CN103259009B - A kind of water-system alkali metal ion electrochemical energy storing device - Google Patents
A kind of water-system alkali metal ion electrochemical energy storing device Download PDFInfo
- Publication number
- CN103259009B CN103259009B CN201310135859.9A CN201310135859A CN103259009B CN 103259009 B CN103259009 B CN 103259009B CN 201310135859 A CN201310135859 A CN 201310135859A CN 103259009 B CN103259009 B CN 103259009B
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- China
- Prior art keywords
- alkali metal
- mno
- sodium
- anode
- energy storing
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- 229910001413 alkali metal ion Inorganic materials 0.000 title claims abstract description 20
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims abstract description 65
- 239000011572 manganese Substances 0.000 claims abstract description 54
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 36
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 28
- 239000011734 sodium Substances 0.000 claims abstract description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011149 active material Substances 0.000 claims abstract description 23
- 239000006104 solid solution Substances 0.000 claims abstract description 20
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- 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 14
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 7
- 239000011029 spinel Substances 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- 239000001103 potassium chloride Substances 0.000 claims abstract description 4
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 230000002441 reversible effect Effects 0.000 claims description 10
- 229910001415 sodium ion Inorganic materials 0.000 claims description 10
- -1 potassium halide Chemical class 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 5
- 229910000651 0.4Li2MnO3 Inorganic materials 0.000 claims description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000003780 insertion Methods 0.000 claims description 4
- 230000037431 insertion Effects 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 235000007686 potassium Nutrition 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 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
- 238000012545 processing Methods 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
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 230000005611 electricity Effects 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
- 238000009831 deintercalation Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates 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
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 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
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical group [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 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
- 238000004146 energy storage Methods 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 8
- 239000002585 base Substances 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- 229910052804 chromium Inorganic materials 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 5
- 230000001052 transient effect Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 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
- 238000000034 method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910018434 Mn0.5O2 Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 229910052723 transition metal Inorganic materials 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
- 238000001035 drying Methods 0.000 description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 4
- 229910018416 Mn0.33O2 Inorganic materials 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 4
- 229910021311 NaFeO2 Inorganic materials 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 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
- 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
- 150000003624 transition metals Chemical class 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000000843 powder 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
- 229910011638 LiCrO2 Inorganic materials 0.000 description 2
- 229910010584 LiFeO2 Inorganic materials 0.000 description 2
- 229910013825 LiNi0.33Co0.33Mn0.33O2 Inorganic materials 0.000 description 2
- 229910012528 LiNi0.4Co0.4Mn0.2O2 Inorganic materials 0.000 description 2
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 description 2
- 229910014485 Na0.44MnO2 Inorganic materials 0.000 description 2
- 229910021271 NaCrO2 Inorganic materials 0.000 description 2
- 229910019338 NaMnO2 Inorganic materials 0.000 description 2
- 229910018970 NaNi0.5Mn0.5O2 Inorganic materials 0.000 description 2
- 229910015150 Ni1/3Co1/3Mn1/3(OH)2 Inorganic materials 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 229910032387 LiCoO2 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
- 229910021225 NaCoO2 Inorganic materials 0.000 description 1
- 229910021312 NaFePO4 Inorganic materials 0.000 description 1
- 229910019475 NaV3O8 Inorganic materials 0.000 description 1
- 229910001222 NaVPO4F Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 229910000540 VOPO4 Inorganic materials 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229940061631 citric acid acetate Drugs 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229910052593 corundum 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction 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
- 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
- 230000002427 irreversible effect Effects 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 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
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 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 compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 1
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of water-system alkali metal ion electrochemical energy storing devices.A kind of water system electrochemical energy storing device of the invention, the water phase electrolyte including anode, cathode, diaphragm and alkali metal containing ion, which is characterized in that the active material of the anode is with general formula xA2MnO3·(1‑x)AMO2Rich alkali metal manganese based solid solution or compound, wherein A is selected from one of Li, Na and K or a variety of；M is selected from one of transient metal Mn, Ni, Co, Cr, Al, Ru and Fe or a variety of；0≤x≤1, the richness alkali metal manganese based solid solution of the active material of the anode or the crystal structure of compound contain layer structure or spinel structure；The electrolyte is the aqueous solution containing sodium or sylvite；The positive electrode can carry out stable charge and discharge cycles in the electrolyte.Aquo-base electrochemical metal energy storage device of the invention, capacity is high, at low cost, safety and environmental protection, can be used in the energy storage device of various scales.
