CN114132973A - 一种改性氢氧化镍正极材料的制备方法 - Google Patents
一种改性氢氧化镍正极材料的制备方法 Download PDFInfo
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- CN114132973A CN114132973A CN202010914256.9A CN202010914256A CN114132973A CN 114132973 A CN114132973 A CN 114132973A CN 202010914256 A CN202010914256 A CN 202010914256A CN 114132973 A CN114132973 A CN 114132973A
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- positive electrode
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- conductive material
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- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical class [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 239000010406 cathode material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004020 conductor Substances 0.000 claims abstract description 20
- 239000010405 anode material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 32
- 239000007774 positive electrode material Substances 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 229920000547 conjugated polymer Polymers 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000002861 polymer material Substances 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229920000767 polyaniline Polymers 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229920001197 polyacetylene Polymers 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 229920000123 polythiophene Polymers 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 229960001701 chloroform Drugs 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000002848 electrochemical method Methods 0.000 abstract 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 229940010048 aluminum sulfate Drugs 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- FHMRWRBNAIDRAP-UHFFFAOYSA-N 5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=C(Br)SC(Br)=C21 FHMRWRBNAIDRAP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 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
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 229960003390 magnesium sulfate Drugs 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—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
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种改性氢氧化镍正极材料的制备方法,包括以下步骤:1、通过电化学法或者化学共沉淀法得到正极;2、通过电化学法或者固相聚合法将导电材料包覆到正极。该方法制备得到的正极材料具有高电导率,优越的循环性能,高容量以及高倍率等特点。
Description
技术领域
本发明涉及碱性电池制造技术领域,具体涉及一种改性氢氧化镍正极材料的制备方法。
背景技术
