CN104466120B - Magnesium-based composite material and application thereof in lead acid storage battery as well as method for preparing lead acid storage battery by utilizing material - Google Patents
Magnesium-based composite material and application thereof in lead acid storage battery as well as method for preparing lead acid storage battery by utilizing material Download PDFInfo
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- CN104466120B CN104466120B CN201410728265.3A CN201410728265A CN104466120B CN 104466120 B CN104466120 B CN 104466120B CN 201410728265 A CN201410728265 A CN 201410728265A CN 104466120 B CN104466120 B CN 104466120B
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- China
- Prior art keywords
- lead
- magnesium
- sulfate
- composite material
- magnesio
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000002253 acid Substances 0.000 title claims abstract description 125
- 239000011777 magnesium Substances 0.000 title claims abstract description 61
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000003860 storage Methods 0.000 title abstract description 16
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 47
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 239000011133 lead Substances 0.000 claims description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 59
- 229910021389 graphene Inorganic materials 0.000 claims description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- 239000002114 nanocomposite Substances 0.000 claims description 24
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical group [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 22
- 239000011505 plaster Substances 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- 239000001117 sulphuric acid Substances 0.000 claims description 15
- 235000011149 sulphuric acid Nutrition 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 13
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229950000845 politef Drugs 0.000 claims description 12
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 12
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 12
- 235000011151 potassium sulphates Nutrition 0.000 claims description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 12
- 235000011152 sodium sulphate Nutrition 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 11
- 229910000464 lead oxide Inorganic materials 0.000 claims description 11
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 11
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 11
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000005253 cladding Methods 0.000 claims description 10
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 10
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 10
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052756 noble gas Inorganic materials 0.000 claims description 5
- 150000002835 noble gases Chemical class 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- -1 graphite alkene Chemical class 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
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- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
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- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 150000002680 magnesium Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 2
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- 239000010931 gold Substances 0.000 claims 2
- 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 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
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- MXEJFXMHLHQKRP-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Pb++] Chemical compound [O--].[O--].[Ti+4].[Pb++] MXEJFXMHLHQKRP-UHFFFAOYSA-N 0.000 claims 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- SMBGWMJTOOLQHN-UHFFFAOYSA-N lead;sulfuric acid Chemical compound [Pb].OS(O)(=O)=O SMBGWMJTOOLQHN-UHFFFAOYSA-N 0.000 description 1
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- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- ILRLTAZWFOQHRT-UHFFFAOYSA-N potassium;sulfuric acid Chemical compound [K].OS(O)(=O)=O ILRLTAZWFOQHRT-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a magnesium-based composite material and application of the material in a lead acid storage battery as well as a method for preparing the lead acid storage battery by utilizing the material. The preparation method of the magnesium-based lead acid storage battery with ultra-low temperature, long service life and high capacity comprises the following steps: preparing a magnesium alloy at first; preparing the magnesium-based composite material; mixing the prepared magnesium-based composite material with positive and negative electrode materials of the lead acid battery to prepare paste; preparing an un-formed magnesium-based lead acid storage battery according to the preparation method and the process condition of the standard lead acid storage battery; and preparing the magnesium-based lead acid storage battery according to a certain formation condition. The prepared magnesium-based lead acid storage battery has the characteristics of ultra-low temperature, high capacity, high magnification and long cycle life, and has a good industrial application prospect; the performance of the magnesium-based lead acid storage battery is obviously superior to that of the traditional lead acid storage battery.
Description
Technical field
The invention belongs to battery material and cell art and in particular to a kind of new preparation containing magnesium cell material and
Application on lead-acid battery.
Background technology
Lead-acid accumulator has a wide range of applications in power and energy storage.But, due to traditional lead-acid accumulator low temperature-
40 DEG C be unable to discharge and recharge, battery energy density is little, capacity is low and cycle life is short, limit its application.
Content of the invention
In order to improve low temperature charge-discharge performance, battery capacity and the cycle performance of lead-acid accumulator simultaneously, the present invention proposes
The application in lead-acid accumulator of a kind of magnesium base composite material and this material and the side of preparing lead-acid accumulator using this material
Method.
The technical solution of the present invention is as follows：
A kind of preparation method of magnesium base composite material, it is characterized in that：Comprise the following steps：
1.1) prepare magnesium alloy powder
By magnesium metal and other metals and/or nonmetallic mix homogeneously, melting in vacuum or protective gas atmosphere, preparation
Obtain magnesium alloy compound MgXMY, by magnesium alloy chemical compound crush be prepared into magnesium alloy powder, wherein, M represent other metals and/
Or nonmetallic, X is the molal quantity of magnesium, and Y is other metals and/or nonmetallic total molal quantity,
1.2) prepare magnesium alloy/graphene nanocomposite material
1.3) prepare the magnesium alloy/graphene nanocomposite material of oxide cladding
1.3.1) salt and/or ester are dissolved in water and the mixed solution of alcohol, under intense agitation, lead in the solution
Enter noble gases, remove the oxygen of dissolving and carbon dioxide in solution,
1.3.2) in inert gas atmosphere, under intense agitation, by step 1.2) magnesium alloy/stone of preparing
Black alkene composite adds solution, the suspension of prepared mix homogeneously；In inert gas atmosphere, under intense agitation,
Slowly dropwise Deca ammonia, makes ammonia and soluble-salt and/or ester react generation hydroxide precipitation, is uniformly coated on
Magnesium alloy/graphene composite material surface,
1.3.3) by step 1.3.2) solution for preparing filtering in inert gas atmosphere, obtains hydroxide bag
Magnesium alloy/the graphene composite material covering, with washing with alcohol for several times, will obtain the magnesium alloy/stone of hydroxide cladding after washing
Black alkene composite is calcined in an inert atmosphere and is cooled to room temperature, and the magnesium alloy/graphene nano obtaining oxide cladding is combined
Material.