Description
Technical field
The present invention relates to a kind of water-system alkali metal ion electrochemical energy storing devices.
Background technique
With the development of science and technology, economy and society, energy and environmental problem more and more attention has been paid to hold in terms of the energy by demand
Continuous to rise suddenly and sharply, the shortage of fossil energy and the destruction caused by environment make focus turn to these renewable moneys of wind energy, solar energy
Source, however these renewable energy are affected by weather and period, are had apparent unstable, discontinuous and uncontrollable
The features such as, need to develop and build matched electric energy storage (energy storage) device to guarantee the stability of power generation, power supply.
Therefore, extensive energy storage technology is the key that greatly develop the renewable energy utilizations such as solar energy, wind energy and smart grid.Institute
In some energy storage technologies, the efficient conversion between chemical energy and electric energy is may be implemented in battery, is a kind of optimal energy storage skill
Art.Rechargeable pond is a kind of current most popular energy storage mode.Compared with other energy storage modes, electrochemical energy storage energy
Different power grid function needs are enough adapted to, especially there is advantage at the grid-connected aspect that integrates of wind-powered electricity generation, photoelectricity etc..For chargeable battery
For the popularization practical of energy storage technology, there are this two big challenges.First is the battery system that exploitation has high voltage and high-energy,
Second is that use cost is low, stable, completely friendly to environment, the long-life battery system, with guarantee endlessly electric energy from
It is integrated into power grid in renewable and clean energy resource.
Currently, being used for the mode of large-scale power grid energy storage, it is in the case that practical cloth is built, or with traditional lead-acid battery
It is main.The main materials such as lead-acid battery is at low cost but the service life is short, lead and the concentrated sulfuric acid cause seriously to pollute to environment, need to recycle.
Therefore, there is an urgent need to find a kind of new technology that can substitute lead-acid battery.
In the latest 20 years, the development of lithium ion battery technology is increasingly mature, and since its energy density is big, output voltage is high,
So that lithium ion battery is also grown rapidly in the application of different field.But since lithium ion battery uses organic solvent
As electrolyte, it is higher and have inflammable and explosive security risk in use manufacturing cost has been thereby resulted in.Chinese patent is awarded
Power notification number CN1328818C discloses a kind of mixed aquo-lithium ion battery.Its working principle is that: it is first to the battery dressed up
It must first charge.In charging process, lithium ion is deviate from from anode, and by electrolyte, lithium ion is adsorbed on the materials such as activated carbon
Expect the cathode being made into.In discharge process, lithium ion is desorbed from cathode, passes through electrolyte, lithium ion insertion anode.Charge and discharge
Journey only relates to lithium ion in two interelectrode transfers.The positive electrode of the mixed aquo-lithium ion battery uses LiMn2O4、
LiCoO2、LiCo1/3Ni1/3Mn1/3O2、LiMg0.2Mn1.8O4Etc. the material of insertion abjection lithium ion that can be reversible, cathode is then adopted
With specific surface area in 1000m2Active carbon, mesoporous carbon or carbon nanotube of/g or more etc..
In addition, with the large-scale application of lithium ion battery, the demand of lithium can be increasing, due to limited in the earth's crust
Reserves cause the price of lithium material can be higher and higher.People, which begin to focus on, in recent years uses more cheap alkali metal such as sodium, and potassium is very
Replace lithium for energy storage device to being alkaline-earth metal magnesium.Reserves of the sodium in the earth's crust are very rich, account for about 2.74%, are the 6th
Abundant element, widely distributed, the cost of material containing sodium is lower；And electrochemical properties similar with lithium, the battery of sodium base is gradually
Become the alternative of lithium ion battery.