随着人类社会进步发展,能源越来越重要,能源安全保障已经成为国家经济的安全保障。传统不可再生能源日益消耗,显已经无法满足社会发展的需求,因此寻找一种高效的能源迫在眉睫。化学电源具有显著的优点。化学电源是一种将化学反应产生的化学能转换成电能的装置,该装置可以储存电能并释放电能。
目前,使用较为广泛的化学电源有锂离子电池、铅酸电池、燃料电池、镍镉电池和镍氢电池等。上述的化学电源存在一定的缺点,在应用过程中存在难以避免的障碍。比如锂离子电池的安全性较差;铅酸电池不仅笨重,而且体积很大,其比能量密度也比较低,对环境有污染;燃料电池的成本太高,而且目前的技术还不是很成熟;镍镉电池存在记忆效应,污染较为严重,很难满足当代可持续发展的要求;镍氢电池在高温条件下循环性较差,体积能量密度比较低,自放电能力与氢气的压力成正比关系,且研究开发成本太高。
然而,镍锌电池价格低廉、安全环保、性价比高,其电池正极活性物质主要为氢氧化镍,传统的Ni(OH)2电子电导非常差,导致电池极化严重,循环性能差,倍率性能不佳。
专利CN 201380060405.8公开了“碱性二次电池正极活性物质用的包覆氢氧化镍粉末及其制造方法”,该发明提供由钴化合物包覆层包覆氢氧化镍的粒子得到包覆氢氧化镍粉末;专利CN 201711309094.0公开了“一种碱性二次电池用氧化钴包覆氢氧化镍复合材料的制备方法”,该专利通过掺杂钇的球形氢氧化镍前躯体经过氧化得到氧化钴包覆的氢氧化镍材料。上述公开的专利中都是使用价格昂贵的钴、钇等无机材料包覆改性提高材料导电性,但是成本较高,性能提升有限。
发明内容
本发明的目的在于提供一种改性氢氧化镍正极材料的制备方法,通过对氢氧化镍掺杂锌、锰、铝、镁元素,分别可以减小电极反应中电化学极化、稳定结构,提升容量,控制晶型,同时提升电导率。再用共轭聚合物材料包覆,解决了氢氧化镍正极电子电导性能差的问题,有效延长了正极循环寿命,在高倍率的条件下性能更加显著,另外使用聚合物包覆可以形成致密膜体,抑制破碎。因此改善镍正极材料电化学性能能够提高镍锌电池整体的电化学性能。
本发明的技术方案如下:
一种改性氢氧化镍正极材料的制备方法,包括如下步骤:
(1)正极前驱体材料的制备:
在装有隔膜的电解槽中,阴极室加入0.5-2M/L浓度的金属盐溶液,阳极室加入0.5-2M/L的钾盐溶液,以泡沫镍作为阴极,铂作为阳极;0.1-1M/L氯化铵和氨水为络合剂,碱液调节pH至8-12,以1-3mA/cm2恒电流电解5-10h,50℃条件下电解,得到泡沫镍上沉积正极材料;
(2)导电材料包覆:
将0.1-2M/L的包覆材料超声处理30-60min溶于有机溶剂中得到胶体悬浮液,加入带有正极材料的泡沫镍或前驱体粉末搅拌均匀,挥发溶剂获得导电材料包覆的改性氢氧化镍正极材料。
进一步地,步骤(1)还包括如下步骤:
将金属盐配置成浓度在0.5-2M/L的溶液A,配置浓度为0.5-2M/L的碱液B以及0.1-1M/L的氨水溶液C;在机械搅拌400-1000r/min的条件下,反应温度控制在50-60℃,同时滴加A、B、C三种溶液控制pH至10-12之间,连续反应8-48h,经过去离子水洗涤、烘干得到正极材料。
进一步地,步骤(2)还包括如下步骤:
以石墨和沉积过正极材料的泡沫镍为电极,于电解池中加入0.1-2M/L的共轭聚合物单体溶液,以及前驱体粉末,在0.5-5v的电位区间高速搅拌30-60min进行电化学包覆,得到导电材料包覆的改性氢氧化镍正极材料。
进一步地,步骤(2)还包括如下步骤:
将上述带有正极材料的泡沫镍或者前驱体粉末,浸没于含有共轭聚合物单体盐以及氧化剂的溶液中,包覆材料与正极材料按照质量比1:5-20的比例,在40-100℃下保温2-5h,再经过多次洗涤后60℃烘干,即可得到导电材料包覆的改性氢氧化镍正极材料。
进一步地,所述正极为Ni1-x-y-z(M1)x(M2)y(M3)z(OH)2,其中0≤x≤0.05,0≤y≤0.03,0≤z≤0.02,M1、M2、M3为金属盐中的金属元素。
进一步地,所述金属M1、M2、M3为Zn、Mn、Al和Mg中的任意一种。
进一步地,所述金属盐溶液为Ni、Zn、Mn、Al和Mg相对应的硫酸盐、硝酸盐、氯化盐中的一种或多种混合溶液。
进一步地,所述包覆材料为导电材料,电子电导率大于1S/cm。
进一步地,所述导电材料为无机导电材料或共轭聚合物材料。
进一步地,所述包覆材料为共轭聚合物材料,包括聚乙炔(PA)、聚苯胺(PANI)、聚吡咯(PPY)、聚噻吩(PTH)及其衍生物等其中一种或多种。
进一步地,所述包覆材料为共轭聚合物材料基体,包括乙炔、苯胺、吡咯、噻吩、3,4-乙撑二氧噻吩(EDOT)及其衍生物中一种或多种。
进一步地,所述钾盐为硫酸钾、硝酸钾、氯化钾等中的一种或多种。
进一步地,所述碱液为氢氧化钾或氢氧化钠溶液中的一种或多种。
进一步地,所述有机溶剂包括四氢呋喃、乙腈、二氯甲烷、三氯甲烷等其中一种或多种。
进一步地,所述氧化剂包括无水氯化铁、碘单质、过硫酸铵中的一种或多种。
相对于现有技术,本发明具有以下有益效果:
1、对氢氧化镍掺杂锌、锰、铝或镁元素,分别可以减小电极反应中电化学极化,稳定结构,提升容量,控制晶型,同时提升了电导率;
2、不使用钴元素,有效降低了成本;
3、使用共轭聚合物材料包覆,可以形成致密膜体抑制破碎,大大提高了材料导电性和循环稳定性,使得电池具有高的比容量以及较长的循环寿命。
附图说明
图1为实施例1的正极材料扫面电镜图;
图2为实施例1的正极材料能谱图;
图3为实施例4的正极材料扫面电镜图;
图4为实施例4的正极材料能谱图。
具体实施方式
下面结合附图和实施例对本发明作详细描述,但本发明的实施不仅限于此。
实施例1.
