CN110350142A - The sodium electrode of integrated Porous Polypyrrole load and the preparation method of sulfur electrode - Google Patents
The sodium electrode of integrated Porous Polypyrrole load and the preparation method of sulfur electrode Download PDFInfo
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- CN110350142A CN110350142A CN201910580605.5A CN201910580605A CN110350142A CN 110350142 A CN110350142 A CN 110350142A CN 201910580605 A CN201910580605 A CN 201910580605A CN 110350142 A CN110350142 A CN 110350142A
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- sodium
- pyrroles
- polypyrrole
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- 239000011734 sodium Substances 0.000 title claims abstract description 100
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 87
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 87
- 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 title claims abstract description 86
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000011593 sulfur Substances 0.000 title claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 37
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000725 suspension Substances 0.000 claims abstract description 28
- 239000005864 Sulphur Substances 0.000 claims abstract description 24
- 239000012876 carrier material Substances 0.000 claims abstract description 23
- 239000006210 lotion Substances 0.000 claims abstract description 21
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 20
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 claims abstract description 14
- 239000011888 foil Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 230000010354 integration Effects 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 239000007772 electrode material Substances 0.000 claims abstract description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 239000012065 filter cake Substances 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 150000004862 dioxolanes Chemical class 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000008901 benefit Effects 0.000 claims description 3
- 125000001165 hydrophobic group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 2
- 235000015424 sodium Nutrition 0.000 abstract description 79
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 29
- 239000005077 polysulfide Substances 0.000 description 27
- 229920001021 polysulfide Polymers 0.000 description 26
- 150000008117 polysulfides Polymers 0.000 description 26
- 229910052799 carbon Inorganic materials 0.000 description 14
- 229910001415 sodium ion Inorganic materials 0.000 description 13
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 210000001787 dendrite Anatomy 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- -1 ester sodium salt Chemical class 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 229910006587 β-Al2O3 Inorganic materials 0.000 description 3
- 206010011224 Cough Diseases 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910020275 Na2Sx Inorganic materials 0.000 description 1
- 229910017435 S2 In Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- VMLAJPONBZSGBD-UHFFFAOYSA-L calcium;hydrogen carbonate;hydroxide Chemical compound [OH-].[Ca+2].OC([O-])=O VMLAJPONBZSGBD-UHFFFAOYSA-L 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003981 vehicle Substances 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to sode cell technical fields, it is desirable to provide a kind of preparation method for the sodium electrode and sulfur electrode that integration Porous Polypyrrole loads.It include: to remove ionized water, pyrroles and Na salt anionic surfactant, ultrasonic vibration disperses to obtain pyrroles's lotion；Ionized water, nanometer calcium carbonate template, initiator sodium peroxydisulfate and Na salt anionic surfactant are removed again, is uniformly mixed so as to obtain suspension, polymerize to obtain integrated Porous Polypyrrole carrier material by pyrroles；The metal sodium foil of homalographic is pressed with it in glove box, the heating at 100 DEG C is until sodium foil melting obtains the sodium electrode for low temperature sodium-sulphur battery into carrier material.The present invention, which obtains Porous Polypyrrole, has the characteristics that large specific surface area and macropore are held, and the pyrroles's nitrogen on polypyrrole, which becomes metallic sodium nucleating center, can support more metallic sodiums, is suitble to preparation high-performance sulfur electrode material.Porous Polypyrrole carries sodium and load sulphur is simple for process, is conducive to large-scale production, reduces cost, has the market competitiveness.
Description
Technical field
The present invention relates to sode cell technical field, in particular to the sodium electrode and sulphur electricity of integrated Porous Polypyrrole load
The preparation method of pole.
Background technique
Sodium-sulphur battery (NaS) is used as a kind of mechanism of new electrochemical power sources, and since the advent of the world there has been to develop on a large scale very much.Sodium-sulphur battery body
Product is small, capacity is big, the service life is long, high-efficient, is widely used in peak load shifting, emergency power supply, wind-power electricity generation etc. in power energy storage
In terms of energy storage.Under normal conditions, sodium-sulphur battery is made of anode, cathode, electrolyte, diaphragm and shell.