Above-mentioned steps 1.1) in other metals be cobalt (Co), nickel (Ni), lead (Pb), copper (Cu), silver-colored (Ag), golden (Au),
Aluminum (Al), titanium (Ti), vanadium (V), zinc (Zn), germanium (Ge), molybdenum (Mo), indium (In), antimony (Sb), bismuth (Bi), barium (Ba), tungsten (W), palladium
(Pd), one or more of niobium (Nb), zirconium (Zr) and gallium (Ga)；
Other nonmetallic for one or more of boron (B), carbon (C), nitrogen (N), silicon (Si), phosphorus (P) and sulfur (S)；
Smelting temperature is 500～1000 DEG C, and protective gas is one or more of nitrogen, helium and argon.
Above-mentioned steps 1.2) in graphene powder be using improve Hummers method preparation；Magnesium alloy and Graphene powder
The mass ratio at end is 100:30～1.
Above-mentioned steps 1.3.1) in salt be one or more of water-soluble sulfate, nitrate and acetate；
The cation of salt is one or more of aluminum, titanium, magnesium, zinc, stannum, zirconium, cobalt, nickel, copper, tungsten, gallium and yttrium,
Described alcohol includes one or more of ethanol, propanol, isopropanol, butanol, isobutanol and ethylene glycol；Described water and
The volume ratio of alcohol is 100～40:1～60,
Described noble gases are one or more of nitrogen, helium and argon,
It is passed through noble gases, the time removing the oxygen of dissolving and carbon dioxide in solution is 1～10 hour in solution,
Step 1.3.2) in Deca ammonia amount be that ammonia and anions in solution generate hydroxide molal quantity 1～2 times,
Step 1.3.3) in calcining heat be 150～500 DEG C,
The mass ratio of described magnesium alloy/graphene nanocomposite material and oxide is 100:20～0.1.
Magnesium base composite material prepared by said method in lead-acid battery as battery active material and prepare plumbic acid electricity
As the application of both positive and negative polarity pole plate active material during pond.
A kind of preparation method of ultralow temperature long life high capacity magnesio lead-acid accumulator, it is characterized in that：
In the lead plaster of the positive plate preparing lead-acid accumulator and negative plate, all add in positive plate lead paste and negative plate lead plaster
Enter a kind of active substance, this active substance is magnesium base composite material, the preparation method such as said method of this magnesium base composite material
Described.
The raw material of above-mentioned positive plate lead paste also includes in addition to magnesium base composite material：Hydrocerussitum (Ceruse), Lead oxide brown, four alkali formula sulphuric acid
Lead, chopped fiber, graphite, sulfate, sulphuric acid, politef and water；
The raw material of negative plate lead plaster also includes in addition to magnesium base composite material：Hydrocerussitum (Ceruse), Lead oxide brown, four basic lead sulphates, short
Fiber, graphite, sulfate, sulphuric acid, politef and water；
Sulfate in both positive and negative polarity pole plate lead plaster is magnesium sulfate, cobaltous sulfate, barium sulfate, copper sulfate, stannous sulfate, potassium sulfate
One or more of with sodium sulfate；
Chopped fiber in both positive and negative polarity pole plate lead plaster is one of polypropylene chopped fiber peacekeeping polyester staple fiber or two kinds.
Each constituent mass percentage ratio in above-mentioned anode plate lead plaster raw material is：Magnesium base composite material 1～20%, Hydrocerussitum (Ceruse) 1
～6%, Lead oxide brown 60～65%, four basic lead sulphates 1～7%, chopped fiber 0.001～1%, graphite 0.001～1%, sulfur
Sour magnesium 0.01～3%, cobaltous sulfate 0.01～1%, barium sulfate 0.01～1%, copper sulfate 0.01～2%, stannous sulfate 0.01～
1%th, potassium sulfate 0.01～2%, sodium sulfate 0.01～2%, sulphuric acid 3～10%, politef 0.01～0.1%, water 5～
15%；
Each constituent mass percentage ratio of described negative plate lead plaster is：Magnesium base composite material 1～20%, Hydrocerussitum (Ceruse) 1～6%, two
Lead oxide 60～66%, four basic lead sulphates 1～7%, chopped fiber 0.001～1%, graphite 0.001～1%, magnesium sulfate 0.01
～3%, cobaltous sulfate 0.01～1%, barium sulfate 0.01～1%, copper sulfate 0.01～2%, stannous sulfate 0.01～1%, sulphuric acid
Potassium 0.01～2%, sodium sulfate 0.01～2%, sulphuric acid 3～10%, politef 0.01～0.1%, water 5～15%.
The lead plaster coating plate of above-mentioned positive plate and negative plate is latticed metal grid, and latticed metal grid is
Lead calcium stannum aluminum conduction volume grating；
Prepare lead plaster solidification temperature when positive plate and negative plate and be 35～85 DEG C, solidification relative humidity is 85～98%,
Hardening time is 20～80 hours；Baking temperature be 20～80 DEG C, be dried relative humidity be 10～40%, drying time be 2～
40 hours.