一种改性氢氧化镍正极材料的制备方法,步骤如下:
(1)正极材料的制备:
在装有隔膜的电解槽中,阴极室加入0.5M/L浓度的硫酸镍、硫酸锌、硫酸锰和硫酸铝溶液,各盐摩尔比例为9:0.5:0.3:0.2。阳极室加入0.5M/L的硫酸钾溶液,以泡沫镍作为阴极,铂作为阳极。0.1M/L氯化铵和0.5M/L氨水为络合剂,氢氧化钠溶液调节pH至8,以3mA/cm2恒电流电解10h,50℃条件下电解,得到泡沫镍上沉积正极材料。
多元正极经过扫面电镜和能谱测试,如图1和图2所示。
(2)导电材料包覆:
将聚苯胺材料在甲基吡咯烷酮中超声处理30min得到0.1M/L胶体悬浮液,将沉积过正极材料的泡沫镍沉浸于该液中30min后取出,加热至110℃挥发溶剂,得到包覆聚苯胺的正极材料。
实施例2
一种改性氢氧化镍正极材料的制备方法,步骤如下:
(1)正极材料的制备:
将硫酸镍、硫酸锌、硫酸锰和硫酸铝以配置成浓度在0.5M/L的混合液A,各盐摩尔比例为9:0.5:0.3:0.2。配置浓度为0.5M/L的氢氧化钠溶液B以及0.1M/L的氨水溶液C;在机械搅拌400r/min的条件下,反应温度控制在50℃,同时滴加A、B、C三种溶液控制pH至10,连续反应8h,经过去离子水洗涤、烘干得到正极材料Ni0.9Zn0.05Mn0.03Al0.02(OH)2。
(2)导电材料包覆:
将盐酸苯胺盐与正极材料以5:100的质量比例在水中混合2h,再滴加过硫酸铵,在0-25℃保温2h,接着迅速搅拌4h,放置过夜。再经过多次洗涤至无硫酸根检出后60℃烘干,即可得到聚苯胺包覆的正极材料。
实施例3
一种改性氢氧化镍正极材料的制备方法,步骤如下:
(1)正极材料的制备:
在装有隔膜的电解槽中,阴极室加入2M/L浓度的氯化镍、氯化锌、氯化锰和氯化镁溶液,各盐摩尔比例为9:0.5:0.3:0.2。阳极室加入2M/L的硝酸钾溶液,以泡沫镍作为阴极,铂作为阳极。1M/L氯化铵和1M/L氨水为络合剂,氢氧化钠溶液调节pH至10,以1mA/cm2恒电流电解5h,50℃条件下电解,得到泡沫镍上沉积正极材料。
(2)导电材料包覆:
在电解槽中,以石墨和沉积过正极材料的泡沫镍为电极,沉浸在含有0.2M/L苯胺单体的0.25M/L KOH水溶液中,保持1.1v电位区间,通过电化学聚合法在泡沫镍上沉积制备出聚苯胺包覆的正极材料。
实施例4
一种改性氢氧化镍正极材料的制备方法,步骤如下:
(1)正极材料的制备:
将硝酸镍、硝酸锌、硝酸锰和硝酸铝溶液配置成浓度在2M/L的混合液A,各盐摩尔比例为9.5:0.2:0.2:0.1。配置浓度为2M/L的氢氧化钾B以及1M/L的氨水溶液C;在机械搅拌800r/min的条件下,反应温度控制在60℃,同时滴加A、B、C三种溶液控制pH至12,连续反应24h,经过去离子水洗涤、烘干得到正极材料Ni0.95Zn0.02Mn0.02Al0.01(OH)2。
(2)导电材料包覆:
在电解槽中,加入含有0.1M/L的3-甲基噻吩和0.1M/L高氯酸锂的乙腈溶剂,随后加入正极材料前驱体粉末,设定电极电压区间为5V,高速搅拌30min,过滤后多次洗涤置于60℃烘干,即可得到聚3-甲基噻吩包覆的正极材料。聚3-甲基噻吩包覆后的正极材料经过扫面电镜和能谱测试结果见图3和图4。
实施例5
一种改性氢氧化镍正极材料的制备方法,步骤如下:
(1)正极材料的制备:
将硫酸镍、硫酸锰、硫酸铝和硫酸镁配置成浓度在2M/L的混合液A,各盐摩尔比例为9.3:0.3:0.2:0.2。配置浓度为2M/L的氢氧化钠溶液B以及0.8M/L的氨水溶液C,在机械搅拌750r/min的条件下,反应温度控制在50℃,同时滴加A、B、C三种溶液控制pH至11.2,连续反应20h,经过去离子水洗涤、烘干得到正极材料Ni0.93Zn0.03Al0.02Mg0.0.2(OH)2。
(2)导电材料包覆:
将2,5-二溴3,4-乙撑二氧噻吩(DBEDOT)与正极材料前驱体粉末以5:100的比例在二氯甲烷中混合2.5h,室温真空除去二氯甲烷,在60℃保温8h,洗涤干燥后即可得到聚2,5-二溴3,4-乙撑二氧噻吩包覆的正极材料。
表1为本发明实施例1~5的室温下相关测试结果:
项目 | 粉体阻抗(Ω) | 电池1000次循环容量保持率 |
实施例1 | 2.1 | 82.3% |
实施例2 | 2.4 | 83.5% |
实施例3 | 2.5 | 80.1% |
实施例4 | 1.8 | 85.6% |
实施例5 | 1.5 | 86.2% |
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种改性氢氧化镍正极材料的制备方法,其特征在于,包括如下步骤:
(1)正极前驱体材料的制备:
在装有隔膜的电解槽中,阴极室加入0.5-2M/L浓度的金属盐溶液,阳极室加入0.5-2M/L的钾盐溶液,以泡沫镍作为阴极,铂作为阳极;0.1-1M/L氯化铵和氨水为络合剂,碱液调节pH至8-12,以1-3mA/cm2恒电流电解5-10h,50℃条件下电解,得到泡沫镍上沉积正极材料。
(2)导电材料包覆:
将0.1-2M/L的包覆材料超声处理30-60min溶于有机溶剂中得到胶体悬浮液,加入带有正极材料的泡沫镍或前驱体粉末搅拌均匀,挥发溶剂获得导电材料包覆的改性氢氧化镍正极材料。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)还包括如下步骤:
将金属盐配置成浓度在0.5-2M/L的溶液A,配置浓度为0.5-2M/L的碱液B以及0.1-1M/L的氨水溶液C;在机械搅拌400-1000r/min的条件下,反应温度控制在50-60℃,同时滴加A、B、C三种溶液控制pH至10-12之间,连续反应8-48h,经过去离子水洗涤、烘干得到正极材料。
3.根据权利要求1所述的制备方法,其特征在于,步骤(2)还包括如下步骤:
以石墨和沉积过正极材料的泡沫镍为电极,于电解池中加入0.1-2M/L的共轭聚合物单体溶液,以及前驱体粉末,在0.5-5v的电位区间高速搅拌30-60min进行电化学包覆,得到导电材料包覆的改性氢氧化镍正极材料。
4.根据权利要求1所述的制备方法,其特征在于,步骤(2)还包括如下步骤:
将上述带有正极材料的泡沫镍或者前驱体粉末,浸没于含有共轭聚合物单体盐以及氧化剂的溶液中,包覆材料与正极材料按照质量比1:5-20的比例,在40-100℃下保温2-5h,再经过多次洗涤后60℃烘干,即可得到导电材料包覆的改性氢氧化镍正极材料。
5.根据权利要求2所述的制备方法,其特征在于,所述正极为Ni1-x-y-z(M1)x(M2)y(M3)z(OH)2,其中0≤x≤0.05,0≤y≤0.03,0≤z≤0.02,M1、M2、M3为金属盐中的金属元素,优选地,所述金属M1、M2、M3为Zn、Mn、Al和Mg中的任意一种。
6.根据权利要求1所述的制备方法,其特征在于,所述金属盐溶液为Ni、Zn、Mn、Al和Mg相对应的硫酸盐、硝酸盐、氯化盐中的一种或多种混合溶液;
所述包覆材料为导电材料,电子电导率大于1S/cm;
所述导电材料为无机导电材料或共轭聚合物材料。
7.根据权利要求6所述的制备方法,其特征在于,所述包覆材料为共轭聚合物材料,包括聚乙炔(PA)、聚苯胺(PANI)、聚吡咯(PPY)、聚噻吩(PTH)及其衍生物等其中一种或多种;或,
所述包覆材料为共轭聚合物材料基体,包括乙炔、苯胺、吡咯、噻吩、3,4-乙撑二氧噻吩(EDOT)及其衍生物中一种或多种。
8.根据权利要求1所述的制备方法,其特征在于,所述钾盐为硫酸钾、硝酸钾、氯化钾等中的一种或多种;
所述碱液为氢氧化钾或氢氧化钠溶液中的一种或多种;
所述有机溶剂包括四氢呋喃、乙腈、二氯甲烷、三氯甲烷等其中一种或多种;
所述氧化剂包括无水氯化铁、碘单质、过硫酸铵中的一种或多种。
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