Traditional sodium-sulphur battery is made of melt electrode and solid electrolyte, and the active material of cathode is molten metal sodium,
Positive active material is liquid sulfur and sodium polysulfide fused salt, and operating temperature is 300~350 DEG C.Presently used electrolyte is
β-Al2O3, only temperature is at 300 degrees Celsius or more, β-Al2O3Just there is good ionic conductivity.When battery discharge, electricity
Son is transported to sulphur cathode (anode) by sodium anode (cathode) by external circuit, and sodium ion then passes through solid electrolyte β-Al2O3With
S2-In conjunction with sodium polysulfide product is formed, in charging, electrode reaction is opposite with electric discharge.Sodium directly reacts acutely with sulphur, therefore two
It must be separated with solid electrolyte between kind reactant, while solid electrolyte must be sodium ion conductor again.According to unit matter
The elemental sulfur of amount becomes S completely2-The electricity that can be provided can show that the theoretical discharge specific discharge capacity of sulphur is 1675mAh g-1。
The chemical equation of sodium-sulphur battery is as follows: 2Na+xS=Na2Sx.It is 100%~78% in the initial stage sulfur content of electric discharge, just
Pole by liquid sulfur and liquid Na2S3.2Non- solution phase altogether is formed, the electromotive force of battery is about 2.076V；When being discharged to Na2S3Out
Now, the electromotive force of battery is down to 1.78V；When being discharged to Na2S2.7When appearance, corresponding electromotive force is down to 1.74V, until liquid
Mutually disappear.
Sodium-sulphur battery mainly has following feature: 1, theoretical energy density is up to 760Wh kg-1.Practical specific energy is high,
The volume and weight that energy-storage system can effectively be lowered, is suitable for the application of large capacity, powerful device；2, energy conversion efficiency
Height, wherein DC terminal is greater than 90%, and exchange end is greater than 75%；3, without electrochemistry side reaction, no self discharge, long service life can
Up to 15 years or more；4, the running temperature of sodium-sulphur battery is constant at 300~350 DEG C, therefore its use condition is not by external environment
The limitation of temperature, and the temperature stability of system is good；5, with high power characteristic, through high current and deep discharge without damaging
Battery；Instantaneous velocity with nanosecond within system number millisecond, is suitably applied all kinds of spare and emergency power station；6, former material
To expect resourceful, price is low, and it is pollution-free, it is suitble to large-scale promotion application.However there are problems for sodium-sulphur battery: (1) operating temperature
It is high；(2) it is unsuitable for discontinuous operation, the continuous switching of high/low temperature easily causes the leakage of pile, fatigue of materials damage；(3) opposite liquid
The problems such as galvanic battery scale cannot be too big.
Conventional high-temperature sodium-sulphur battery is with the obvious advantage as energy-storage battery, and is used as the electricity of electric car or other movement utensils
When source, without superiority, it is not fully solved the security reliability problem of sodium-sulphur battery, therefore the high temperature sodium-sulphur battery is not suitable for
Application in terms of vehicle used energy.To solve the problems, such as that the high temperature sodium-sulphur battery exists, it is crucial for reducing sodium-sulphur battery operating temperature.Low temperature
The specific power and specific energy of sodium-sulphur battery are high, raw material cost is low, prominent without self discharge, safety etc. advantage, so that low temperature
Sodium-sulphur battery becomes at present the power battery of most application prospect.
Low temperature sodium-sulphur battery uses liquid electrolyte, is easy to penetrate in charge and discharge process generation sodium dendrite using conventional membrane
Diaphragm is easy when use to cause short circuit, causes battery to use dangerous.Secondly, can be generated in the sodium-sulphur battery course of work
It is largely dissolved in the polysulfide ion of electrolyte, because its molecule is relatively small, most of polysulfide ion often can be in electrolyte
In with the effect of concentration gradient and electric field force it is mobile.It is short with the generation of sodium metal reaction when long-chain polysulfide ion is moved to cathode
Chain polysulfide ion, short chain polysulfide ion are moved to anode and sulphur simple substance reaction weight again under the action of concentration gradient power and electric field force
Newly-generated long-chain polysulfide ion is formed so-called " shuttle effect ".These polysulfide ions do not stop to move in the electrolytic solution, are reacting
In consume big energy so that the actual efficiency of cell reaction reduces.With the progress of discharge and recharge reaction, polysulfide ion is worn
Shuttle and with metallic sodium cathode formed vulcanized sodium and deposit, constantly reduce the effective active material sulphur of battery content, battery capacity hair
Raw circulation decline.
In order to avoid the generation of cathode sodium dendrite and the poly- vulcanized sodium of anode shuttle, the present invention proposes integrated Porous Polypyrrole
Material carries out carrying sodium and carrying sulphur respectively obtaining sodium electrode and sulfur electrode, generates sodium dendrite and the poly- vulcanized sodium of anode to avoid cathode
It is migrated to cathode, obtains high performance low temperature sodium-sulphur battery.