The sodium sulphur and Na/NiCl2 battery based on sodium metal of early stage research, although having ideal energy density,
But the sodium of molten state is used as cathode, running temperature is between 300~350 DEG C, it is therefore desirable to match great number
Heat management system and special ceramiic solid electrolyte.In addition if ceramiic solid electrolyte is once damaged to form short circuit, high temperature
Liquid potassium and sulphur will directly contact, occur violent exothermic reaction, generate 2000 DEG C of high temperature, have biggish safety hidden
Suffer from.Based on these backgrounds and reason, room temperature sodium-ion battery becomes the research hotspot of people again.
China Patent Publication No. CN102027625A discloses a kind of water phase electrolyte electrochemical two based on sodium ion
Secondary energy storage device comprising anode electrode, partition and contains sodium at the cathode electrode that sodium cation invertibity can be made to be embedded in
Cation water phase electrolyte, wherein initial activity cathode electrode material include the device initial charge during make alkali metal
The activated cathode electrode material of the alkali metal containing of ion deinsertion.The activated cathode electrode material can be the λ-MnO for mixing aluminium2、
NaMnO2(birnessite structure), Na2Mn3O7、NaFePO4F、Na0.44MnO2.The anode electrode includes porous activated carbon, and electric
Solving matter includes sodium sulphate.
China Patent Publication No. CN1723578A discloses a kind of sodium-ion battery, including positive electrode, negative electrode and electrolysis
Matter.Positive electrode includes a kind of electrochemical active material for capableing of invertibity circulation sodium ion, and negative electrode includes that one kind can be embedded in
The carbon of kalium ion and natrium ion.The active material includes potassium transition metal phosphate.Transition metal includes being selected from vanadium (V), manganese (Mn), iron
(Fe), one of cobalt (Co), copper (Cu), nickel (Ni), titanium (Ti) transition metal and its mixture.
China Patent Publication No. CN101241802A discloses a kind of non symmetric water natrium/kalium ion battery capacitor,
It is made of anode, cathode, diaphragm and electrolyte.The active material of anode is NaMnO2、NaCoO2、NaV3O8、NaVPO4F and
Na2VOPO4.Positive electrode active materials are uniformly mixed with carbon black, binder, is coated on nickel screen collector, electricity is pressed into after drying
Pole.Active carbon is mixed with conductive agent and binder, is uniformly coated on nickel screen collector, electrode is pressed into after drying.Using nothing
Woven fabric uses sodium chloride or sodium sulphate as electrolyte, is assembled into battery as diaphragm.
But it is above studied with spinel structure and birnessite structure manganate or with the phosphorus of core-shell structure
Hydrochlorate positive electrode, it is effective in the aqueous solution containing sodium ions to potassium ions although its theoretical specific capacity is mostly in 100mAh/g or more
Recyclable specific capacity becomes the popularization of sodium ions to potassium ions energy storage technology in 100mAh/g hereinafter, cause the energy density of device relatively low
A bottleneck, need exploitation have high capacity novel anode material, to improve sodium/potassium energy storage device energy density.
Summary of the invention
In order to develop a kind of high capacity, low cost, safe and environment-friendly type water system energy storage device, the present invention provides a kind of water
It is alkali metal ion electrochemical energy storing device, the water phase electrolyte including anode, cathode, diaphragm and alkali metal containing ion is special
Sign is that the active material of the anode is with general formula xA2MnO3·(1-x)AMO2Rich alkali metal manganese based solid solution or compound
Object, wherein A is selected from one of Li, Na and K or a variety of；M is selected from one of transient metal Mn, Ni, Co, Cr, Al, Ru and Fe
Or it is a variety of；0≤x≤1, the manganese based solid solution of the richness alkali metal of the active material of the anode or the crystal structure of compound contain
Layer structure or spinel structure, and stable structure, the electrolyte are the aqueous solution containing sodium or sylvite；The positive electrode exists
Stable charge and discharge cycles can be carried out in the electrolyte.
In Water-system alkali metal ion power storage device of the invention, the active material of the anode is with general formula
xA2MnO3·(1-x)AMO2Rich alkali metal manganese-based compound in, in the mixed layer of transition metal element and alkali metal element,
Alkali metal and transition metal element form the ordered arrangement of superlattice structure.The material can be A2MnO3Component and AMO2Component
The two forms the manganese base layed solid-solution of stable rich alkali metal, so as to improve layer structure AMO2Stable structure in the circulating cycle
Property.In addition, the material is also possible to A2MnO3Component and AMO2Two-phase of the component on nanoscale is uniformly mixed compound
Object, wherein AMO2Contain spinel structure.
