CN103259009A - Water system alkaline metal ion electrochemical energy-storing device - Google Patents
Water system alkaline metal ion electrochemical energy-storing device Download PDFInfo
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- CN103259009A CN103259009A CN2013101358599A CN201310135859A CN103259009A CN 103259009 A CN103259009 A CN 103259009A CN 2013101358599 A CN2013101358599 A CN 2013101358599A CN 201310135859 A CN201310135859 A CN 201310135859A CN 103259009 A CN103259009 A CN 103259009A
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- mno
- xli
- storing device
- water system
- sodium
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Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910021645 metal ion Inorganic materials 0.000 title abstract description 12
- 239000011572 manganese Substances 0.000 claims abstract description 76
- 239000011734 sodium Substances 0.000 claims abstract description 35
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 32
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011149 active material Substances 0.000 claims abstract description 23
- 239000006104 solid solution Substances 0.000 claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 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 abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 7
- 239000011029 spinel Substances 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 35
- 150000001340 alkali metals Chemical class 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 230000002441 reversible effect Effects 0.000 claims description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 229910021260 NaFe Inorganic materials 0.000 claims description 6
- 229910021314 NaFeO 2 Inorganic materials 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims description 6
- 229910015645 LiMn Inorganic materials 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 230000001052 transient effect Effects 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- -1 potassium halide Chemical class 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 229910010586 LiFeO 2 Inorganic materials 0.000 claims description 3
- 229910013716 LiNi Inorganic materials 0.000 claims description 3
- 229910013825 LiNi0.33Co0.33Mn0.33O2 Inorganic materials 0.000 claims description 3
- 229910012528 LiNi0.4Co0.4Mn0.2O2 Inorganic materials 0.000 claims description 3
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 claims description 3
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 claims description 3
- 229910018970 NaNi0.5Mn0.5O2 Inorganic materials 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 238000003487 electrochemical reaction Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- 235000007686 potassium Nutrition 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 235000015424 sodium Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 12
- 239000000243 solution Substances 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 abstract description 2
- 239000008247 solid mixture Substances 0.000 abstract 2
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 238000004146 energy storage Methods 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 229910001416 lithium ion Inorganic materials 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- 239000010953 base metal Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000012983 electrochemical energy storage Methods 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910015150 Ni1/3Co1/3Mn1/3(OH)2 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910012735 LiCo1/3Ni1/3Mn1/3O2 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015297 LiMg0.2Mn1.8O4 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 229910021311 NaFeO2 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229940061631 citric acid acetate Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
-
- 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
Abstract
The invention relates to a water system alkaline metal ion electrochemical energy-storing device. The water system electrochemical energy-storing device disclosed by the invention comprises an anode, a cathode, a membrane and a water-phase electrolyte containing alkaline metal ions, and is characterized in that an active material of the anode is an alkali-enriched metal manganese-based solid solution or composition with the formula of xA2MnO3.(1-x)AMO2, wherein A is selected from one or more of Li, Na and K, M is selected from one or more of Mn, Ni, Co, Cr, Al, Ru and Fe, and x is more than or equal to 0 and less than or equal to 1; the crystal structure of the active material of the anode, namely the alkali-enriched metal manganese-based solid solution or composition, contains a stratified structure or a spinel structure; the electrolyte is a water solution containing sodium or potassium salt; and the anode material can be subjected to stable charging/discharging circulation in the electrolyte. The water system alkaline metal electrochemical energy-storing device disclosed by the invention has the advantages of high capacity, low cost, safety and environmental friendliness, and can be used for energy-storing devices with various scales.
Description
Technical field
The present invention relates to a kind of aquo-base metal ion electrochemical energy storage device.
Background technology
Along with science and technology, economic and social development, the energy and environmental problem more and more receive publicity, energy aspect demand continues to rise suddenly and sharply, the shortage of fossil energy and make focus turn to wind energy, these renewable resources of solar energy to the destruction that environment causes, yet these regenerative resources are subjected to the influence of weather and time period bigger, have tangible instability, characteristics such as discontinuous and uncontrollable, need exploitation and build supporting electrical power storage (energy storage) device to guarantee continuity and the stability of generating electricity, powering.Therefore, extensive energy storage technology is the key of greatly developing renewable energy utilization such as solar energy, wind energy and intelligent grid.In all energy storage technologies, battery can be realized the efficient conversion between chemical energy and the electric energy, is a kind of energy storing technology of the best.The rechargeable pond is present most popular a kind of energy storage mode.Compare with other energy storage mode, electrochemical energy storage can adapt to different electrical network function needs, especially has advantage aspect integrated being incorporated into the power networks of wind-powered electricity generation, photoelectricity etc.For the popularization aspect of chargeable battery energy storage technology, there is this two challenge greatly.The firstth, exploitation has high voltage and a high-octane battery system, second be to use cost low, stable, to the complete close friend of environment, long-life battery system, to guarantee that electric energy is incorporated in the electrical network endlessly from renewable and clean energy resource.