Use carbon coating sulphur as positive electrode in the lithium-sulfur cell similar with low temperature sodium-sulphur battery, its object is to avoid
Polysulfide ion moves to cathode, inhibits the shuttle of poly- lithium sulfide.But lithium ion is compared, sodium ion radius is bigger, polysulfide ion
Active force between sodium ion is weaker, it is easier to be dissolved in electrolyte, it is easier to polysulfide ion shuttle occur.Due to lithium ion
Radius is small, and the resistance that carbon-coating spacing conducts lithium is little, cause high resistance to larger-sized sodium ion-conductive to meeting.It passes
The carbon coating of system realizes lithium ion conduction but hinders polysulfide ion transmitting, if but carbon coating is simply applied to sodium sulphur electricity
Pond also counteracts the conduction of sodium ion although can also polysulfide ion be hindered to transmit simultaneously, to exacerbate the pole of sulfur electrode
Change, leads to reduced performance.Since the radius of sodium ion is close to sulphur atom radius, polysulfide ion is linear molecular structure again, tradition
Carbon material be difficult to hinder polysulfide ion transmitting but do not interfere sodium ion-conductive.Generally, the conduction pathway of sodium ion is increased
Radius can only promote the shuttle of polysulfide ion, it is difficult to improve the performance of sodium-sulphur battery.For this purpose, design sodium ion and polysulfide ion
Selective conducting path it is very necessary, however traditional carbon material cannot achieve this target.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of integrated Porous Polypyrrole
The sodium electrode of load and the preparation method of sulfur electrode.
In order to solve technical problem, solution of the invention is:
A kind of preparation method of the sodium electrode of integrated Porous Polypyrrole load is provided, comprising the following steps:
(1) 100mL deionized water is taken, 0.15~0.9g pyrroles and Na salt anionic surfactant 1g, ultrasound vibration is added
Dynamic dispersion obtains pyrroles's lotion after five minutes；50mL deionized water is taken again, and 0.5~3g nanometer calcium carbonate template, initiator mistake is added
Sodium sulphate 0.1~0.5g and Na salt anionic surfactant 1g, is uniformly mixed so as to obtain suspension；It, will under ice bath and stirring condition
Suspension is added dropwise in pyrroles's lotion, and the reaction was continued one hour after dripping；Then it is carried out with the filter paper of polyacrylate material
Filter paper is dissolved away with acetone after vacuum filtration, filter cake and filter paper are dry, obtains filter cake；Filter cake is washed into nano-sized carbon by dilute hydrochloric acid
Sour calcium template, is rinsed with deionized water, obtains the integrated Porous Polypyrrole carrier material of sheet after dry；
(2) the integrated Porous Polypyrrole carrier material that 150mg step (1) obtains is taken, by homalographic in glove box
Metal sodium foil is pressed with it, and the thickness of control metal sodium foil makes 1~10:1 of mass ratio of metallic sodium and carrier material；Then exist
Heating at 100 DEG C is until sodium foil melting obtains the sodium electrode for low temperature sodium-sulphur battery into carrier material.
The present invention provides a kind of preparation methods of the sulfur electrode of integrated Porous Polypyrrole load, comprising the following steps:
(1) 100mL deionized water is taken, 0.15~0.9g pyrroles and Na salt anionic surfactant 1g, ultrasound vibration is added
Dynamic dispersion obtains pyrroles's lotion after five minutes；50mL deionized water is taken again, and 0.5~3g nanometer calcium carbonate template, initiator mistake is added
Sodium sulphate 0.1~0.5g and Na salt anionic surfactant 1g, is uniformly mixed so as to obtain suspension；It, will under ice bath and stirring condition
Suspension is added dropwise in pyrroles's lotion, and the reaction was continued one hour after dripping；Then it is carried out with the filter paper of polyacrylate material
Filter paper is dissolved away with acetone after vacuum filtration, filter cake and filter paper are dry, obtains filter cake；Filter cake is washed into nano-sized carbon by dilute hydrochloric acid
Sour calcium template, is rinsed with deionized water, obtains the integrated Porous Polypyrrole carrier material of sheet after dry；
(2) 1:1 disperses elemental sulfur in DMSO in mass ratio, in ZrO2It obtains within ball milling 30 minutes in ball grinder suspended
Liquid；The integrated Porous Polypyrrole carrier material that 150mg step (1) obtains is taken, suspension is coated on polypyrrole carrier, control
The mass ratio of sulphur and carrier material is 1~10:1；After heating 1 hour at 90 DEG C, DMSO is removed in vacuum drying；Then nitrogen is moved to
It under atmosphere, is warming up to 155 DEG C and is kept for 2 hours, melt elemental sulfur completely and enter carrier material, obtain for low temperature sodium-sulphur battery
Sulfur electrode.