Electrolyte each constituent mass percentage ratio of the battery prepared by said method is：Sulphuric acid 32%, water 60%, magnesium sulfate
1%th, cobaltous sulfate 0.2～2%, copper sulfate 0.1～1%, zinc sulfate 0.1～3%, aluminum sulfate 0.1～5%, potassium sulfate 0.1～
2%th, sodium sulfate 0.1～2%, ammonium sulfate 0.1～2%, disodiumedetate 0.2～3%.
For after standing 4～6 hours after fluid injection, with 0.15C, 10A's chemical conversion condition of battery charges, and accumulator voltage stablizes 1
After～3 hours, during change in voltage ± 0.03V, with 0.10C after standing, 10A is discharged to during accumulator voltage 10.5V and terminates putting
Electricity.
The invention has the beneficial effects as follows：
1st, the present invention adds a kind of advanced composite material (ACM) for lead-acid accumulator positive and negative pole material, provides this material simultaneously
Preparation method, and be obtained magnesio plumbic acid positive and negative pole material there is high power capacity, circulating ratio performance, low temperature and have a safety feature
Feature.
2nd, the present invention adds magnesium base composite material on the basis of traditional lead acid batteries, the magnesio lead acid storage battery preparing
Pond is compared with traditional lead acid batteries, has good low temperature performance, high power capacity, high magnification and longevity advantage, has
Well application prospect, be embodied in following some：
2.1) same volume significantly improves 10～20% with battery capacity under weight condition；
2.2) frozen 24 hours under -40 DEG C of low temperature, nominal capacity >=45% can be released, traditional lead acid batteries -
It is unable to discharge and recharge under 40 DEG C of low temperature；
2.3) high current continuous discharge effect is significant is higher than other lead-acid accumulator, and 3C final discharging voltage is 9.6V, can
Release nominal capacity 50%；
2.4) magnesium lead energy storage accumulator, passes through《GB/T 22473-2008 energy storage lead-acid accumulator》Detection, the life-span is followed
Ring is high, circulates more than 5 cycles, and standard is 3 cycles circulation (cycle circulated as 150 circulation/cycles).
Brief description
Fig. 1 is that embodiment 1 is prepared into according under conventional 12V-200Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 discharge voltage testing to obtain under the conditions of 23 DEG C of 10h of room temperature lead and capacity curve；
Fig. 2 is that embodiment 1 is prepared into according under conventional 12V-200Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 discharge voltage testing to obtain under the conditions of 23 DEG C of discharge current 1C of room temperature and capacity curve；
Fig. 3 is that embodiment 1 is prepared into according under conventional 12V-200Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 discharge voltage testing to obtain under the conditions of 23 DEG C of discharge current 3C of room temperature and capacity curve；
Fig. 4 is that embodiment 1 is prepared into according under conventional 12V-200Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 lead in -40 DEG C of 10h and under discharging condition, test the discharge voltage obtaining and capacity curve；
Fig. 5 is that embodiment 1 is prepared into according under conventional 12V-38Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 lead the discharge voltage testing to obtain under discharging condition and capacity curve in 23 DEG C of 10h；
Fig. 6 is that embodiment 1 is prepared into according under conventional 12V-38Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 lead the discharge voltage testing to obtain under discharging condition and capacity curve in 23 DEG C of 120h；
Fig. 7 is that embodiment 1 is prepared into according under conventional 12V-38Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 lead in -10 DEG C of 10h and under discharging condition, test the discharge voltage obtaining and capacity curve；
Fig. 8 is that embodiment 1 is prepared into according under conventional 12V-38Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 lead in -40 DEG C of 10h and under discharging condition, test the discharge voltage obtaining and capacity curve；
Fig. 9 is the reduced graphene SEM image that embodiment 1 prepares；
Figure 10 is the magnesium base composite material SEM image that embodiment 1 prepares；
Figure 11 is the granularmetric analyses collection of illustrative plates of the magnesium base composite material that embodiment 1 prepares；
Figure 12 is the magnesium base composite material specific surface area test result that embodiment 1 prepares.
Specific embodiment
The present invention, when preparing ultralow temperature long life high capacity magnesio lead-acid accumulator, prepares magnesium base composite material first,
Prepare magnesio lead-acid accumulator both positive and negative polarity pole plate again.Prepare magnesio on the basis of existing lead-acid accumulator preparation process condition
Lead-acid accumulator.
With reference to specific embodiment, the present invention is further illustrated, but the invention is not limited in this.
Embodiment raw materials, are pure, content >=99.9% of analysis.
Embodiment 1
A kind of preparation method of ultralow temperature long life high capacity magnesio lead-acid accumulator, comprises the following steps：
1) prepare magnesium base composite material
1.1) prepare magnesium alloy
By magnesium metal, cobalt, nickel, lead, copper, titanium, vanadium and zinc powder (200 mesh) in mass ratio 20:0.2:0.5:0.3:0.2:
0.1:0.2:0.1 uniformly mixes, and under an argon atmosphere, 900 DEG C of meltings prepare magnesium alloy, and the magnesium alloy preparing is broken
Broken ball milling becomes 350 mesh magnesium alloy powders.
1.2) prepare magnesium alloy/graphene composite material
Graphene powder preparation method is using improvement Hummer method.