At present, be used for the mode of large-scale power grid energy storage, in the case that actual cloth is built, still based on traditional lead-acid battery.But main materials such as the low life-span weak point of lead-acid battery cost, lead and the concentrated sulfuric acid cause severe contamination to environment, need to reclaim.Therefore, press for and find a kind of new technology that can substitute lead-acid battery.
Recent two decades comes, and the development of lithium-ion electric pool technology is increasingly mature, because its energy density is big, the output voltage height makes lithium ion battery also obtain fast development in the application of different field.But because lithium ion battery is with an organic solvent as electrolyte, caused manufacturing cost higher and inflammable and explosive potential safety hazard in use arranged thus.Chinese patent Granted publication CN1328818C discloses a kind of mixed aquo-lithium ion battery.Its operation principle is: to the battery of dressing up, at first must charge.In the charging process, lithium ion is deviate from from positive pole, and by electrolyte, lithium ion is adsorbed on the negative pole that materials such as activated carbon are made.In the discharge process, lithium ion desorption from the negative pole, by electrolyte, lithium ion embeds anodal.Charge and discharge process only relates to lithium ion in two interelectrode transfers.The positive electrode of this mixed aquo-lithium ion battery adopts LiMn
2O
4, LiCoO
2, LiCo
1/3Ni
1/3Mn
1/3O
2, LiMg
0.2Mn
1.8O
4Deng the material of can reversible embedding deviating from lithium ion, negative pole then adopts specific area at 1000m
2Active carbon, mesoporous carbon or carbon nano-tube etc. that/g is above.
In addition, along with the large-scale application of lithium ion battery, the demand of lithium can be increasing, because limited reserves in the earth's crust, causes the price of lithium material can be more and more higher.People begin to pay close attention to alkali metal such as the sodium with more cheap in recent years, and potassium or even alkaline-earth metal magnesium replace lithium and is used for energy storage device.The reserves of sodium in the earth's crust are very abundant, account for 2.74%, are the 6th to enrich element, and widely distributed, the cost of material that contains sodium is lower; And the electrochemical properties similar with lithium, the battery of sodium base becomes the alternative of lithium ion battery gradually.
Sodium sulphur and the Na/NiCl2 battery based on the sodium metal of early stage research, though have comparatively desirable energy density, but use the sodium of molten state as negative pole, therefore operating temperature needs the heat management system of supporting use great number and special solid ceramic electrolyte between 300～350 ℃.If the solid ceramic electrolyte is in case breakage forms short circuit in addition, the liquid potassium of high temperature will directly contact with sulphur, and violent exothermic reaction takes place, and produces 2000 ℃ high temperature, and bigger potential safety hazard is arranged.Based on these backgrounds and reason, the room temperature sodium-ion battery becomes people's research focus again.
Chinese patent publication number CN102027625A discloses a kind of water electrolyte electrochemical secondary energy sources storage device based on sodium ion, it comprises anode electrode, can make cathode electrode, the dividing plate that the sodium cation invertibity embeds and the water electrolyte that contains sodium cation, and wherein the initial activity cathode electrode material makes alkali metal ion take off the activated cathode electrode material of the alkali metal containing of embedding during being included in the initial charge of this device.This activated cathode electrode material can be the λ-MnO that mixes aluminium
2, NaMnO
2(birnessite structure), Na
2Mn
3O
7, NaFePO
4F, Na
0.44MnO
2This anode electrode comprises porous activated carbon, and electrolyte comprises sodium sulphate.
Chinese patent publication number CN1723578A discloses a kind of sodium-ion battery, comprises positive electrode, negative electrode and electrolyte.Positive electrode comprises a kind of electrochemical active material that can invertibity circulation sodium ion, and negative electrode comprises a kind of carbon that can embed the potassium sodium ion.This active material comprises the potassium transition metal phosphate.Transition metal comprises a kind of transition metal that is selected from vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), nickel (Ni), the titanium (Ti) and composition thereof.
Chinese patent publication number CN101241802A discloses a kind of asymmetric water system sodium/kalium ion battery capacitor, is made up of positive pole, negative pole, barrier film and electrolyte.Anodal active material is NaMnO
2, NaCoO
2, NaV
3O
8, NaVPO
4F and Na
2VOPO
4Positive electrode active materials and carbon black, binding agent are mixed, be coated on the nickel screen collector, be pressed into electrode after the oven dry.Active carbon is mixed with conductive agent and binding agent, be uniformly coated on the nickel screen collector, be pressed into electrode after the oven dry.Adopt nonwoven fabrics as barrier film, as electrolyte, be assembled into battery with sodium chloride or sodium sulphate.
