CN114497539A - 基于亚铁氰化铜正极和吩嗪类有机物负极的水系可充电电池 - Google Patents
基于亚铁氰化铜正极和吩嗪类有机物负极的水系可充电电池 Download PDFInfo
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- CN114497539A CN114497539A CN202210035452.8A CN202210035452A CN114497539A CN 114497539 A CN114497539 A CN 114497539A CN 202210035452 A CN202210035452 A CN 202210035452A CN 114497539 A CN114497539 A CN 114497539A
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- copper ferrocyanide
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- 239000010949 copper Substances 0.000 title claims abstract description 48
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 title claims abstract description 9
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 title claims abstract description 6
- 239000005416 organic matter Substances 0.000 title claims abstract description 6
- -1 phenazine compound Chemical class 0.000 claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 6
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 6
- 239000003014 ion exchange membrane Substances 0.000 claims abstract 2
- 150000003839 salts Chemical class 0.000 claims abstract 2
- 239000007773 negative electrode material Substances 0.000 claims description 19
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 239000001103 potassium chloride Substances 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 150000002988 phenazines Chemical class 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims 2
- VJTZHXQAZLGBHV-UHFFFAOYSA-N 3-n-phenylbenzene-1,3-diamine Chemical compound NC1=CC=CC(NC=2C=CC=CC=2)=C1 VJTZHXQAZLGBHV-UHFFFAOYSA-N 0.000 claims 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical group [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims 1
- 125000003368 amide group Chemical group 0.000 claims 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- 235000011164 potassium chloride Nutrition 0.000 claims 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims 1
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 claims 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 claims 1
- 150000001768 cations Chemical class 0.000 abstract description 10
