns turbid, thereby proving that an inclusion compound is formed. Freeze drying to obtain
And (4) inclusion compound solid.
The procedure for preparing a battery by using the inclusion compound was the same as in example 3.
Example 10
Taking 1mol L-1KCl solution 20mL, a mixed solution of 2.8mmol of beta-CD and 0.7mmol of 4-OMe-TEMPO was weighed in a round-bottomed flask and allowed to stand at room temperatureAfter stirring vigorously for more than 24h, the solution was found to be cloudy, demonstrating the formation of inclusion compounds. Freeze drying to obtain
And (4) inclusion compound solid.
The procedure for preparing a battery by using the inclusion compound was the same as in example 3.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A piperidine nitroxide radical/zinc composite redox flow battery is characterized by comprising a positive electrode and a negative electrode; the positive electrode is a subject-guest inclusion compound, the subject-guest inclusion compound is a substance formed by bonding a host substance and a guest substance, the host substance is TEMPO or a TEMPO derivative, and the guest substance is a cyclodextrin substance or a cyclodextrin substance derivative; the TEMPO has a structural formula as follows:
the TEMPO derivative has a structural formula:
r is-OCH3Or OC7H7。
2. The battery of claim 1, wherein the solubility of the inclusion compound of host and guest in electrolyte is 0.01-10 mol/L.
3. The piperidine nitroxide/zinc composite redox flow battery of claim 2, wherein the electrolyte is one or more of an acid solution, an alkali solution, or an aqueous solution.
4. The piperidine nitroxide/zinc composite redox flow battery of claim 1, wherein the cyclodextrin species comprises α -CD, β -CD and γ -CD; the cyclodextrin derivative is HP-beta-CD.
5. The preparation method of the piperidine nitroxide free radical/zinc composite redox flow battery is characterized in that Zn is used as a negative electrode, a host-guest inclusion compound is used as a positive electrode, the guest substance is TEMPO or TEMP derivative, and the host substance is cyclodextrin substance or cyclodextrin derivative; sequentially assembling the battery according to the sequence of a copper current collector, a graphite plate flow channel, a carbon paper/graphite felt electrode, a perfluorinated sulfonic acid-polytetrafluoroethylene copolymer film, an electrode, a graphite plate flow channel and a copper current collector;
the preparation method of the host-guest inclusion compound comprises the following steps: mixing a host substance and a guest substance in a KCl solution, stirring or ultrasonically treating, confirming to form a host-guest inclusion compound when the solution becomes turbid, and cooling and drying the host-guest inclusion compound to obtain a final host-guest inclusion compound; the guest substance is TEMPO or a TEMPO derivative, and the host substance is a cyclodextrin substance or a cyclodextrin derivative.
6. The preparation method of the piperidine nitroxide radical/zinc composite redox flow battery according to claim 5, wherein the molar ratio of the host substance to the guest substance is (0.1-1): (1-3).
7. The preparation method of the piperidine nitroxide radical/zinc composite redox flow battery according to claim 5, wherein the stirring time is longer than 24h, and the ultrasonic time is longer than 40 min.
8. The method for preparing the piperidine nitroxide radical/zinc composite redox flow battery according to claim 5, wherein the electrode is graphite felt, carbon paper or metal electrode; the metal electrode is one or more of a combination of a gold electrode, a platinum electrode and a silver electrode.
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