But, what more than be studied has spinel structure and birnessite structure manganate or has the phosphate cathode material of nucleocapsid structure, although its theoretical specific capacity is many more than 100mAh/g, but the specific capacity effective capable of circulation in containing the aqueous solution of sodium/potassium ion is all below 100mAh/g, cause the energy density of device on the low side, become the bottleneck that sodium/potassium ion energy storage technology is promoted, need the novel anode material that exploitation has high power capacity badly, thereby improve the energy density of sodium/potassium energy storage device.
Summary of the invention
In order to develop a kind of high power capacity, low cost, safety, environment-friendly type water system energy storage device, the invention provides a kind of aquo-base metal ion electrochemical energy storage device, the water electrolyte that comprises positive pole, negative pole, barrier film and alkali metal containing ion, it is characterized in that this anodal active material is for having general formula xA
2MnO
3(1-x) AMO
2Rich alkali metal manganese based solid solution or compound, wherein A is selected from one or more among Li, Na and the K; M is selected from one or more among transient metal Mn, Ni, Co, Cr, Al, Ru and the Fe; 0≤x≤1, the rich alkali-metal manganese based solid solution of the active material of described positive pole or the crystal structure of compound contain layer structure or spinel structure, and Stability Analysis of Structures, and described electrolyte is the aqueous solution that contains sodium or sylvite; Described positive electrode can carry out stable charge and discharge cycles in described electrolyte.
In aquo-base metal ion energy storage device of the present invention, the active material of described positive pole is for having general formula xA
2MnO
3(1-x) AMO
2Rich alkali metal manganese-based compound in, in the mixed layer of transition metal and alkali metal, alkali metal and transition metal form the orderly arrangement of superlattice structure.This material can be A
2MnO
3Component and AMO
2The two forms stable rich alkali-metal manganese basic unit shape solid solution component, thereby improves layer structure AMO
2Structural stability in circulation.In addition, this material also can be A
2MnO
3Component and AMO
2The compound that the two-phase of component on nanoscale evenly mixes, wherein AMO
2Contain spinel structure.
In aquo-base metal ion energy storage device of the present invention, the active material of described negative pole can be selected from one or more in active carbon, Graphene, carbon nano-tube, carbon fiber and the mesoporous carbon, these materials all are to carry out non-faraday's electric double layer electronics adsorption process by big surface area, form with positive pole and mix capacitor batteries.Also can be selected from the material of the reversible redox reaction that can in water electrolyte, contain faraday's electronics transfer process.This type of material comprises that alkali metal ion can reversible embedding and take off oxide, the phosphate material of embedding.Be also included within the metal or alloy material that aqueous phase can carry out reversible dissolving and deposition reaction.The reversible redox reaction potential of the negative material that the above-mentioned reversible redox that can contain faraday's electronics transfer process in water electrolyte reacts can not be lower than the hydrogen-evolution overpotential of this water electrolyte, to avoid discharging and recharging owing to the device that generation was caused of this irreversible electrochemical reaction of evolving hydrogen reaction the decline of coulombic efficiency.
In aquo-base metal ion energy storage device of the present invention, the rich alkali metal manganese based solid solution of described positive electrode or the crystal structure of compound contain layer structure or spinel structure.This richness alkali metal manganese based solid solution or compound are selected from xLi
2MnO
3(1-x) LiCrO
2, xLi
2MnO
3(1-x) LiFeO
2, xLi
2MnO
3(1-x) LiMn
2O
4, xLi
2MnO
3(1-x) LiNi
0.5Mn
0.5O
2, xLi
2MnO
3(1-x) LiNi
2/3Mn
1/3O
2, xLi
2MnO
3(1-x) LiFe
0.5Ni
0.5O
2, xLi
2MnO
3(1-x) LiNi
0.33Co
0.33Mn
0.33O
2, xLi
2MnO
3(1-x) LiNi
0.4Co
0.4Mn
0.2O
2, xLi
2MnO
3(1-x) LiNi
0.5Co
0.2Mn
0.3O
2, xLi
2MnO
3(1-x) NaCrO
2, xLi
2MnO
3(1-x) NaFeO
2, xLi
2MnO
3(1-x) NaNi
0.5Mn
0.5O
2, xLi
2MnO
3(1-x) NaNi
0.33Co
0.33Mn
0.33O
2, xLi
2MnO
3(1-x) NaNi
0.4Co
0.4Mn
0.2O
2, xLi
2MnO
3(1-x) NaNi
0.5Co
0.2Mn
0.3O
2, xLi
2MnO
3(1-x) NaFe
0.5Mn
0.5O
2, xNa
2MnO
3(1-x) NaFeO
2, xNa
2MnO
3(1-x) NaFe
0.5Mn
0.5O
2, xLi
2MnO
3(1-x) KNi
0.33Co
0.33Mn
0.33O
2, xLi
2MnO
3(1-x) KNi
0.5Co
0.2Mn
0.3O
2, xLi
2MnO
3(1-x) KNi
0.4Co
0.4Mn
0.2O
2, xLi
2MnO
3(1-x) KNi
0.5Mn
0.5O
2In (0≤x≤1) one or more, or the material that coated by metal oxide, nonmetal oxide of above-mentioned rich alkali metal manganese based solid solution or compound.The metal or the nonmetal oxide that wherein are used for coating comprise Al
2O
3, TiO
2, ZnO, CeO
2, MgO, ZrO
2Deng.