Using 2 grams of natural flake graphite powder (Qingdao City Laixi Jin Lai electronics material factory 325 mesh, more than 99.4%),
It is placed in three-neck flask in ice-water bath, under Teflon stir bar stirring, be slowly added into 46ml 98%H2SO4, stir 2 little
When；In ice-water bath, continue stirring, add 1 gram of pure NaNO of analysis3, 6 grams of pure KMnO of analysis4, solution becomes brown-green, stirs 45
Minute；Plus 60 milliliters of ultra-pure water, solution becomes brown color, is warming up to 40 DEG C, stirs 45 minutes；Then heat to 90 DEG C, stir 15
Minute；Plus 30% and analyze pure H2O260 milliliters, 90 DEG C are stirred 40 minutes；Solution filtered while hot, first pure with 350 milliliter of 5% analysis
HCl solution wash, then with milli-Q water to pH value be 7, collect black oxidation powdered graphite；It is little that 60 DEG C of vacuum dries 12
When, vacuum cooled to room temperature, then grind alms bowl with Achatess and pulverize, make graphite oxide powder (Graphite Oxide).
Graphite oxide lower black graphite oxide is taken to precipitate, milli-Q water puts 1000 milliliters of beakers, to 500 milliliters, plus
Ammonia adjusts pH value to 11, and ultrasound wave disperses 30 minutes；Add 60 milliliters of hydrazine hydrates, 90 DEG C of constant temperature, 8 hours, be then cooled to room
Temperature, can see floating transparent monolayer and multi-layer graphene fragment in solution surface；Sucking filtration solution, 1500 milliliters of milli-Q water
Black puffy filter cake, to cleaning mixture clarification, pH value to 7.It is little that graphite oxide and Graphene mixture are placed in 60 DEG C 5 of vacuum drying oven
When dry, canescence voluminous powder, naturally cool to room temperature, Achatess grind alms bowl and are ground into fine powder, preserve in exsiccator.
By the magnesium alloy powder preparing in mass ratio 100:10 and graphene powder mixing, add agitating ball mill,
Under argon gas atmosphere, ball milling 72 hours, prepare magnesium alloy/graphene nanocomposite material.
Step 1.2) in concentration be mass concentration.
1.3) prepare oxide cladding magnesium alloy/graphene nanocomposite material
By 2800 milliliters of water and 200 milliliters of ethanol mixing, it is passed through high-purity argon gas (>=99.9%) in the solution 6 hours, removes
Remove the oxygen in mixed solution and carbon dioxide；
Then, under high-purity argon gas protection, add 13.418 grams of anhydrous slufuric acid aluminum, be passed through high-purity argon gas 5 in the solution little
When, it is stirred vigorously, remove the oxygen in mixed solution and carbon dioxide；
Then, under high-purity argon gas protection, add 200 grams of magnesium alloy/graphene nanocomposite materials, be passed through in the solution
High-purity argon gas 1 hour, are stirred vigorously, the suspension of prepared mix homogeneously, remove the oxygen in mixed solution and carbon dioxide；
Then, under high-purity argon gas protection, under intense agitation, it is added dropwise over 3 mol/L excessive ammonia 100 milli
Rise, generate 6.118 grams of white aluminum hydroxide precipitations, be evenly coated at magnesium alloy/graphene nanocomposite material surface；
By the solution generating under high-purity argon gas protection, filter, obtain the tin alloy/graphene nano of aluminium hydroxide cladding
Composite；By filtered product, under high-purity argon gas protection, with absolute ethanol washing 5 times；
Tin alloy/the graphene nanocomposite material of aluminium hydroxide cladding will be obtained under high-purity argon gas protection after washing,
350 DEG C of calcinings, are then cooled to room temperature, obtain 4 grams of (percent mass of aluminium oxide and magnesium alloy/graphene nanocomposite material
Than for 2%) magnesium alloy/graphene nanocomposite material of alumina-coated.
2) prepare magnesio lead-acid battery electrode plate
By magnesium base composite material, Hydrocerussitum (Ceruse), Lead oxide brown, four basic lead sulphates, polyester staple fiber, graphite, magnesium sulfate, sulphuric acid
Cobalt, copper sulfate, stannous sulfate, potassium sulfate, sodium sulfate, sulphuric acid, politef and water mixing and cream are obtained magnesio lead acid storage battery
Pond positive plate lead paste.Each constituent mass percentage ratio of lead plaster is：Magnesium base composite material 20%, Hydrocerussitum (Ceruse) 2%, Lead oxide brown 65%,
Four basic lead sulphates 4%, polyester staple fiber 0.02%, graphite 0.03%, magnesium sulfate 0.2%, cobaltous sulfate 0.1%, copper sulfate
0.1%th, stannous sulfate 0.2%, potassium sulfate 0.1%, sodium sulfate 0.2%, sulphuric acid 5%, politef 0.05% and water 7%.
By magnesium base composite material, Hydrocerussitum (Ceruse), Lead oxide brown, four basic lead sulphates, polyester staple fiber, graphite, magnesium sulfate, sulphuric acid
Cobalt, copper sulfate, stannous sulfate, potassium sulfate, sodium sulfate, sulphuric acid, politef and water are mixed to prepare magnesio lead-acid storage battery negative
Pole plate lead plaster.Each constituent mass percentage ratio of lead plaster is：Magnesium base composite material 20%, Hydrocerussitum (Ceruse) 5%, Lead oxide brown 66%, four alkali
Formula lead sulfate 3%, polyester staple fiber 0.02%, graphite 0.03%, magnesium sulfate 0.2%, cobaltous sulfate 0.1%, copper sulfate 0.1%,
Stannous sulfate 0.2%, potassium sulfate 0.1%, sodium sulfate 0.2%, sulphuric acid 5%, politef 0.05%, water 7%.