In the present invention, the hydrophobic group of Na salt anionic surfactant described in step (1) be chain alkyl, secondary alkyl or
Alkylaryl, hydrophilic group are carboxyl (RCOO), sulfonic group (R-SO3) or sulfate group (R-OSO3)；Correspondingly, anionic surface
Activating agent general formula is expressed as RCOONa, R-SO3Na or R-OSO3Na, R is chain alkyl, secondary alkyl or alkylaryl in formula.
In the present invention, in step (1), control supersonic frequency is 40kHz when carrying out ultrasonic vibration dispersion.
In the present invention, in step (1), control rate of addition is 10mL/ hours when suspension is added dropwise to pyrroles's lotion.
Invention further provides a kind of low temperature sodium-sulphur batteries, including diaphragm, anode, cathode and electrolyte；The sodium sulphur
Battery is sodium electrode to prepare as cathode, the sulfur electrode to prepare as anode, is separately positioned on diaphragm two
Side forms sandwich structure, and makes the electrode material side on anode and cathode towards diaphragm, and electrolyte is built in sandwich structure
In；
The electrolyte is with Na [CF3SO2)2N] it is solute, using dioxolanes and the mixture of ethylene glycol monomethyl ether as solvent；
The volume ratio of dioxolanes and ethylene glycol monomethyl ether is 1:1, contains a mole of solute in every liter of electrolyte.
Inventive principle description:
The present invention carries sodium using porous material, so that the electrochemical reaction of metallic sodium is confined to carry out in hole, it can be effective
Inhibit the growth of sodium dendrite.Meanwhile the porous material for using sodium ion selective to conduct carries out load sodium as carrier, can strengthen
Sodium ion-conductive effectively lowers the polarization of sodium cathode.Colourless oil liquid is presented under pure pyrrole monomer room temperature, is a kind of C, N five
Circle heterocyclic ring molecule.Polypyrrole is a kind of common conducting polymer, is heterocycle conjugated type conducting polymer, usually unformed black
Color solid is that a kind of air stability is good, be easy to electrochemical polymerization film forming conducting polymer, it is insoluble not melt, conductivity and
The polymerizing conditions such as the properties such as mechanical strength and electrolysis solution anion, solvent, pH value and temperature are closely related.Using pyrroles as monomer,
It is made through oxidation polymerization, oxidant is usually ferric trichloride, ammonium persulfate etc..Electric polypyrrole has conjugated chain oxidation, corresponds to
Anion doped structure, conductivity is up to 102~103S/cm, and tensile strength is up to 50~100MPa and good electrochemistry
Oxidationreduction invertibity.Electrical conduction mechanism are as follows: the conjugation knot that polypyrrole structure has carbon-carbon single bond and carbon-carbon double bond to be alternately arranged
Structure, double bond are made of sigma electrons and pi-electron, and sigma electrons, which are fixed, to be moved freely, and covalent bond is formed between carbon atom.
2 pi-electrons in conjugated double bond are not fixed on some carbon atom, they can from a carbon atom indexing to another
On carbon atom, that is, there is the tendency extended on entire strand.That is the overlapping of the pi-electron cloud of intramolecular produces entire molecule
Shared energy band, pi-electron are similar to the free electron in metallic conductor.In the presence of having electric field, the electronics for forming pi bond can edge
Strand it is mobile.In the polymer, it is mainly coupled to each other between pyrrole structure unit with α, big hydrophobic anion doping
Polypyrrole can save in air the several years and without significant change.Pyrroles's hydrogen on polypyrrole can become Na with Na ion exchange
The good conductor of ion.The polypyrrole especially prepared with macroanion type surfactant, it is real while synthesizing polypyrrole
The insertion of existing anion just forms the adsorption site of polysulfide ion using anion exchange, plays and polysulfide ion is inhibited to shuttle
Effect.
The present invention interferes the defect of sodium ion-conductive for traditional carbon coating, propose integrated Porous Polypyrrole material and
It carries sodium and carries cathode and anode preparation method that sulphur obtains.It is living by the way that Na salt anionic surfactant is added in pyrroles's polymerization process
Property agent, such as sodium soap surfactant (RCOONa), sulfonic acid sodium form surfactant (RSO3Na), sulfuric ester sodium salt surface is living
Property agent (ROSO3Na), in pyrroles's polymerization process, sodium ion is exchanged with pyrroles's hydrogen, forms the conducting networks of sodium ion.Realize sodium
Transmission of the ion on polypyrrole chain relies on the three-dimensional polypyrrole network structure of Porous Polypyrrole, strengthens sodium ion in porous material
Transmitting in material, sodium eliminates the sodium dendrite problems of sodium-sulphur battery in hole external sediment when inhibiting to charge.Anion RCOO-,
RSO3―、ROSO3, insertion formed polypyrrole, exchanged using polysulfide ion, just formed polysulfide ion adsorption site, make
It carries sulfur materials for anode to play the role of that polysulfide ion is inhibited to shuttle, to obtain high reliablity, safety, long-life Sulfur-Vapor of Lower Temperature sodium
Battery.