In aquo-base metal ion energy storage device of the present invention, the rich alkali metal manganese based solid solution of described positive electrode has general formula xA
2MnO
3(1-x) AMO
2, wherein A is selected from one or more among Li, Na and the K; M is selected from one or more among transient metal Mn, Ni, Co, Cr, Al, Ru and the Fe; 0≤x≤1.This richness alkali metal manganese based solid solution material can obtain by methods such as coprecipitation, sol-gal process, solid phase method, hydro thermal method are synthetic.Wherein the maximum characteristics of solid phase method and coprecipitation are to be convenient to industrialization, are applicable to that cost is regarded as the energy storage material field of popularization and application bottleneck.
In aquo-base metal ion energy storage device of the present invention, the rich alkali metal manganese based solid solution of described positive electrode has general formula xA
2MnO
3(1-x) AMO
2, wherein A is selected from one or more among Li, Na and the K; M is selected from one or more among transient metal Mn, Ni, Co, Cr, Al, Ru and the Fe; 0≤x≤1.This material structure can characterize with X-ray diffractometer, and its XRD spectrum can belong to for space group and is
The α of type-NaFeO2 type layer structure.Wherein, the diffraction maximum of the angle of diffraction between 20 °-28 ° is that the superlattice of alkali metal ion and transition metal ions are arranged in order and caused.The alkali metal that does not enter lattice remains in particle surface, can wash off through washing.The ratio of alkali metal and transition metal can be surveyed wherein alkali metal and transition metal content in the rich alkali metal manganese based solid solution material after washing, and namely provable alkali metal has entered intracell.
In aquo-base metal ion energy storage device of the present invention, described water electrolyte is including but not limited to one or more mixed liquors in sodium sulphate, sodium nitrate, sodium halide, sodium carbonate, sodium phosphate, sodium acetate, NaOH, sodium perchlorate, potassium sulfate, potassium nitrate, potassium halide, potash, potassium phosphate, potassium acetate, potassium hydroxide, the potassium hyperchlorate.Concentration of electrolyte is 0.5-10mol.L
-1, the pH value is between 3-12.
Low in order to solve existing room temperature water system alkali metal ion cell positive material energy density, the problem that performance is performed poor the invention provides a kind of rich alkali metal manganese based solid solution or compound positive electrode.Rich alkali metal manganese based solid solution of the present invention or compound have general formula xA
2MnO
3(1-x) AMO
2, wherein A is selected from one or more among Li, Na and the K; M is selected from one or more among transient metal Mn, Ni, Co, Cr, Al, Ru and the Fe; 0≤x≤1.Particularly, rich alkali metal manganese based solid solution or the compound of described positive electrode are selected from xLi
2MnO
3(1-x) LiCrO
2, xLi
2MnO
3(1-x) LiFeO
2, xLi
2MnO
3(1-x) LiMn
2O
4, xLi
2MnO
3(1-x) LiNi
0.5Mn
0.5O
2, xLi
2MnO
3(1-x) LiNi
2/3Mn
1/3O
2, xLi
2MnO
3(1-x) LiFe
0.5Ni
0.5O
2, xLi
2MnO
3(1-x) LiNi
0.33Co
0.33Mn
0.33O
2, xLi
2MnO
3(1-x) LiNi
0.4Co
0.4Mn
0.2O
2, xLi
2MnO
3(1-x) LiNi
0.5Co
0.2Mn
0.3O
2, xLi
2MnO
3(1-x) NaCrO
2, xLi
2MnO
3(1-x) NaFeO
2, xLi
2MnO
3(1-x) NaNi
0.5Mn
0.5O
2, xLi
2MnO
3(1-x) NaNi
0.33Co
0.33Mn
0.33O
2, xLi
2MnO
3(1-x) NaNi
0.4Co
0.4Mn
0.2O
2, xLi
2MnO
3(1-x) NaNi
0.5Co
0.2Mn
0.3O
2, xLi
2MnO
3(1-x) NaFe
0.5Mn
0.5O
2, xNa
2MnO
3(1-x) NaFeO
2, xNa
2MnO
3(1-x) NaFe
0.5Mn
0.5O
2, xLi
2MnO
3(1-x) KNi
0.33Co
0.33Mn
0.33O
2, xLi
2MnO
3(1-x) KNi
0.5Co
0.2Mn
0.3O
2, xLi
2MnO
3(1-x) KNi
0.4Co
0.4Mn
0.2O
2, xLi
2MnO
3(1-x) KNi
0.5Mn
0.5O
2In (0≤x≤1) one or more.The conductive agent (graphite, carbon black, acetylene black etc.) that described positive electrode also need add 5%-10% improves material conductivity, also need add the composite material that the binding agent (polytetrafluoroethylene, Kynoar etc.) of 5%-10% is made evenly, had viscosity simultaneously, again this composite material is fixed on the collector electrode by pressure or conducting resinl.Collector electrode includes stainless steel, nickel, titanium, graphite cake, carbon paper etc.