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 230000005611 electricity Effects 0.000 abstract description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 239000002002 slurry Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000003575 carbonaceous material Substances 0.000 description 10
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- 238000000576 coating method Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- BVQAWSJMUYMNQN-UHFFFAOYSA-N dipyridophenazine Chemical compound C1=CC=C2C3=NC4=CC=CC=C4N=C3C3=CC=CN=C3C2=N1 BVQAWSJMUYMNQN-UHFFFAOYSA-N 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 229920000554 ionomer Polymers 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- UVPLITJCYDVORW-UHFFFAOYSA-N phenazine-2,3-diol Chemical compound C1=CC=C2N=C(C=C(C(O)=C3)O)C3=NC2=C1 UVPLITJCYDVORW-UHFFFAOYSA-N 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- FGTANLQTJUKAOO-UHFFFAOYSA-N Oc1cc2nc3c(Br)ccc(Br)c3nc2cc1O Chemical compound Oc1cc2nc3c(Br)ccc(Br)c3nc2cc1O FGTANLQTJUKAOO-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007086 side 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
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- MJEPCYMIBBLUCJ-UHFFFAOYSA-K sodium titanium(4+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Na+] MJEPCYMIBBLUCJ-UHFFFAOYSA-K 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910019670 (NH4)H2PO4 Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- 229910013578 LiCo0.33Ni0.33Mn0.33O2 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010951 LiH2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
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- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
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- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229960003943 hypromellose Drugs 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 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
- 238000002360 preparation method Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
- Y02E60/10—Energy storage using batteries
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Abstract