Preparation method explanation of the invention:
In step (1), hydrophilic nanometer calcium carbonate template is difficult to keep well directly contacting with lipophilic pyrroles.?
Na salt anionic surfactant is added in pyrroles-water mixed liquid body, ultrasonic emulsification obtains pyrroles's lotion, anion surface active
Agent molecule is arranged in emulsion droplets surface, while its hydrophilic radical is unanimously outwardly.Na is added in nanometer calcium carbonate-aqueous suspension body
Salt anionic surfactant, anionic surfactant molecules are arranged in cium carbonate nanoparticles surface, hydrophilic radical with
Chemisorption occurs for nano grain surface oxygen, and hydrophobic group is unanimously outwardly.When nanometer calcium carbonate-water containing initiator is suspended
Drop, which adds, to meet with pyrroles's emulsion droplets and is merged with the cium carbonate nanoparticles in pyrroles's lotion, having adsorbed surfactant, pyrrole
It coughs up nature and is coated on cium carbonate nanoparticles, pyrroles's polymerization occurs under the action of initiator, forms polypyrrole coated caco3
Particle, while intergranular polypyrrole interlinks to form aggregate.These aggregates are self-assembly of one during suction filtration
Body polypyrrole coated caco3 material, polypyrrole constitute continuous phase, and nano-calcium carbonate particles are as dispersed phase distribution in wherein.
In acid cleaning process, Decomposition of Calcium Carbonate generates the calcium chloride and gas CO for being dissolved in water2, hole, shape are left in polypyrrole matrix
Integralization Porous Polypyrrole carrier material.
The inner hole that melting enters Porous Polypyrrole occurs for the pressing object of heated porous polypyrrole and metallic sodium at 100 DEG C, sodium,
Obtain sodium electrode.The pyrroles's nitrogen of Porous Polypyrrole Dispersed precipitate plays the role of metallic sodium nucleating center, inducing metal sodium hole
Interior formation, the good macropore appearance of high-specific surface area has ensured high load sodium ability and reaction speed, to avoid the formation of sodium dendrite.
The integrated Porous Polypyrrole of the lower 155 DEG C of heating coating elemental sulfur of nitrogen atmosphere, elemental sulfur are melted completely into porous
The inner hole of polypyrrole, obtains sulfur electrode.The pyrroles's nitrogen of Porous Polypyrrole Dispersed precipitate and the interaction of sulphur enhance porous poly-
Pyrroles improves battery to effectively inhibit the shuttle phenomenon of polysulfide ion in sodium-sulphur battery to the adsorption capacity of polysulfide ion
Service life.
Compared with prior art, the beneficial effects of the present invention are:
The present invention, which obtains Porous Polypyrrole, has the characteristics that large specific surface area and macropore are held, and the pyrroles's nitrogen on polypyrrole becomes
Metallic sodium nucleating center can support more metallic sodiums, and polypyrrole hole wall assigns the ability for resisting the puncture of sodium dendrite, avoids
Sodium dendrite is grown to diaphragm, prevents battery short circuit.Equally, the pyrroles's nitrogen on polypyrrole has polysulfide ion very strong affine
Power, the pyrroles's nitrogen of Dispersed precipitate on the carbon wall of hole are conducive to adsorb polysulfide ion, polysulfide ion are inhibited to shuttle, and are suitble to prepare high property
It can sulfur electrode material.Porous Polypyrrole carries sodium and load sulphur is simple for process, is conducive to large-scale production sodium electrode and sulfur electrode, drop
Low cost has the market competitiveness.
Detailed description of the invention
Fig. 1 is the Porous Polypyrrole material (electromicroscopic photograph) prepared in embodiment 3.
Specific embodiment
Present invention is further described in detail with specific embodiment with reference to the accompanying drawing:
The following examples can make the professional technician of this profession that the present invention be more fully understood, but not with any side
The formula limitation present invention.