The active material of described positive pole is for having general formula xA
2MnO
3(1-x) AMO
2Rich alkali metal manganese based solid solution or compound, wherein said alkali metal A contains lithium (Li), and the described active material that contains the lithium positive pole before described water system electrochemical energy storing device assembling or after the assembling through chemistry or electrochemical alkali metal ion exchange processing.The active material that contains the lithium positive pole can be assembled the capable chemical treatment of advancing at device, is active material to be positioned in the dilute acid soln soak, thereby lithium ion is broken away from.The active material that will contain the lithium positive pole carries out the exchange of electrochemistry alkali metal ion to be handled, be that active material is placed the electrochemical cell that contains sodium or potassium salt soln, in the certain voltage scope, carry out long-time charge and discharge cycles, lithium ion is taken off from the structure of positive electrode, and the structure that makes sodium or potassium ion enter into positive electrode goes, thereby realizes the exchange between sodium or potassium ion and the lithium ion.The exchange of electrochemistry alkali metal ion is handled and can be assembled the row that advances at device, also can realize by discharging and recharging activation after the device assembling again.
The present invention will realize the application of alkali metal ion positive electrode in water alkali metal ion electrolyte easily, can reduce cost and improve the device security energy.
Description of drawings
Fig. 1 is that positive electrode is 0.16Li in the embodiment of the invention 1
2MnO
30.84LiNi
0.4Co
0.4Mn
0.2O
2, negative material is the structure chart of the energy storage device of active carbon.
Fig. 2 is that positive electrode is 0.16Li in the embodiment of the invention 1
2MnO
30.84LiNi
0.4Co
0.4Mn
0.2O
2, mix capacitor batteries at 1M Na with activated carbon negative electrode is formed
2SO
4Charging and discharging curve in the aqueous solution.
Fig. 3 is that positive electrode is 0.16Li in the embodiment of the invention 1
2MnO
30.84LiNi
0.4Co
0.4Mn
0.2O
2, mix capacitor batteries at 0.5M K with activated carbon negative electrode is formed
2SO
4Charging and discharging curve in the aqueous solution.
Fig. 4 is that positive electrode is 0.4Li in the embodiment of the invention 2
2MnO
30.6LiNi
2/3Mn
1/3O
2, mix capacitor batteries at 1M Na with activated carbon negative electrode is formed
2SO
4Charging and discharging curve in the aqueous solution.
Fig. 5 is that positive electrode is 0.4Li in the embodiment of the invention 2
2MnO
30.6LiNi
2/3Mn
1/3O
2X-ray powder diffraction (XRD) figure.
Embodiment
The present invention will carry out more detailed description by specific embodiment, but protection scope of the present invention is not limited to these embodiment.