In Water-system alkali metal ion power storage device of the invention, the active material of the cathode can selected from active carbon,
One of graphene, carbon nanotube, carbon fiber and mesoporous carbon are a variety of, these materials are carried out illegally by big surface area
Electric double layer electron adsorption process is drawn, mixes capacitor batteries with anode composition.Can also selected from can in water phase electrolyte into
The material of Reversible redox reaction of the row containing faraday's electronic transfer process.Such material includes that alkali metal ion can
Oxide, the phosphate material of inverse insertion and deintercalation.Reversible dissolution and deposition reaction can be carried out by being also included in water phase
Metal or alloy material.It is above-mentioned that can to carry out the reversible redox containing faraday's electronic transfer process in water phase electrolyte anti-
The Reversible redox reaction current potential for the negative electrode material answered cannot be below the hydrogen-evolution overpotential of the water phase electrolyte, to avoid due to analysis
Hydrogen reacts the decline of device charge and discharge coulombic efficiency caused by the generation of this irreversible electrochemical reaction.
In Water-system alkali metal ion power storage device of the invention, the richness alkali metal manganese based solid solution of the positive electrode or
The crystal structure of compound contains layer structure or spinel structure.The richness alkali metal manganese based solid solution or compound are selected from
xLi2MnO3·(1-x)LiCrO2、xLi2MnO3·(1-x)LiFeO2、xLi2MnO3·(1-x)LiMn2O4、xLi2MnO3·(1-
x)LiNi0.5Mn0.5O2、xLi2MnO3·(1-x)LiNi2/3Mn1/3O2、xLi2MnO3·(1-x)LiFe0.5Ni0.5O2,
xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2、xLi2MnO3·(1-x)LiNi0.4Co0.4Mn0.2O2、xLi2MnO3·(1-
x)LiNi0.5Co0.2Mn0.3O2、xLi2MnO3·(1-x)NaCrO2、xLi2MnO3·(1-x)NaFeO2、xLi2MnO3·(1-x)
NaNi0.5Mn0.5O2、xLi2MnO3·(1-x)NaNi0.33Co0.33Mn0.33O2、xLi2MnO3·(1-x)NaNi0.4Co0.4Mn0.2O2、
xLi2MnO3·(1-x)NaNi0.5Co0.2Mn0.3O2、xLi2MnO3·(1-x)NaFe0.5Mn0.5O2、xNa2MnO3·(1-x)
NaFeO2、xNa2MnO3·(1-x)NaFe0.5Mn0.5O2、xLi2MnO3·(1-x)KNi0.33Co0.33Mn0.33O2、xLi2MnO3·
(1-x)KNi0.5Co0.2Mn0.3O2、xLi2MnO3·(1-x)KNi0.4Co0.4Mn0.2O2、xLi2MnO3·(1-x)KNi0.5Mn0.5O2
One of (0≤x≤1) or a variety of or above-mentioned rich alkali metal manganese based solid solution or compound are by metal oxide, nonmetallic oxygen
The material of compound cladding.The metal or nonmetal oxide for wherein being used to coat include Al2O3、TiO2、ZnO、CeO2、MgO、ZrO2
Deng.
In Water-system alkali metal ion power storage device of the invention, the richness alkali metal manganese based solid solution of the positive electrode has
There is general formula xA2MnO3·(1-x)AMO2, wherein A is selected from one of Li, Na and K or a variety of；M be selected from transient metal Mn, Ni,
One of Co, Cr, Al, Ru and Fe or a variety of；0≤x≤1.The richness alkali metal manganese based solid solution material can pass through co-precipitation
The synthesis of the methods of method, sol-gal process, solid phase method, hydro-thermal method obtains.Wherein the maximum feature of solid phase method and coprecipitation is just
In industrialization, it is considered as the energy storage material field of popularization and application bottleneck suitable for cost.