The Porous Polypyrrole that embodiment 1 is prepared using sodium soap as surfactant
Soap is the most common fatty acid salt anions surfactant, take 100mL deionized water be added 0.15g pyrroles and
Soap 1g, ultrasonic vibration (supersonic frequency 40kHz) dispersion obtains pyrroles's lotion after five minutes, then 50mL deionized water is taken to be added
0.5g nanometer calcium carbonate template, initiator sodium peroxydisulfate 0.1g and soap 1g obtain suspension, drip while stirring under ice bath
Add suspension in pyrroles's lotion, rate of addition is 10mL/ hours；It is filtered by vacuum, is passed through after reaction being added dropwise one hour
Dilute hydrochloric acid washes templating nanoparticles calcium carbonate, obtains the integrated Porous Polypyrrole carrier of sheet after rinsing drying with deionized water
Material.
The Porous Polypyrrole that embodiment 2 is prepared using petroleum sodium sulfonate as surfactant
Petroleum sodium sulfonate is that sulfonated, caustic soda neutralizes by natural oil fraction or chemical reaction gained high-carbon hydrocarbon by-product
The anionic surfactant arrived is the mixture of hydrocarbons sulfonated products.Take 100mL deionized water that 0.5g pyrroles and stone is added
Oily sodium sulfonate 1g, ultrasonic vibration (supersonic frequency 40kHz) dispersion obtains pyrroles's lotion after five minutes, then 50mL deionized water is taken to add
Enter 1g nanometer calcium carbonate template, initiator sodium peroxydisulfate 0.25g and petroleum sodium sulfonate 1g and obtains suspension, it is following in ice bath
It stirs side and suspension is added dropwise in pyrroles's lotion, rate of addition is 10mL/ hours；Vacuum pumping is carried out after being added dropwise reaction one hour
Filter, washes templating nanoparticles calcium carbonate by dilute hydrochloric acid, and the integration that sheet is obtained after dry with deionized water rinsing is porous poly-
Pyrroles's carrier material.
The Porous Polypyrrole that embodiment 3 is prepared using sodium alkyl sulfate as surfactant
Sulfuric ester salt form anionic surfactant mainly have fatty alcohol sulfate salt (also known as primary ester salt) and
Two class of secondary alkyl sulphate salt.Fatty alcohol sulphuric acid (ester) sodium is the earliest anionic surfactant occurred after soap, be by
C12~C14 the fatty alcohol and Sulfation and neutralization that coconut oil hydrogenolysis generates are made.
Take 100mL deionized water that 0.9g pyrroles and NaLS (C is added12H25OSO3Na) 1g, ultrasonic vibration (ultrasound
Frequency 40kHz) dispersion obtains pyrroles's lotion after five minutes, then takes 50mL deionized water that 3g nanometer calcium carbonate template, initiator is added
Sodium peroxydisulfate 0.5g and NaLS 1g obtain suspension, and suspension is added dropwise while stirring under ice bath in pyrroles's cream
Liquid, rate of addition are 10mL/ hours；It is filtered by vacuum after reaction being added dropwise one hour, template is washed by dilute hydrochloric acid
Nanometer calcium carbonate obtains the integrated Porous Polypyrrole carrier material of sheet, electromicroscopic photograph after rinsing drying with deionized water
As shown in Figure 1.
4 Porous Polypyrrole of embodiment carries sodium
Take 100mL deionized water that 0.5g pyrroles and neopelex 1g, ultrasonic vibration (supersonic frequency is added
40kHz) dispersion obtains pyrroles's lotion after five minutes, then takes 50mL deionized water that 1g nanometer calcium carbonate template, initiator over cure is added
Sour sodium 0.25g and neopelex 1g obtain suspension, and suspension is added dropwise while stirring under ice bath in pyrroles's cream
Liquid, rate of addition are 10mL/ hours；It is filtered by vacuum after reaction being added dropwise one hour, filter paper uses polyacrylate material
After the filter paper of matter, filter cake and filter paper are dry, filter paper is dissolved away with acetone, obtains filter cake.Filter cake is washed into template by dilute hydrochloric acid
Nanometer calcium carbonate obtains the integrated Porous Polypyrrole carrier material of sheet after rinsing drying with deionized water.
Above-mentioned 150mg integration Porous Polypyrrole is taken, by the metal sodium foil (150mg) of homalographic and one in glove box
The mass ratio of change Porous Polypyrrole pressing, metallic sodium and polypyrrole is 1:1, and heating enters one until sodium foil melts at 100 DEG C
Body Porous Polypyrrole.
The preparation of 5 sodium electrode of embodiment
Take 100mL deionized water that 0.5g pyrroles and lauryl sodium sulfate 1g, ultrasonic vibration (supersonic frequency 40kHz) is added
Dispersion obtains pyrroles's lotion after five minutes, then takes 50mL deionized water that 1g nanometer calcium carbonate template, initiator sodium peroxydisulfate is added
0.25g and lauryl sodium sulfate 1g obtain suspension, and suspension is added dropwise while stirring under ice bath in pyrroles's lotion, drop
Acceleration is 10mL/ hours；It is filtered by vacuum after reaction being added dropwise one hour, filter paper uses the filter of polyacrylate material
After paper, filter cake and filter paper are dry, filter paper is dissolved away with acetone, obtains filter cake.Filter cake is washed into templating nanoparticles carbon by dilute hydrochloric acid
Sour calcium obtains the integrated Porous Polypyrrole carrier material of sheet after rinsing drying with deionized water.