Magnesio lead-acid accumulator positive/negative plate lead plaster solidification temperature is 55 DEG C, and solidification relative humidity is 85%, hardening time
For 30 hours；Baking temperature is 50 DEG C, and it is 20% that relative humidity is dried, and drying time is 5 hours.
Magnesium lead storage battery electrolytic solution each constituent mass percentage ratio is：Sulphuric acid 32%, water 60%, magnesium sulfate 1%, cobaltous sulfate
1%th, copper sulfate 0.5%, zinc sulfate 0.5%, aluminum sulfate 1%, potassium sulfate 1%, sodium sulfate 1%, ammonium sulfate 1% and ethylenediamine tetraacetic
Acetic acid disodium 1%.
4) it is melted into
The chemical conversion condition of magnesio lead-acid accumulator be fluid injection after standing 5 hours after with 0.15C10A charges, accumulator voltage
After stablizing 2.5 hours, when change in voltage is ± 0.03V, standing is after 1 hour with 0.10C10A is discharged to accumulator voltage
Terminate electric discharge during 10.5V.
Other magnesio lead-acid accumulator preparation technologies and condition are entered according to traditional lead acid batteries preparation technology and condition
Row completes.
Preparing overall dimensions length × width × height (mm) according to above step is 494 × 238 × 224, and quality is
The 12V magnesio lead acid traction battery of 63.55Kg；
Preparing overall dimensions length × width × height (mm) according to above step is 197 × 160 × 174, and quality is
The 12V magnesio plumbic acid energy storage battery of 13.50Kg.
Embodiment 2
A kind of preparation method of ultralow temperature long life high capacity magnesio lead-acid accumulator, comprises the following steps：
Embodiment 2 reaction environment and condition with embodiment 1, except that：
Step 1) prepare magnesium alloy/graphene nanocomposite material (magnesium oxide and the magnesium alloy/stone that magnesium oxide coats
The mass percent of black alkene nano composite material is 2%).
Step 2) magnesium base composite material and both positive and negative polarity other components mass ratio be 18:82.
Preparing overall dimensions length × width × height (mm) according to above step is 494 × 238 × 224, and quality is
The 12V magnesio lead acid traction battery of 63.55Kg；
Preparing overall dimensions length × width × height (mm) according to above step is 197 × 160 × 174, and quality is
The 12V magnesio plumbic acid energy storage battery of 13.50Kg.
Embodiment 3
A kind of preparation method of ultralow temperature long life high capacity magnesio lead-acid accumulator, comprises the following steps：
Embodiment 3 reaction environment and condition with embodiment 1, except that：
Step 1) prepare magnesium alloy/graphene nanocomposite material (zinc oxide and the magnesium alloy/stone of oxide coated by zinc
The mass percent of black alkene nano composite material is 2%).
Step 2) magnesium base composite material and both positive and negative polarity other components mass ratio be 15:85.
Preparing overall dimensions length × width × height (mm) according to above step is 494 × 238 × 224, and quality is
The 12V magnesio lead acid traction battery of 63.55Kg；
Preparing overall dimensions length × width × height (mm) according to above step is 197 × 160 × 174, and quality is
The 12V magnesio plumbic acid energy storage battery of 13.50Kg.
Embodiment 4
A kind of preparation method of ultralow temperature long life high capacity magnesio lead-acid accumulator, comprises the following steps：
Embodiment 4 reaction environment and condition with embodiment 1, except that：
Step 1) magnesium alloy/graphene nanocomposite material of coated by titanium dioxide is prepared using tetrabutyl titanate
(titanium dioxide is 2% with the mass percent of magnesium alloy/graphene nanocomposite material).
Step 2) magnesium base composite material and both positive and negative polarity other components mass ratio be 10:90.
Preparing overall dimensions length × width × height (mm) according to above step is 494 × 238 × 224, and quality is
The 12V magnesio lead acid traction battery of 63.55Kg；
Preparing overall dimensions length × width × height (mm) according to above step is 197 × 160 × 174, and quality is
The 12V magnesio plumbic acid energy storage battery of 13.50Kg.
Embodiment 5
A kind of preparation method of ultralow temperature long life high capacity magnesio lead-acid accumulator, comprises the following steps：
Embodiment 5 reaction environment and condition with embodiment 1, except that：
Step 1) prepare magnesium alloy/graphene nanocomposite material (copper oxide and the magnesium alloy/stone aoxidizing copper clad
The mass percent of black alkene nano composite material is 2%).
Step 2) magnesium base composite material and both positive and negative polarity other components mass ratio be 8:92.
Preparing overall dimensions length × width × height (mm) according to above step is 494 × 238 × 224, and quality is
The 12V magnesio lead acid traction battery of 63.55Kg；
Preparing overall dimensions length × width × height (mm) according to above step is 197 × 160 × 174, and quality is
The 12V magnesio plumbic acid energy storage battery of 13.50Kg.
Embodiment 6
A kind of preparation method of ultralow temperature long life high capacity magnesio lead-acid accumulator, comprises the following steps：
Embodiment 6 reaction environment and condition with embodiment 1, except that：
Step 1) prepare magnesium alloy/graphene nanocomposite material (ferrum oxide and the magnesium alloy/stone that ferrum oxide coats
The mass percent of black alkene nano composite material is 2%).