In Water-system alkali metal ion power storage device of the invention, the richness alkali metal manganese based solid solution of the positive electrode has
There is general formula xA2MnO3·(1-x)AMO2, wherein A is selected from one of Li, Na and K or a variety of；M be selected from transient metal Mn, Ni,
One of Co, Cr, Al, Ru and Fe or a variety of；0≤x≤1.The material structure can be characterized with X-ray diffractometer,
XRD spectrum can be attributed to space group and beα-NaFeO2 type the layer structure of type.Wherein, the angle of diffraction spreading out between 20 ° -28 °
Caused by penetrating the superlattices ordered arrangement that peak is alkali metal ion and transition metal ions.The alkali metal element of lattice is not entered into
Remain in particle surface, can be washed off through washing.The ratio of alkali metal and transition metal in rich alkali metal manganese based solid solution material
Alkali metal and transition metal content therein can be surveyed after washing, i.e., provable alkali metal element comes into lattice
Portion.
In Water-system alkali metal ion power storage device of the invention, the water phase electrolyte is including but not limited to sulfuric acid
Sodium, sodium nitrate, sodium halide, sodium carbonate, sodium phosphate, sodium acetate, sodium hydroxide, sodium perchlorate, potassium sulfate, potassium nitrate, potassium halide,
One of potassium carbonate, potassium phosphate, potassium acetate, potassium hydroxide, potassium hyperchlorate or a variety of mixed liquors.Concentration of electrolyte is 0.5-
10mol.L-1, pH value is between 3-12.
Low in order to solve existing room temperature water system alkali metal-ion battery positive electrode energy density, performance is bad
Problem, the present invention provides a kind of rich alkali metal manganese based solid solution or composite anode materials.Rich alkali metal manganese base of the invention
Solid solution or compound have general formula xA2MnO3·(1-x)AMO2, wherein A is selected from one of Li, Na and K or a variety of；M is selected from
One of transient metal Mn, Ni, Co, Cr, Al, Ru and Fe are a variety of；0≤x≤1.Specifically, the richness alkali of the positive electrode
Manganese metal based solid solution or compound are selected from xLi2MnO3·(1-x)LiCrO2、xLi2MnO3·(1-x)LiFeO2、xLi2MnO3·
(1-x)LiMn2O4、xLi2MnO3·(1-x)LiNi0.5Mn0.5O2、xLi2MnO3·(1-x)LiNi2/3Mn1/3O2、xLi2MnO3·
(1-x)LiFe0.5Ni0.5O2,xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2、xLi2MnO3·(1-x)
LiNi0.4Co0.4Mn0.2O2、xLi2MnO3·(1-x)LiNi0.5Co0.2Mn0.3O2、xLi2MnO3·(1-x)NaCrO2、
xLi2MnO3·(1-x)NaFeO2、xLi2MnO3·(1-x)NaNi0.5Mn0.5O2、xLi2MnO3·(1-x)
NaNi0.33Co0.33Mn0.33O2、xLi2MnO3·(1-x)NaNi0.4Co0.4Mn0.2O2、xLi2MnO3·(1-x)
NaNi0.5Co0.2Mn0.3O2、xLi2MnO3·(1-x)NaFe0.5Mn0.5O2、xNa2MnO3·(1-x)NaFeO2、xNa2MnO3·(1-
x)NaFe0.5Mn0.5O2、xLi2MnO3·(1-x)KNi0.33Co0.33Mn0.33O2、xLi2MnO3·(1-x)KNi0.5Co0.2Mn0.3O2、
xLi2MnO3·(1-x)KNi0.4Co0.4Mn0.2O2、xLi2MnO3·(1-x)KNi0.5Mn0.5O2It is one of (0≤x≤1) or more
Kind.The positive electrode also needs conductive agent (graphite, carbon black, acetylene black etc.) Lai Tigao material conductivity that 5%-10% is added, together
When also need the binder (polytetrafluoroethylene (PTFE), Kynoar etc.) that 5%-10% is added be made uniformly, the sticking mixing material of tool
Material, then the mixing material is fixed on collector by pressure or conducting resinl.Collector includes stainless steel, nickel, titanium, graphite
Plate, carbon paper etc..