本发明属于新能源领域,具体涉及一种基于亚铁氰化铜正极和吩嗪类有机物负极的水系可充电电池。正极采用具有金属有机框架结构的亚铁氰化铜,负极为能够可逆储存阳离子的电活性共轭吩嗪类化合物,支持电解质溶液为具有离子导电性的可溶性盐的水溶液,使用多孔膜或离子交换膜隔开正负极,其充放电过程涉及两种或两种以上阳离子在两极间的可逆转移。该电池体系具有较高的放电电压平台,高比容量、长寿命和绿色环保等优点,可为可再生能源的大规模储电提供一种成本低廉、安全可靠的电化学储能方案。
Description
技术领域
本发明属于新能源领域,具体涉及一种基于亚铁氰化铜正极和吩嗪类有机物负极的水系可充电电池。
背景技术
水系可充电电池由于其高离子电导率、内在安全性和水系电解质的成本优势而受到广泛关注[Nat.Energy 2019,4,495;Chem 2020,6,2442;J.Mater.Chem.A 2020,8,26013;CN 105047933A]。
然而,铅酸电池和镍氢电池等商业化水系可充电电池虽然具有很高的安全性和可靠性,但普遍存在能量密度偏低、循环寿命短和自放电等问题[Nano Res.2020,13,676]。因而迫切需要开发高性能和耐久性的新型水系可充电电池体系。
水系可充电电池的负极材料通常是具有高比容量的金属(如锌和铅)或含金属离子的无机插层化合物。然而,锌负极通常会发生溶解、枝晶生长和寄生副反应,导致循环寿命不高[J.Power Sources 2008,184,610],而无机插层化合物无论是作为正极材料还是负极材料,都需要选择合适的金属离子作为穿梭离子,以避免副反应的发生[Chem.Rev.2014,114,11503],而且通常可逆比容量较低。
有机电极材料完全由地球上丰富的元素(比如碳、氢、氧、氮和硫)组成,通常可经由化学反应大规模合成。不仅如此,通过分子结构的理性设计,可以获得高理论比容量和电化学性质或物化性质可调的有机电极材料[Chem.Soc.Rev.2016,45,6345]。大量包含一种或多种不同类型氧化还原活性单元的有机化合物或聚合物(如醌类[Sci.Adv.2018,4,1761]、嗪类[ACS Appl.Energy Mater.2018,1,7199]、酰亚胺类[J.Power Sources 2014,249,367]和硝基自由基[Green Chem.2010,12,1573]等)被开发作为水系可充电电池的电极材料。然而,多数工作中有机电极材料的理论比容量有限,且通常仅使用单一的金属离子作为插层离子,导致工作电压和可达比容量较低,循环稳定性较差。
专利CN1328818C公开了一种混合型水系可充电电池,正极材料为富锂化合物(LiCoO2、LiMn2O4、LiCo0.33Ni0.33Mn0.33O2等),负极材料为碳基材料,该电池体系不仅正负极材料成本较高,而且碳基负极的比容量较低。专利CN108075131B则使用磷酸钛钠化合物代替碳基材料作为负极材料,正极使用NayNixMn1-xO2结构的富钠层状化合物,其电极材料比容量低于100mAh/g,循环性能不佳。
发明内容
本发明的目的在于克服现有使用无机负极材料的水系可充电电池比容量低,循环性能差的问题,提供一种由亚铁氰化铜正极材料和吩嗪类有机物负极材料组成的高比容量的水系可充电电池体系。
该水系可充电电池由正极部分、负极部分、具有离子导电性的水系支持电解质溶液及隔膜组成,所述正极部分包括质量百分比为50~85%的正极活性材料,所述正极活性材料的结构通式为MxCuyFe(CN)6(0<x≤2;1≤y<2)。
具有金属有机框架结构的亚铁氰化铜由共沉淀法制备得到。
本发明采用可脱嵌各种一价阳离子、低成本的金属有机框架化合物亚铁氰化铜MxCuyFe(CN)6作为正极活性材料。充电过程中,一价阳离子(Li+、Na+、K+、NH4 +、H+或由其构成的混合离子)从正极材料脱出至电解质溶液,同时有机负极材料发生还原反应,结合电解质溶液中的一价阳离子,储存电子。放电过程中,从正极材料脱出的一价阳离子又嵌入到正极,同时负极则发生氧化反应,与负极有机物结合的一价阳离子脱出到电解液中,释放电子。该体系具有较高的放电电压平台,高能量密度、长寿命和绿色环保等优点,可为可再生能源的大规模储电提供一种成本低廉、安全可靠的电化学储能方案。
较佳地,所述正极部分还包括质量百分比为10~40%的导电性碳材料和质量百分比为5~10%的粘结剂。
所述负极部分包括质量百分比为50~85%的负极活性材料,所述负极活性材料为具有平面共轭π环结构的吩嗪衍生物,其结构式如下:
吩嗪衍生物具有快速、可逆的多电子氧化还原反应动力学,化学结构稳定,其水溶液中的标准电位接近标准氢电极的电位,适合用于水系电池的负极。
较佳地,负极活性材料为二吡啶吩嗪(dipyridophenazine)、四吡啶吩嗪(tetrapyridophenazine)、2,3-二羟基吩嗪(2,3-dihydroxyphenazine)、2,3-二羟基-6,9-二溴吩嗪(2,3-dihydroxy-6,9-dibromophenylzine)。
较佳地,所述负极部分还包括质量百分比为10~40%的导电性碳材料和质量百分比为5~10%的粘结剂。