Step 2) magnesium base composite material and both positive and negative polarity other components mass ratio be 5:95.
Preparing overall dimensions length × width × height (mm) according to above step is 494 × 238 × 224, and quality is
The 12V magnesio lead acid traction battery of 63.55Kg；
Preparing overall dimensions length × width × height (mm) according to above step is 197 × 160 × 174, and quality is
The 12V magnesio plumbic acid energy storage battery of 13.50Kg.
Material property characterizes
The analysis test of magnesium base composite material various metallic element weight/mass percentage composition is in U.S. Leeman (Riemann) company electricity
Carry out in sense coupled plasma optical emission spectrogrph PROFILE SPEC type.
Table 1 is the magnesium base composite material each element weight/mass percentage composition that test obtains.
Material surface pattern is carried out in Zeiss, Germany company EV018 type scanning electron microscope SEM, and X-ray energy dissipates
Penetrate EDS spectrum and Element area profile to carry out on Oxford X-MAX 20 type energy disperse spectroscopy.
Fig. 9 is the reduced graphene SEM image that embodiment 1 prepares；
Figure 10 is the magnesium base composite material SEM image that embodiment 1 prepares.
Embodiment 1 magnesium base composite material X-ray powder energy dispersive EDS spectrum, measure containing magnesium, cobalt, nickel, lead, copper, titanium,
Vanadium, zinc, aluminum, carbon and oxygen element.
Magnesium base composite material powder diameter D50 value is carried out in Britain Malvern Mastersizer 2000 type.
Figure 11 is the granularmetric analyses collection of illustrative plates of the magnesium base composite material that embodiment 1 prepares, and D50 value is 3.286 microns.
Specific surface area is tested in the full-automatic specific surface area of Kang Ta company of U.S. QUADRASORB SI type and lacunarity analysis instrument
On carry out.
Figure 12 is the specific surface area test result of the magnesium base composite material that embodiment 1 prepares, institute measured value 5.354m2/
g.
Battery performance test
The battery testing of magnesio plumbic acid power and energy storage battery is in the micro- electricity of Jiangsu Jinfan Power Science and Technology Co., Ltd μ C-DF
Carry out in brain accumulator capacity and discharge performance tester (1000A/12V), equipment precision 0.01A/V.Low-temperature test cabinet in
Carry out in Ke Meiling low temperature Science and Technology Ltd. DW-HW328 low-temperature cabinet, equipment precision ± 1 DEG C.
Magnesio energy storage lead-acid battery testing standard is carried out with lead-acid accumulator GB/T 22473-2008 standard according to energy storage.
Magnesio power lead-acid battery testing standard is according to sealing lead acid storage battery for electric vehicle GB/T22199-2008
Standard is carried out.
Fig. 1 is that embodiment 1 is prepared into according under conventional 12V-200Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 discharge voltage testing to obtain under the conditions of 23 DEG C of 10h of room temperature lead and capacity curve；Test obtains
It is 257.8Ah that 23 DEG C of 10h of the magnesio lead-acid accumulator of same specification size and quality lead discharge capacity；
Fig. 2 is that embodiment 1 is prepared into according under conventional 12V-200Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 discharge voltage testing to obtain under the conditions of 23 DEG C of discharge current 1C of room temperature and capacity curve；Survey
It is 194Ah that examination obtains same specification size and 23 DEG C of 1C discharge capacities of magnesio lead-acid accumulator of quality；
Fig. 3 is that embodiment 1 is prepared into according under conventional 12V-200Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 discharge voltage testing to obtain under the conditions of 23 DEG C of discharge current 3C of room temperature and capacity curve；Survey
It is 151Ah that examination obtains same specification size and 23 DEG C of 3C discharge capacities of magnesio lead-acid accumulator of quality；
Fig. 4 is that embodiment 1 is prepared into according under conventional 12V-200Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 lead in -40 DEG C of 10h and under discharging condition, test the discharge voltage obtaining and capacity curve；Test
- 40 DEG C of 10h of magnesio lead-acid accumulator to same specification size and quality lead discharge capacity for 158Ah；
Table 2 is 12V magnesio lead-acid battery and conventional 12V-200Ah lead-acid power accumulator test result compares
Table 2 may compare and obtains homogenous quantities and same volume magnesio lead-acid battery exceeds 27.0% capacity than conventional lead acid batteries,
Room temperature 1C discharge capacity is nominal capacity 76.4%, and room temperature 3C discharge capacity is nominal capacity 59.5%, multiplying power discharging property
Good, -40 DEG C of low temperature can release 62.2% capacity.In table 2, battery is numbered is that "-" in 2 represents that this parameter is not tested；Battery is numbered
It is to represent that data does not provide with reference to the "-" in 12V-200Ah battery, but this data refers to the electricity of same size on existing market
The test data in pond.