The active material of the anode is with general formula xA2MnO3·(1-x)AMO2Rich alkali metal manganese based solid solution or multiple
Object is closed, wherein the alkali metal A contains lithium (Li), and the active material of the anode containing lithium is in the water system electrochemical energy storage
It has passed through the alkali metal ion exchange processing of chemistry or electrochemistry before device assembling or after assembling.The active material of the anode containing lithium can
It is that active material is placed in dilute acid soln to impregnate, to make lithium ion to be chemically treated before device assembles
It is detached from.The active material of the anode containing lithium is subjected to electrochemistry alkali metal ion exchange processing, be active material is placed in containing sodium or
In the electrochemical cell of potassium salt soln, long-time charge and discharge cycles are carried out within the scope of certain voltage, make lithium ion from positive material
Taken off in the structure of material, and enter sodium or potassium ion in the structure of positive electrode, thus realize sodium or potassium ion with
Exchange between lithium ion.Electrochemistry alkali metal ion exchange processing can carry out before device assembles, can also be in device group
By carrying out, charge and discharge is electro-active to be realized again after dress.
The present invention will realize application of the alkali metal ion positive electrode in water phase alkali metal ion electrolyte easily, can be with
It reduces cost and improves device security energy.
Detailed description of the invention
Fig. 1 is that positive electrode is 0.16Li in the embodiment of the present invention 12MnO3·0.84LiNi0.4Co0.4Mn0.2O2, cathode material
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 present invention 12MnO3·0.84LiNi0.4Co0.4Mn0.2O2, with activity
The mixing capacitor batteries of charcoal cathode composition are in 1M Na2SO4Charging and discharging curve in aqueous solution.
Fig. 3 is that positive electrode is 0.16Li in the embodiment of the present invention 12MnO3·0.84LiNi0.4Co0.4Mn0.2O2, with activity
The mixing capacitor batteries of charcoal cathode composition are in 0.5M K2SO4Charging and discharging curve in aqueous solution.
Fig. 4 is that positive electrode is 0.4Li in the embodiment of the present invention 22MnO3·0.6LiNi2/3Mn1/3O2, with activated carbon negative electrode
The mixing capacitor batteries of composition are in 1M Na2SO4Charging and discharging curve in aqueous solution.
Fig. 5 is that positive electrode is 0.4Li in the embodiment of the present invention 22MnO3·0.6LiNi2/3Mn1/3O2X-ray powder spread out
Penetrate (XRD) figure.
Specific embodiment
The present invention will be further described in more detail by specific embodiment, but protection scope of the present invention is not limited to
These embodiments.
Embodiment 1
Positive electrode active materials use Co deposited synthesis nickel cobalt manganese composite hydroxide presoma, then with Li2CO3Mixing
It is obtained afterwards in high-temperature calcination.It is molten that nickel sulfate, manganese chloride, cobalt chloride are prepared into the metal mixed that nickel cobalt manganese total concentration is 2mo1/L
Liquid, wherein Mn:Ni:Co molar ratio is 1:1:1；5mo1/L sodium hydroxide solution is configured using solid piece alkali；It is configured using ammonium hydroxide
100g/L solution；Cocurrent is passed into reaction kettle above-mentioned three kinds of solution simultaneously, temperature of reaction kettle control at 65 DEG C, metallic solution and
The flow of ammonium hydroxide is constant, the pH value 10-11 of sodium hydroxide solution flow control system；Precipitating preparation is washed using vacuum filtration machine washing
Powder product, 110 DEG C of drying obtain Ni1/3Co1/3Mn1/3(OH)2Presoma.By Ni1/3Co1/3Mn1/3(OH)2And Li2CO3It presses
It weighs according to Li/ (Ni+Mn+Co)=1.16:1 molar ratio proportion, then places weighing material in the ball mill with 150rpm ball milling
10h.It obtains uniformly mixed material to be placed in batch-type furnace, 900 DEG C of heat preservation 10h is warming up to 2 DEG C/min, are then naturally cooled to
Room temperature, and smashed and ground, 0.16Li is made2MnO3·0.84LiNi0.4Co0.4Mn0.2O2Dusty material.Positive electrode according to
0.16Li2MnO3·0.84LiNi0.4Co0.4Mn0.2O2: acetylene black: PTFE binder=80:10:10 mass ratio uniformly mixes,
It by mixture roll-in or is rolled by stainless (steel) wire after drying, the electrode slice of 0.2mm thickness is then made.Negative electrode material is using business
The active carbon of change, according to active carbon: conductive black: PTFE binder=80:10:10 mass ratio will mix after being uniformly mixed and dried
It closes object roll-in or is rolled by stainless (steel) wire, the electrode slice of 1mm thickness is then made.Then positive and negative anodes electrode is cut out according to specification
It cuts, pairing is assembled into CR2032 button cell, the PP base diaphragm that diaphragm uses hydrophilic treated to cross, and electrolyte is the Na of 1M2SO4Or
0.5M K2SO4Aqueous solution, battery structure are as shown in Figure 1.Reversible Cycle charging and discharging curve difference is as shown in Figure 2,3.In 0.2V-
The voltage range of 1.8V, charging and discharging currents 0.1C, in Na2SO4And K2SO4The specific capacity of the electric discharge of Reversible Cycle in aqueous solution
It is 123.5mAh/g, 133.5mAh/g respectively.