较佳地,所述导电性碳材料为乙炔黑、科琴黑、碳纳米管、还原氧化石墨烯、VulcanXC72碳黑、介孔碳微球、中间相炭微球中的至少一种,所述粘结剂为聚四氟乙烯、聚偏氟乙烯、全氟磺酸离聚物、聚乙烯醇、羟丙甲纤维素中的一种。
较佳地,所述水系电解质溶液为含一种或多种一价阳离子的水溶液,所述水系电解质溶液中支持电解质为K2SO4、Na2SO4、Li2SO4、(NH4)2SO4、H2SO4、KCl、NaCl、LiCl、NH4Cl、HCl、KNO3、NaNO3、LiNO3、NH4NO3、HNO3、KClO4、NaClO4、LiClO4、NH4ClO4、HClO4 KH2PO4、NaH2PO4、LiH2PO4、(NH4)H2PO4、H3PO4中的一种或几种。
较佳地,所述水系电解质溶液中的一价阳离子的总浓度为0.5~8mol/L,pH值0.5~8。
较佳地,所述的隔膜为多孔膜或阳离子交换膜,允许水合一价阳离子通过。多孔膜的实例是聚丙烯隔膜Celgard 2400和Whatman玻纤膜GF/D。阳离子交换膜实例是全氟磺酸膜(即Nafion膜)。
有益效果:
本发明提供的水系可充电电池所用的负极材料为低成本、绿色环保、资源可再生的吩嗪衍生物,替代了水系电池常用的负极碳基材料或磷酸钛钠化合物;所用的正极材料为低成本的金属有机框架化合物亚铁氰化铜,替代了水系电池常用的正极富锂化合物。吩嗪衍生物不仅具有结构可设计性、可逆的多电子氧化还原动力学、化学结构稳,而且表现出比传统碳基材料或磷酸钛钠化合物更高的比容量。而亚铁氰化铜能够可逆地嵌入和脱出一价阳离子,具有比传统富锂化合物更佳的倍率性能。
附图说明:
图1是实施例1的亚铁氰化铜的扫描电镜(SEM)图。
图2是实施例1的亚铁氰化铜的透射电镜(TEM)图。
图3是实施例1的亚铁氰化铜的红外光谱图。
图4是实施例1的亚铁氰化铜的X射线光电子能谱(XPS)图。
图5(a)是实施例1的亚铁氰化铜分别在1mol/LKCl和1mol/LNaCl溶液中的循环伏安图;(b)是实施例1的亚铁氰化铜在1mol/LKCl溶液中的100圈循环伏安比较图。
图6是实施例1的亚铁氰化铜电极在1mol/L KCl+10-5mol/L HCl混合水溶液中的充放电曲线图,电流密度2A/g。
图7是实施例1的二吡啶吩嗪在1mol/L KCl+10-5mol/L HCl混合水溶液中的循环伏安(CV)图。
图8是实施例1的基于亚铁氰化铜正极和二吡啶吩嗪负极的水系可充电电池结构示意图。
图9是实施例1的水系可充电电池的充放电曲线图,电流密度1A/g。
图10是实施例1的水系可充电电池的循环寿命图,电流密度2A/g。
具体实施方式
实施例1
室温下配制50mL 25mM K4Fe(CN)6溶液(含质量百分数为1%的盐酸),配制50mL50mM CuCl2溶液(含质量百分数为1%的盐酸)。通过蠕动泵以10mL/min的流速将上述K4Fe(CN)6溶液和CuCl2溶液匀速滴加至剧烈搅拌的质量百分数为1%的盐酸溶液(20mL)中,接着升温至60℃,搅拌反应3小时。随后,反应液在室温下陈化260小时。高速离心分离产物,用去离子水和乙醇多次洗涤。将收集的固体在60℃下真空干燥12小时,得到亚铁氰化铜材料。
图1和图2分别为亚铁氰化铜材料的扫描电镜和透射电镜图。
图3是亚铁氰化铜材料的红外光谱图。2109cm-1处的红外吸收来源于[Fe(CN)6]配体中C-N的拉伸振动。
图4是亚铁氰化铜材料的X射线光电子能谱(XPS)图。亚铁氰化铜材料中存在C、N、Cu和Fe等元素。电感耦合等离子体原子发射光谱(ICP-AES)分析得到亚铁氰化铜材料的化学式为K0.15Cu1.82Fe(CN)6。
图5a是亚铁氰化铜分别在1mol/L KCl和1mol/L NaCl溶液中的循环伏安图。亚铁氰化铜在1mol/L KCl和1mol/L NaCl溶液中的标准电位分别为约1.05和1.1V。图5b是亚铁氰化铜在1mol/L KCl溶液中的100圈循环伏安曲线的比较图,揭示了亚铁氰化铜具有良好的电化学稳定性。
图6是亚铁氰化铜电极在1mol/L KCl+10-5mol/L HCl混合水溶液中的充放电曲线图。亚铁氰化铜材料在2A/g的电流密度下的比容量为76mAh/g。
图7是二吡啶吩嗪在1mol/L KCl溶液(含10-5mol/L的HCl)中的循环伏安图。二吡啶吩嗪的标准电位约-0.24V。
以亚铁氰化铜为正极活性物质。正极电极片的制备如下。按照活性物质(亚铁氰化铜):导电性碳材料(科琴黑,Ketjen Black):粘结剂(聚四氟乙烯,PTFE)=70:20:10的比例均匀混合,加入至异丙醇的水溶液,超声分散形成均匀的浆液。将浆液涂敷在多孔碳毡上,构成正极电极片。
以二吡啶吩嗪为负极活性物质。按照活性物质(二吡啶吩嗪):导电性碳材料(科琴黑,Ketjen Black):粘结剂(聚四氟乙烯,PTFE)=60:30:10的比例均匀混合,加入至异丙醇的水溶液,超声分散形成均匀的浆液。将浆液涂敷在碳纸上,构成负极电极片。使用Celgard2400隔膜,1mol/L的KCl水溶液(含10-5mol/L的HCl)作为电解液,组装成全电池。其结构示意图见图8。