Embodiment 1
Positive electrode active materials adopts the synthetic nickel cobalt manganese composite hydroxide presoma of coprecipitation, then with Li
2CO
3Mixing the back obtains in high-temperature calcination.It is the metal mixed solution of 2mo1/L that nickelous sulfate, manganese chloride, cobalt chloride are prepared nickel cobalt manganese total concentration, and wherein the Mn:Ni:Co mol ratio is 1:1:1; Adopt solid piece alkali configuration 5mo1/L sodium hydroxide solution; Adopt ammoniacal liquor configuration 100g/L solution; Above-mentioned three kinds of solution while and stream are passed in the reactor, and temperature of reaction kettle is controlled at 65 ℃, the constant flow of metallic solution and ammoniacal liquor, the pH value 10-11 of sodium hydroxide solution flow control system; Adopt the vacuum filtration machine washing to wash the powder product of precipitation preparation, 110 ℃ of oven dry obtain Ni
1/3Co
1/3Mn
1/3(OH)
2Presoma.With Ni
1/3Co
1/3Mn
1/3(OH)
2And Li
2CO
3According to Li/ (Ni+Mn+Co)=1.16:1 mol ratio proportioning weighing, the weighing material is placed in the ball mill with 150rpm ball milling 10h then.The material that acquisition mixes places box type furnace, is warming up to 900 ℃ of insulation 10h with 2 ℃/min, naturally cools to room temperature then, and grinds through pulverizing, and makes 0.16Li
2MnO
30.84LiNi
0.4Co
0.4Mn
0.2O
2Dusty material.Positive electrode is according to 0.16Li
2MnO
30.84LiNi
0.4Co
0.4Mn
0.2O
2: acetylene black: the mass ratio of PTFE binding agent=80:10:10 evenly mixes, and with the mixture roll-in or roll on the stainless (steel) wire, makes the thick electrode slice of 0.2mm then after the oven dry.Negative material adopts business-like active carbon, and according to active carbon: conductive black: the mass ratio of PTFE binding agent=80:10:10 evenly mixes, and with the mixture roll-in or roll on the stainless (steel) wire, makes the thick electrode slice of 1mm then after the oven dry.Then the both positive and negative polarity electrode is cut according to specification, matched group is dressed up the CR2032 button cell, the PP base barrier film that barrier film adopts hydrophilic treated to cross, and electrolyte is the Na of 1M
2SO
4Or 0.5M K
2SO
4The aqueous solution, battery structure are as shown in Figure 1.The Reversible Cycle charging and discharging curve is respectively shown in Fig. 2,3.At the voltage range of 0.2V-1.8V, charging and discharging currents is 0.1C, at Na
2SO
4And K
2SO
4The specific capacity of the discharge of Reversible Cycle is respectively 123.5mAh/g, 133.5mAh/g in the aqueous solution.
Embodiment 2
Positive electrode active materials adopts sol-gal process to synthesize, stoichiometric proportion according to manganese acetate and nickel acetate is that 3:2 takes by weighing manganese acetate respectively, nickel acetate is dissolved in the appropriate amount of deionized water, mixture is placed in 80 ℃ of waters bath with thermostatic control stirs, slowly drip the mixed solution of lithium acetate and citric acid then, the mol ratio of lithium acetate and manganese acetate, nickel acetate is 1.47:0.6:0.4, and the mol ratio of citric acid and manganese acetate, nickel acetate is 1:1:1.Dripping off the back is 7.0-8.0 with ammoniacal liquor adjusting pH.Be incubated 80 ℃ until solution formation gel state, be dried back pre-burning 10h in 450 ℃ of air atmospheres, in air atmosphere, calcine 10h behind the grinding compressing tablet again under 900 ℃, be quickly cooled to room temperature, obtain 0.4Li
2MnO
30.6LiNi
2/3Mn
1/3O
2Dusty material.Positive electrode is according to 0.4Li
2MnO
30.6LiNi
2/3Mn
1/3O
2: acetylene black: the mass ratio of PTFE binding agent=80:10:10 evenly mixes, and with the mixture roll-in or roll on the stainless (steel) wire, makes the thick electrode slice of 0.2mm then after the oven dry.Negative material adopts business-like active carbon, and according to active carbon: conductive black: the mass ratio of PTFE binding agent=80:10:10 evenly mixes, and with the mixture roll-in or roll on the stainless (steel) wire, makes the thick electrode slice of 1mm then after the oven dry.Then the both positive and negative polarity electrode is cut according to specification, matched group is dressed up the CR2032 button cell, the PP base barrier film that barrier film adopts hydrophilic treated to cross, and electrolyte is the Na of 1M
2SO
4The aqueous solution, charging and discharging curve are as shown in Figure 4.At the voltage range of 0.2V-1.8V, charging and discharging currents is 0.1C, at Na
2SO
4The specific capacity of the discharge of Reversible Cycle is 90.7mAh/g in the aqueous solution.Fig. 5 is 0.4Li
2MnO
30.6LiNi
2/3Mn
1/3O
2X-ray powder diffraction (XRD) figure.
Following table 1 is different rich alkali metal manganese-based compound and transition metal oxide (LiMn
2O
4And Na
0.44MnO
2) the comparison of Reversible Cycle specific discharge capacity in containing the aqueous solution that Na, karat gold belong to salt.Wherein the active material of negative material is active carbon.Charging and discharging currents (multiplying power) is 0.1C, and the charging/discharging voltage interval is 0.2-1.8V.