Embodiment 2
Positive electrode active materials are synthesized using sol-gal process, are 3 according to the stoichiometric ratio of manganese acetate and nickel acetate:
2 weigh manganese acetate respectively, nickel acetate is dissolved in appropriate amount of deionized water, and mixture is placed in 80 DEG C of waters bath with thermostatic control and is stirred, so
The mixed solution of lithium acetate and citric acid is slowly added dropwise afterwards, the molar ratio of lithium acetate and manganese acetate, nickel acetate is 1.47:0.6:
0.4, citric acid and manganese acetate, nickel acetate molar ratio be 1:1:1.Adjusting pH with ammonium hydroxide after dripping off is 7.0-8.0.80 DEG C of heat preservation
Until solution formed gel state, after being dried in 450 DEG C of air atmospheres pre-burning 10h, grind tabletting after again in air atmosphere
In calcine 10h at 900 DEG C, be rapidly cooled to room temperature, obtain 0.4Li2MnO3·0.6LiNi2/3Mn1/3O2Dusty material.Positive material
Material is according to 0.4Li2MnO3·0.6LiNi2/3Mn1/3O2: acetylene black: PTFE binder=80:10:10 mass ratio uniformly mixes,
It by mixture roll-in or is rolled by stainless (steel) wire after drying, the electrode slice of 0.2mm thickness is then made.Negative electrode material is using business
The active carbon of change, according to active carbon: conductive black: PTFE binder=80:10:10 mass ratio will mix after being uniformly mixed and dried
It closes object roll-in or is rolled by stainless (steel) wire, the electrode slice of 1mm thickness is then made.Then positive and negative anodes electrode is cut out according to specification
It cuts, pairing is assembled into CR2032 button cell, the PP base diaphragm that diaphragm uses hydrophilic treated to cross, and electrolyte is the Na of 1M2SO4Water
Solution, charging and discharging curve are as shown in Figure 4.In the voltage range of 0.2V-1.8V, charging and discharging currents 0.1C, in Na2SO4Aqueous solution
The specific capacity of the electric discharge of middle Reversible Cycle is 90.7mAh/g.Fig. 5 is 0.4Li2MnO3·0.6LiNi2/3Mn1/3O2X-ray powder
Last diffraction (XRD) figure.
Table 1 below is different rich alkali metal manganese-based compound and transition metal oxide (LiMn2O4With
Na0.44MnO2) Reversible Cycle specific discharge capacity in the aqueous solution containing Na, karat gold category salt comparison.The wherein work of negative electrode material
Property material be active carbon.Charging and discharging currents (multiplying power) are 0.1C, and charging/discharging voltage section is 0.2-1.8V.
Table 1
It is apparent to those skilled in the art although describing the present invention by way of examples
It is that, in the case where not departing from the spirit and scope of the present invention defined by the appended claims, can be carried out to the present invention
Variations and modifications, these change and modification are also included in the scope of the present invention.