Above-mentioned 150mg integration Porous Polypyrrole is taken, by the metal sodium foil (750mg) of homalographic and one in glove box
The mass ratio of change Porous Polypyrrole pressing, metallic sodium and polypyrrole is 5:1, and heating enters one until sodium foil melts at 100 DEG C
Body Porous Polypyrrole obtains sodium electrode.
6 Porous Polypyrrole of embodiment carries sulphur
DMSO is dispersed by elemental sulfur (150mg), and the mass ratio of sulphur and DMSO are 1:1, in ZrO2Ball milling 30 in ball grinder
Minute obtains suspension, integration Porous Polypyrrole 150mg obtained in Example 3, and suspension is carried coated on polypyrrole
Body, 90 DEG C of vacuum drying after heating 1 hour remove DMSO, move under nitrogen atmosphere and be heated to 155 DEG C, heating makes elemental sulfur in 2 hours
Melting enters polypyrrole completely, and sulphur and polypyrrole mass ratio are 1:1.
The preparation of 7 sulfur electrode of embodiment
DMSO is dispersed by elemental sulfur (750mg), and the mass ratio of sulphur and DMSO are 1:1, in ZrO2Ball milling 30 in ball grinder
Minute obtains suspension, integration Porous Polypyrrole 150mg obtained in Example 3, and suspension is carried coated on polypyrrole
Body, 90 DEG C of vacuum drying after heating 1 hour remove DMSO, move under nitrogen atmosphere and be heated to 155 DEG C, heating makes elemental sulfur in 2 hours
Melting enters polypyrrole completely, and sulphur and polypyrrole mass ratio are 5:1, obtains the sulfur electrode of sulfur-bearing 83wt%.
Sodium-sulphur battery of the embodiment 8 based on integrated Porous Polypyrrole electrode material
150mg integration Porous Polypyrrole obtained in Example 3, by the metal sodium foil of homalographic in glove box
(1.5g) is pressed with integrated Porous Polypyrrole, and the mass ratio of metallic sodium and polypyrrole is 10:1, and heating is until sodium at 100 DEG C
Foil melting enters integrated Porous Polypyrrole, obtains sodium electrode.
DMSO is dispersed by elemental sulfur (1.5mg), and the mass ratio of sulphur and DMSO are 1:1, in ZrO2Ball milling 30 in ball grinder
Minute obtains suspension, takes integration Porous Polypyrrole 150mg obtained in above-described embodiment 3, and suspension is coated on poly- pyrrole
Cough up carrier, DMSO is removed in 90 DEG C of vacuum drying after heating 1 hour, is moved under nitrogen atmosphere and is heated to 155 DEG C, heating makes list in 2 hours
Matter sulphur melts completely enters polypyrrole, and sulphur and polypyrrole mass ratio are 10:1, obtain the sulfur electrode of sulfur-bearing 91wt%.
Above-mentioned sodium electrode and sulfur electrode and diaphragm is taken to form sandwich structure, built-in electrolyte；Electrolyte is with Na
[CF3SO2)2N] (NaTFSI) be solute, dioxolanes (C3H6O2) and ethylene glycol monomethyl ether (C4H10O2) mixture be solvent, two
The volume ratio of butyl oxide link and ethylene glycol monomethyl ether is 1:1, contains one mole of (279g) NaTFSI in one liter of electrolyte.Obtain low temperature sodium sulphur
Battery.Fig. 1 is the charging and discharging curve of gained sodium-sulphur battery at room temperature.
Finally it should be noted that the above enumerated are only specific embodiments of the present invention.It is clear that the invention is not restricted to
Above embodiments can also have many variations.Those skilled in the art can directly lead from present disclosure
Out or all deformations for associating, it is considered as protection scope of the present invention.