图9为本实施例制备的水系可充电电池的充放电曲线,电流密度为1A/g。在1A/g下,放电比容量高达154mAh/g(基于负极活性物质)。即使电流密度增加到10A/g,电池的放电比容量仍可保持在约107mAh/g。在2A/g的电流密度下,经过1000次循环,放电容量保持率为91.5%,能量效率为70.5%(图10)。
对比例1:正极活性物质为商业化富锂化合物磷酸铁锂。磷酸铁锂正极片的制备过程同实施例1。以实施例1同样的电池组建方式得到水系可充电电池,负极活性物质为二吡啶吩嗪。在电流密度1A/g下,放电比容量为122mAh/g,在2A/g的电流密度下,经过1000次循环,放电容量保持率为76.8%。
对比例2:亚铁氰化铟的合成步骤参照文献(Chem.Commun.,2021,57,4307)。亚铁氰化铟正极片的制备过程同实施例1。以实施例1同样的电池组建方式组装水系可充电电池,负极活性物质为二吡啶吩嗪。电流密度1A/g下,放电比容量为131mAh/g,在2A/g的电流密度下,经过1000次循环,放电容量保持率为85.7%,能量效率为68.6%。
对比例3:正极活性物质为商业化磷酸钛钠。磷酸钛钠负极片的制备过程同实施例1。以实施例1同样的电池组建方式得到水系可充电电池,正极活性物质为亚铁氰化铜。在电流密度1A/g下,放电比容量为118mAh/g,在2A/g的电流密度下,经过1000次循环,放电容量保持率为80.1%。
实施例2:将实施例1中的K4(CN)6换为Na4(CN)6。其余与实施例1相同。通过ICP-AES分析得到亚铁氰化铜的化学式为K0.38Cu1.78Fe(CN)6。亚铁氰化铜在2A/g下的放电比容量为72.6mAh/g。
实施例3:以实施例1的亚铁氰化铜为正极材料制备正极电极片,按照亚铁氰化铜:科琴黑:聚四氟乙烯=70:20:10的比例均匀混合,加入至异丙醇的水溶液,超声分散形成均匀的浆液。将浆液涂敷在多孔碳毡上,构成正极电极片。
以四吡啶吩嗪为负极活性物质制备负极电极片,按照活性物质(四吡啶吩嗪):导电性碳材料(科琴黑,Ketjen Black):粘结剂(全氟磺酸离聚物,Nafion)=50:40:10的比例均匀混合,加入至异丙醇的水溶液,超声分散形成均匀的浆液。将浆液涂敷在碳纸上,构成负极电极片。玻纤膜GF/D为隔膜,1mol/L KCl+0.5mol/L NH4Cl混合溶液作为电解液,组装成全电池。在电流密度1A/g下,电池的放电比容量为约112mAh/g。
实施例4:以实施例1的亚铁氰化铜为正极材料制备正极电极片,按照亚铁氰化铜:科琴黑:聚四氟乙烯=70:20:10的比例均匀混合,加入至异丙醇的水溶液,超声分散形成均匀的浆液。将浆液涂敷在多孔碳毡上,构成正极电极片。以2,3-二羟基吩嗪为负极活性物质,按照2,3-二羟基吩嗪:科琴黑:全氟磺酸离聚物=60:30:10的比例均匀混合,加入至异丙醇的水溶液,超声分散形成均匀的浆液。将浆液涂敷在碳纸上,制备负极电极片。Nafion112膜(50微米)为隔膜,1mol/L Na2SO4+0.2mol/L H2SO4混合溶液作为电解液,组装成全电池。在电流密度0.3A/g和1A/g下,放电比容量分别为108mAh/g和97mAh/g。
实施例5:以亚铁氰化铜为正极活性物质,按照亚铁氰化铜:科琴黑:聚四氟乙烯=70:20:10的比例均匀混合,加入至异丙醇的水溶液,超声分散形成均匀的浆液。将浆液涂敷在多孔碳毡上,制备正极电极片。以2,3-二羟基-6,9-二溴吩嗪为负极活性物质,按照2,3-二羟基-6,9-二溴吩嗪:科琴黑:全氟磺酸离聚物=60:30:10的比例均匀混合,加入至异丙醇的水溶液,超声分散形成均匀的浆液。将浆液涂敷在碳纸上,制备负极电极片。Nafion112膜(50微米)为隔膜,1mol/L KNO3+0.1mol/L HNO3混合溶液作为电解液,组装成全电池。在电流密度1A/g下,放电比容量为129mAh/g。
Claims (6)
1.一种基于亚铁氰化铜正极和吩嗪类有机物负极的水系可充电电池,该电池由正极材料、负极材料、支持电解质和隔膜组成,其特征在于:所述正极材料为具有金属有机框架结构的亚铁氰化铜;所述负极材料为具有平面共轭π环结构的吩嗪衍生物;所述支持电解质为水溶性的盐类。
2.根据权利要求1所述的水系可充电电池,其特征在于:所述亚铁氰化铜的化学通式记为MxCuyFe(CN)6,式中,M=Li+、Na+、K+、NH4 +和H+中的一种或多种,0<x≤2,1≤y<2。
3.根据权利要求1所述的水系可充电电池,其特征在于:所述具有金属有机框架结构的亚铁氰化铜由共沉淀法制备得到。
5.根据权利要求1所述的水系可充电电池,其特征在于:水溶性的支持电解质为氯化钠、氯化钾、氯化锂、有机氯化季铵盐或者它们的混合物;所述的隔膜为多孔膜或离子交换膜。
6.根据权利要求1所述的水系可充电电池,其特征在于:有机氯化季铵盐为四甲基氯化铵、四乙基氯化铵、四丙基氯化铵、四丁基氯化铵、甲基三乙基氯化铵、烯丙基三甲基氯化铵、(3-羧丙基)三甲基氯化铵、苄基三甲基氯化铵。
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