Fig. 5 is that embodiment 1 is prepared into according under conventional 12V-38Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 lead the discharge voltage testing to obtain under discharging condition and capacity curve in 23 DEG C of 10h；Test obtains
It is 48.6Ah that 23 DEG C of 10h of the magnesio lead-acid accumulator of same specification size and quality lead discharge capacity；
Fig. 6 is that embodiment 1 is prepared into according under conventional 12V-38Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 lead the discharge voltage testing to obtain under discharging condition and capacity curve in 23 DEG C of 120h；Test
23 DEG C of 120h of magnesio lead-acid accumulator to same specification size and quality lead discharge capacity for 56.7Ah；
Fig. 7 is that embodiment 1 is prepared into according under conventional 12V-38Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 lead in -10 DEG C of 10h and under discharging condition, test the discharge voltage obtaining and capacity curve；Test
- 10 DEG C of 12h of magnesio lead-acid accumulator to same specification size and quality lead discharge capacity for 43.7Ah；
Fig. 8 is that embodiment 1 is prepared into according under conventional 12V-38Ah lead-acid accumulator identical appearance size and quality requirements
To magnesio lead-acid accumulator 1 lead in -40 DEG C of 10h and under discharging condition, test the discharge voltage obtaining and capacity curve；Test
- 40 DEG C of 120h of magnesio lead-acid accumulator to same specification size and quality lead discharge capacity for 21.2Ah.
Table 3 is 12V magnesio lead-acid battery and conventional 12V-38Ah plumbic acid energy-storage battery test result compares
Table 3 may compare and obtains homogenous quantities and same volume magnesio lead-acid battery exceeds 27.9% capacity than conventional lead acid batteries,
Room temperature 120h leads discharge capacity and leads discharge capacity 116.7% for 10h, and -10 DEG C of low temperature can release 89.9% capacity, -40 DEG C of low temperature
43.6% capacity can be released.In table 2, battery is numbered is that "-" in 2 represents that this parameter is not tested；It is with reference to 12V- that battery is numbered
"-" in 38Ah battery represents that data does not provide, but this data refers to the test number of the battery of same size on existing market
According to.
Above test result indicate that, the magnesio lead-acid accumulator prepared by the present invention has good low temperature discharge property
Energy, high power capacity, high magnification and longevity advantage, have good application prospect.
Claims (11)
1. a kind of preparation method of magnesium base composite material it is characterised in that：Comprise the following steps：
1.1) prepare magnesium alloy powder
By magnesium metal and other metals and/or nonmetallic mix homogeneously, melting in vacuum or protective gas atmosphere, prepare
Magnesium alloy compound MgXMY, magnesium alloy chemical compound is crushed and is prepared into magnesium alloy powder, wherein, M represents other metals and/or non-
Metal, X is the molal quantity of magnesium, and Y is other metals and/or nonmetallic total molal quantity,
1.2) prepare magnesium alloy/graphene nanocomposite material
1.3) prepare the magnesium alloy/graphene nanocomposite material of oxide cladding
1.3.1) salt and/or ester are dissolved in water and the mixed solution of alcohol, under intense agitation, are passed through lazy in the solution
Property gas, remove solution in dissolving oxygen and carbon dioxide,
1.3.2) in inert gas atmosphere, under intense agitation, by step 1.2) magnesium alloy/Graphene of preparing
Composite adds solution, the suspension of prepared mix homogeneously；In inert gas atmosphere, under intense agitation, slowly
Dropwise Deca ammonia, makes ammonia and soluble-salt and/or ester react and generates hydroxide precipitation, be uniformly coated on magnesium and close
Gold/graphene composite material surface,
1.3.3) by step 1.3.2) solution for preparing filters in inert gas atmosphere, obtains the magnesium of hydroxide cladding
Alloy/graphite alkene composite, with washing with alcohol for several times, will be multiple for the magnesium alloy/Graphene obtaining hydroxide cladding after washing
Condensation material is calcined in an inert atmosphere and is cooled to room temperature, obtains the magnesium alloy/graphene nanocomposite material of oxide cladding.
2. magnesium base composite material according to claim 1 preparation method it is characterised in that：
Step 1.1) in other metals be cobalt, nickel, lead, copper, silver, gold, aluminum, titanium, vanadium, zinc, germanium, molybdenum, indium, antimony, bismuth, barium, tungsten,
One or more of palladium, niobium, zirconium and gallium；
Other nonmetallic for one or more of boron, carbon, nitrogen, silicon, p and ses；
Smelting temperature is 500～1000 DEG C, and protective gas is one or more of nitrogen, helium and argon.
3. magnesium base composite material according to claim 2 preparation method it is characterised in that：
Step 1.2) in graphene powder be using improve Hummers method preparation；Magnesium alloy and the quality of graphene powder
Than for 100:30～1.
4. the magnesium base composite material according to one of claims 1 to 3 preparation method it is characterised in that：
Step 1.3.1) in salt be one or more of water-soluble sulfate, nitrate and acetate；The sun of salt from
Son is one or more of aluminum, titanium, magnesium, zinc, stannum, zirconium, cobalt, nickel, copper, tungsten, gallium and yttrium,
Described alcohol includes one or more of ethanol, propanol, isopropanol, butanol, isobutanol and ethylene glycol；Described water and alcohol
Volume ratio is 100～40:1～60,
Described noble gases are one or more of nitrogen, helium and argon,
It is passed through noble gases, the time removing the oxygen of dissolving and carbon dioxide in solution is 1～10 hour in solution,
Step 1.3.2) in Deca ammonia amount be that ammonia and anions in solution generate hydroxide molal quantity 1～2 times,
Step 1.3.3) in calcining heat be 150～500 DEG C,
The mass ratio of described magnesium alloy/graphene nanocomposite material and oxide is 100:20～0.1.