Claims (6)
1. a kind of preparation method of the sodium electrode of integration Porous Polypyrrole load, which comprises the following steps:
(1) 100mL deionized water is taken, 0.15~0.9g pyrroles and Na salt anionic surfactant 1g, ultrasonic vibration point is added
It dissipates and obtains pyrroles's lotion after five minutes；50mL deionized water is taken again, and 0.5~3g nanometer calcium carbonate template, initiator persulfuric acid is added
Sodium 0.1~0.5g and Na salt anionic surfactant 1g, is uniformly mixed so as to obtain suspension；It, will be suspended under ice bath and stirring condition
Drop adds in pyrroles's lotion, and the reaction was continued one hour after dripping；Then vacuum is carried out with the filter paper of polyacrylate material
It filters, dissolves away filter paper with acetone after filter cake and filter paper drying, obtain filter cake；Filter cake is washed into nanometer calcium carbonate by dilute hydrochloric acid
Template is rinsed with deionized water, obtains the integrated Porous Polypyrrole carrier material of sheet after dry；
(2) the integrated Porous Polypyrrole carrier material that 150mg step (1) obtains is taken, by the metal of homalographic in glove box
Sodium foil is pressed with it, and the thickness of control metal sodium foil makes 1~10:1 of mass ratio of metallic sodium and carrier material；Then 100
Heating at DEG C is until sodium foil melting obtains the sodium electrode for low temperature sodium-sulphur battery into carrier material.
2. a kind of preparation method of the sulfur electrode of integration Porous Polypyrrole load, which comprises the following steps:
(1) 100mL deionized water is taken, 0.15~0.9g pyrroles and Na salt anionic surfactant 1g, ultrasonic vibration point is added
It dissipates and obtains pyrroles's lotion after five minutes；50mL deionized water is taken again, and 0.5~3g nanometer calcium carbonate template, initiator persulfuric acid is added
Sodium 0.1~0.5g and Na salt anionic surfactant 1g, is uniformly mixed so as to obtain suspension；It, will be suspended under ice bath and stirring condition
Drop adds in pyrroles's lotion, and the reaction was continued one hour after dripping；Then vacuum is carried out with the filter paper of polyacrylate material
It filters, dissolves away filter paper with acetone after filter cake and filter paper drying, obtain filter cake；Filter cake is washed into nanometer calcium carbonate by dilute hydrochloric acid
Template is rinsed with deionized water, obtains the integrated Porous Polypyrrole carrier material of sheet after dry；
(2) 1:1 disperses elemental sulfur in DMSO in mass ratio, in ZrO2Obtain suspension within ball milling 30 minutes in ball grinder；It takes
The integrated Porous Polypyrrole carrier material that 150mg step (1) obtains, by suspension be coated on polypyrrole carrier, control sulphur with
The mass ratio of carrier material is 1~10:1；After heating 1 hour at 90 DEG C, DMSO is removed in vacuum drying；Then nitrogen atmosphere is moved to
Under, it is warming up to 155 DEG C and is kept for 2 hours, melt elemental sulfur completely and enter carrier material, obtain the sulphur for low temperature sodium-sulphur battery
Electrode.
3. method according to claim 1 or 2, which is characterized in that Na salt anionic surfactant described in step (1)
Hydrophobic group be chain alkyl, secondary alkyl or alkylaryl, hydrophilic group is carboxyl (RCOO), sulfonic group (R-SO3) or sulfuric ester
Base (R-OSO3)；Correspondingly, anionic surfactant general formula is expressed as RCOONa, R-SO3Na or R-OSO3Na, R in formula
For chain alkyl, secondary alkyl or alkylaryl.
4. method according to claim 1 or 2, which is characterized in that in step (1), control when ultrasonic vibration dispersion
Supersonic frequency is 40kHz.
5. method according to claim 1 or 2, which is characterized in that in step (1), suspension is added dropwise to pyrroles's lotion
When control rate of addition be 10mL/ hours.
6. a kind of low temperature sodium-sulphur battery, including diaphragm, anode, cathode and electrolyte；It is characterized in that, the sodium-sulphur battery is to weigh
The sodium electrode that benefit requires 1 the method to prepare is made as cathode, with the sulfur electrode that claim 2 the method prepares
It for anode, is separately positioned on diaphragm two sides and forms sandwich structure, and make electrode material side on anode and cathode towards diaphragm,
Electrolyte is built in sandwich structure；
In the electrolyte: with Na [CF3SO2)2N] it is solute, contain a mole of solute in every liter of electrolyte；With dioxolanes and second
The mixture of glycol methyl ether is solvent, and the volume ratio of dioxolanes and ethylene glycol monomethyl ether is 1:1.
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| CN104466183A (en) * | 2014-12-03 | 2015-03-25 | 湘潭大学 | Positive electrode material of polypyrrole lithium sulfur battery and preparation method of positive electrode material |
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| CN109225326A (en) * | 2018-09-14 | 2019-01-18 | 浙江大学台州研究院 | The preparation method of composite catalyst based on polypyrrole and Carbon foam load gold nano line |
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