Table 1
Though described the present invention in the mode of embodiment, but be apparent that to those skilled in the art, under the situation that does not break away from the spirit and scope of the present invention that appended claims limits, can carry out variations and modifications to the present invention, these variations and modification comprise within the scope of the invention equally.
Claims (10)
1. water system electrochemical energy storing device comprises the water electrolyte of positive pole, negative pole, barrier film and alkali metal containing ion it is characterized in that this anodal active material is for having general formula xA
2MnO
3(1-x) AMO
2Rich alkali metal manganese based solid solution or compound, wherein A is selected from one or more among Li, Na and the K; M is selected from one or more among transient metal Mn, Ni, Co, Cr, Al, Ru and the Fe; 0≤x≤1, the rich alkali-metal manganese based solid solution of the active material of described positive pole or the crystal structure of compound contain layer structure or spinel structure; Described electrolyte is the aqueous solution that contains sodium or sylvite; Described positive electrode can carry out stable charge and discharge cycles in described electrolyte.
2. water system electrochemical energy storing device according to claim 1 is characterized in that, the active material of described positive pole is for having general formula xA
2MnO
3(1-x) AMO
2Rich alkali metal manganese based solid solution, its crystal structure contains layer structure.
3. water system electrochemical energy storing device according to claim 1 is characterized in that, the active material of described positive pole is for having general formula xA
2MnO
3(1-x) AMO
2Rich alkali metal manganese-based compound, its crystal structure contains spinel structure.
4. water system electrochemical energy storing device according to claim 1 is characterized in that, the active material of described positive pole is for having general formula xA
2MnO
3(1-x) AMO
2Rich alkali metal manganese based solid solution or compound, wherein said alkali metal A contains lithium, and the described active material that contains the lithium positive pole before described water system electrochemical energy storing device assembling or after the assembling through chemistry or electrochemical alkali metal ion exchange processing.
5. water system electrochemical energy storing device according to claim 1 is characterized in that, described negative material comprise at least a kind of can be in water electrolyte with sodium ion or/and potassium ion carries out the material of reversible electrochemical reaction.
6. water system electrochemical energy storing device according to claim 1 is characterized in that, described negative material comprises at least a kind ofly can carry out sodium ion or/and potassium ion embeds and takes off the material of embedding in water electrolyte.
7. water system electrochemical energy storing device according to claim 1 is characterized in that, the active material of described negative pole is selected from one or more materials in active carbon, Graphene, carbon nano-tube, carbon fiber and the mesoporous carbon.
8. water system electrochemical energy storing device according to claim 1 is characterized in that, described water electrolyte includes one or more in sodium salt, the sylvite electrolyte.
9. water system electrochemical energy storing device according to claim 1, it is characterized in that described water electrolyte is selected from one or more in sodium sulphate, sodium nitrate, sodium halide, sodium carbonate, sodium phosphate, sodium acetate, NaOH, sodium perchlorate, potassium sulfate, potassium nitrate, potassium halide, potash, potassium phosphate, potassium acetate, potassium hydroxide, the potassium hyperchlorate.
10. water system electrochemical energy storing device according to claim 1 is characterized in that, described rich alkali metal manganese based solid solution or compound are selected from xLi
2MnO
3(1-x) LiCrO
2, xLi
2MnO
3(1-x) LiFeO
2, xLi
2MnO
3(1-x) LiMn
2O
4, xLi
2MnO
3(1-x) LiNi
0.5Mn
0.5O
2, xLi
2MnO
3(1-x) LiNi
2/3Mn
1/3O
2, xLi
2MnO
3(1-x) LiFe
0.5Ni
0.5O
2, xLi
2MnO
3(1-x) LiNi
0.33Co
0.33Mn
0.33O
2, xLi
2MnO
3(1-x) LiNi
0.4Co
0.4Mn
0.2O
2, xLi
2MnO
3(1-x) LiNi
0.5Co
0.2Mn
0.3O
2, xLi
2MnO
3(1-x) NaCrO
2, xLi
2MnO
3(1-x) NaFeO
2, xLi
2MnO
3(1-x) NaNi
0.5Mn
0.5O
2, xLi
2MnO
3(1-x) NaNi
0.33Co
0.33Mn
0.33O
2, xLi
2MnO
3(1-x) NaNi
0.4Co
0.4Mn
0.2O
2, xLi
2MnO
3(1-x) NaNi
0.5Co
0.2Mn
0.3O
2, xLi
2MnO
3(1-x) NaFe
0.5Mn
0.5O
2, xNa
2MnO
3(1-x) NaFeO
2, xNa
2MnO
3(1-x) NaFe
0.5Mn
0.5O
2, xLi
2MnO
3(1-x) KNi
0.33Co
0.33Mn
0.33O
2, xLi
2MnO
3(1-x) KNi
0.5Co
0.2Mn
0.3O
2, xLi
2MnO
3(1-x) KNi
0.4Co
0.4Mn
0.2O
2, xLi
2MnO
3(1-x) KNi
0.5Mn
0.5O
2In (0≤x≤1) one or more, or the material that coated by metal oxide, nonmetal oxide of above-mentioned rich alkali metal manganese based solid solution or compound.