Claims (9)
1. a kind of water system electrochemical energy storing device, the water phase electrolyte including anode, cathode, diaphragm and alkali metal containing ion,
It is characterized in that, the active material of the anode is with general formula xA2MnO3·(1-x)AMO2Rich alkali metal manganese based solid solution or multiple
Object is closed, the specific chemical formula of the active material of the anode is 0.16Li2MnO3·0.84LiNi0.4Co0.4Mn0.2O2Or
0.4Li2MnO3·0.6LiNi2/3Mn1/3O2；The manganese based solid solution of the richness alkali metal of the active material of the anode or compound
Crystal structure contains layer structure or spinel structure；The electrolyte is the aqueous solution containing sodium or sylvite；The positive electrode
Stable charge and discharge cycles can be carried out in the electrolyte.
2. water system electrochemical energy storing device according to claim 1, which is characterized in that the active material of the anode is tool
There is general formula xA2MnO3·(1-x)AMO2Rich alkali metal manganese based solid solution, crystal structure contains layer structure.
3. water system electrochemical energy storing device according to claim 1, which is characterized in that the active material of the anode is tool
There is general formula xA2MnO3·(1-x)AMO2Rich alkali metal manganese-based compound, crystal structure contains spinel structure.
4. water system electrochemical energy storing device according to claim 1, which is characterized in that the active material of the anode is tool
There is general formula xA2MnO3·(1-x)AMO2Rich alkali metal manganese based solid solution or compound, wherein the alkali metal A contains lithium, and
And the active material of the anode containing lithium have passed through chemistry or electricity before water system electrochemical energy storing device assembling or after assembling
The alkali metal ion exchange processing of chemistry.
5. water system electrochemical energy storing device according to claim 1, which is characterized in that the negative electrode material includes at least one
Kind can carry out the material that reversible electrochemical react with sodium ion or/and potassium ion in water phase electrolyte.
6. water system electrochemical energy storing device according to claim 1, which is characterized in that the negative electrode material includes at least one
Kind can carry out the material of sodium ion or/and potassium ion insertion and deintercalation in water phase electrolyte.
7. water system electrochemical energy storing device according to claim 1, which is characterized in that the active material of the cathode is selected from
One of active carbon, graphene, carbon nanotube, carbon fiber and mesoporous carbon or multiple material.
8. water system electrochemical energy storing device according to claim 1, which is characterized in that the water phase electrolyte includes sodium
One of salt, sylvite electrolyte are a variety of.
9. water system electrochemical energy storing device according to claim 1, which is characterized in that the water phase electrolyte is selected from sulfuric acid
Sodium, sodium nitrate, sodium halide, sodium carbonate, sodium phosphate, sodium acetate, sodium hydroxide, sodium perchlorate, potassium sulfate, potassium nitrate, potassium halide,
One of potassium carbonate, potassium phosphate, potassium acetate, potassium hydroxide, potassium hyperchlorate are a variety of.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN103259009B (en) * | 2013-04-18 | 2019-06-14 | 恩力能源科技有限公司 | A kind of water-system alkali metal ion electrochemical energy storing device |
| 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 |
| 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 |
| CN106602054B (en) * | 2016-12-26 | 2019-08-16 | 东北大学 | Kalium ion battery positive electrode and preparation method thereof, application |
| CN106800312B (en) * | 2017-03-08 | 2019-11-19 | 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 |
| CN107403915B (en) * | 2017-07-13 | 2020-01-14 | 南京大学 | Manganese-based positive electrode 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 |
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| US10665892B2 (en) * | 2007-01-10 | 2020-05-26 | Eocell Limited | Lithium batteries with nano-composite positive electrode material |
| CA2720600C (en) * | 2008-04-07 | 2017-09-12 | Jay Whitacre | Sodium ion based aqueous electrolyte electrochemical secondary energy storage device |
| JP5625390B2 (en) * | 2009-03-13 | 2014-11-19 | 住友化学株式会社 | Composite metal oxide, electrode and sodium secondary battery |
| CN102263280A (en) * | 2011-06-28 | 2011-11-30 | 中国科学院物理研究所 | Flow aqueous chargeable alkali metal ion battery |
| CN103219551A (en) * | 2013-03-27 | 2013-07-24 | 恩力能源科技（南通）有限公司 | Water-system alkali metal ion power storage device |
| CN103259009B (en) * | 2013-04-18 | 2019-06-14 | 恩力能源科技有限公司 | A kind of water-system alkali metal ion electrochemical energy storing device |
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