5. the magnesium base composite material prepared by one of Claims 1 to 4 methods described in lead-acid battery as battery-active material
Expect and prepare the application as both positive and negative polarity pole plate active material during lead-acid battery.
6. a kind of preparation method of ultralow temperature long life high capacity magnesio lead-acid accumulator it is characterised in that：
In the lead plaster of the positive plate preparing lead-acid accumulator and negative plate, all add in positive plate lead paste and negative plate lead plaster
A kind of active substance, this active substance is magnesium base composite material, the preparation method such as Claims 1-4 of this magnesium base composite material
One of described.
7. the preparation method of a kind of ultralow temperature long life high capacity magnesio lead-acid accumulator according to claim 6, it is special
Levy and be：
The raw material of described positive plate lead paste also includes in addition to magnesium base composite material：Hydrocerussitum (Ceruse), Lead oxide brown, four basic lead sulphates, short
Fiber, graphite, sulfate, sulphuric acid, politef and water；
The raw material of negative plate lead plaster also includes in addition to magnesium base composite material：Hydrocerussitum (Ceruse), Lead oxide brown, four basic lead sulphates, chopped fiber,
Graphite, sulfate, sulphuric acid, politef and water；
Sulfate in both positive and negative polarity pole plate lead plaster is magnesium sulfate, cobaltous sulfate, barium sulfate, copper sulfate, stannous sulfate, potassium sulfate and sulfur
One or more of sour sodium；
Chopped fiber in both positive and negative polarity pole plate lead plaster is one of polypropylene chopped fiber peacekeeping polyester staple fiber or two kinds.
8. the preparation method of a kind of ultralow temperature long life high capacity magnesio lead-acid accumulator according to claim 7, it is special
Levy and be：
Each constituent mass percentage ratio in described anode plate lead plaster raw material is：Magnesium base composite material 1～20%, Hydrocerussitum (Ceruse) 1～
6%th, Lead oxide brown 60～65%, four basic lead sulphates 1～7%, chopped fiber 0.001～1%, graphite 0.001～1%, sulphuric acid
Magnesium 0.01～3%, cobaltous sulfate 0.01～1%, barium sulfate 0.01～1%, copper sulfate 0.01～2%, stannous sulfate 0.01～
1%th, potassium sulfate 0.01～2%, sodium sulfate 0.01～2%, sulphuric acid 3～10%, politef 0.01～0.1%, water 5～
15%；
Each constituent mass percentage ratio of described negative plate lead plaster is：Magnesium base composite material 1～20%, Hydrocerussitum (Ceruse) 1～6%, titanium dioxide
Lead 60～66%, four basic lead sulphates 1～7%, chopped fiber 0.001～1%, graphite 0.001～1%, magnesium sulfate 0.01～
3%th, cobaltous sulfate 0.01～1%, barium sulfate 0.01～1%, copper sulfate 0.01～2%, stannous sulfate 0.01～1%, potassium sulfate
0.01～2%, sodium sulfate 0.01～2%, sulphuric acid 3～10%, politef 0.01～0.1%, water 5～15%.
9. the preparation side of a kind of ultralow temperature long life high capacity magnesio lead-acid accumulator according to one of claim 6～8
Method it is characterised in that：
The lead plaster coating plate of positive plate and negative plate is latticed metal grid, and latticed metal grid is lead calcium stannum aluminum
Conductive volume grating；
Prepare lead plaster solidification temperature when positive plate and negative plate and be 35～85 DEG C, solidification relative humidity is 85～98%, solidification
Time is 20～80 hours；Baking temperature is 20～80 DEG C, and it is 10～40% that relative humidity is dried, and drying time is little for 2～40
When.
10. the preparation method of a kind of ultralow temperature long life high capacity magnesio lead-acid accumulator according to claim 9, it is special
Levy and be：
Electrolyte each constituent mass percentage ratio of prepared battery is：Sulphuric acid 32%, water 60%, magnesium sulfate 1%, cobaltous sulfate 0.2
～2%, copper sulfate 0.1～1%, zinc sulfate 0.1～3%, aluminum sulfate 0.1～5%, potassium sulfate 0.1～2%, sodium sulfate 0.1～
2%th, ammonium sulfate 0.1～2%, disodiumedetate 0.2～3%.
A kind of 11. preparation methoies of ultralow temperature long life high capacity magnesio lead-acid accumulator according to claim 10, its
It is characterised by：
For after standing 4～6 hours after fluid injection, with 0.15C, 10A's chemical conversion condition of battery charges, and accumulator voltage stablizes 1～3
After hour, during change in voltage ± 0.03V, with 0.10C after standing, 10A is discharged to during accumulator voltage 10.5V and terminates electric discharge.
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| CN109585798A (en) * | 2017-09-29 | 2019-04-05 | 超威电源有限公司 | Graphene lead composite material and its preparation method and application and anode diachylon, cathode lead plaster |
| CN108666577A (en) * | 2018-04-28 | 2018-10-16 | 骆驼集团襄阳蓄电池有限公司 | A kind of lead-acid battery suitable for PHEV |
| CN112271274B (en) * | 2020-11-06 | 2022-03-29 | 大连理工大学 | High-safety and high-energy quasi-solid lithium secondary battery based on lithium sulfide anode and preparation method thereof |
| CN113540701B (en) * | 2021-06-28 | 2023-08-04 | 天能电池集团股份有限公司 | Lead storage battery wiring terminal and preparation method thereof |
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