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| CN201310135859.9A CN103259009B (en) | 2013-04-18 | 2013-04-18 | A kind of water-system alkali metal ion electrochemical energy storing device |
| PCT/CN2014/070718 WO2014169717A1 (en) | 2013-04-18 | 2014-01-16 | Electrochemical energy storage device of aqueous alkali metal ions |
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| CN201310135859.9A CN103259009B (en) | 2013-04-18 | 2013-04-18 | A kind of water-system alkali metal ion electrochemical energy storing device |
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Cited By (9)
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| CN103531778A (en) * | 2013-10-28 | 2014-01-22 | 北京理工大学 | Solid solution sodium-ion battery positive material and preparation method therefor |
| CN103854877A (en) * | 2013-12-23 | 2014-06-11 | 燕山大学 | Self-supporting grapheme-manganese oxide combined electrode material and manufacturing method thereof |
| WO2014169717A1 (en) * | 2013-04-18 | 2014-10-23 | 恩力能源科技（南通）有限公司 | Electrochemical energy storage device of aqueous alkali metal ions |
| CN105226264A (en) * | 2014-06-16 | 2016-01-06 | 北京理工大学 | Rich sodium positive electrode of a kind of sodium-ion battery and preparation method thereof and sodium-ion battery |
| CN106602054A (en) * | 2016-12-26 | 2017-04-26 | 东北大学 | Lithium ion battery positive electrode material and preparation method and application thereof |
| CN106800312A (en) * | 2017-03-08 | 2017-06-06 | 济南大学 | A kind of preparation method for sodium-ion battery positive material manganous acid sodium |
| CN107403915A (en) * | 2017-07-13 | 2017-11-28 | 南京大学 | The manganese-based anode material of sodium-ion battery |
| CN107871861A (en) * | 2017-05-15 | 2018-04-03 | 中国科学院金属研究所 | A kind of water system sodium ion electrochemical energy storage device |
| CN109546115A (en) * | 2018-11-19 | 2019-03-29 | 安徽安凯汽车股份有限公司 | A kind of NCA ternary battery of nickelic rich lithium manganese base solid solution positive electrode |
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| WO2014169717A1 (en) * | 2013-04-18 | 2014-10-23 | 恩力能源科技（南通）有限公司 | Electrochemical energy storage device of aqueous alkali metal ions |
| CN103531778A (en) * | 2013-10-28 | 2014-01-22 | 北京理工大学 | Solid solution sodium-ion battery positive material and preparation method therefor |
| CN103854877A (en) * | 2013-12-23 | 2014-06-11 | 燕山大学 | Self-supporting grapheme-manganese oxide combined electrode material and manufacturing method thereof |
| CN105226264A (en) * | 2014-06-16 | 2016-01-06 | 北京理工大学 | Rich sodium positive electrode of a kind of sodium-ion battery and preparation method thereof and sodium-ion battery |
| CN105226264B (en) * | 2014-06-16 | 2018-12-14 | 北京理工大学 | A kind of sodium-ion battery richness sodium positive electrode and preparation method thereof and sodium-ion battery |
| CN106602054A (en) * | 2016-12-26 | 2017-04-26 | 东北大学 | Lithium ion battery positive electrode material and preparation method and application thereof |
| CN106602054B (en) * | 2016-12-26 | 2019-08-16 | 东北大学 | Kalium ion battery positive electrode and preparation method thereof, application |
| CN106800312A (en) * | 2017-03-08 | 2017-06-06 | 济南大学 | A kind of preparation method for sodium-ion battery positive material manganous acid sodium |
| CN107871861A (en) * | 2017-05-15 | 2018-04-03 | 中国科学院金属研究所 | A kind of water system sodium ion electrochemical energy storage device |
| CN107403915A (en) * | 2017-07-13 | 2017-11-28 | 南京大学 | The manganese-based anode material of sodium-ion battery |
| CN109546115A (en) * | 2018-11-19 | 2019-03-29 | 安徽安凯汽车股份有限公司 | A kind of NCA ternary battery of nickelic rich lithium manganese base solid solution positive electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103259009B (en) | 2019-06-14 |
| WO2014169717A1 (en) | 2014-10-23 |
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