CN107394172A - Tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof - Google Patents
Tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode and preparation method thereof Download PDFInfo
- Publication number
- CN107394172A CN107394172A CN201710632461.4A CN201710632461A CN107394172A CN 107394172 A CN107394172 A CN 107394172A CN 201710632461 A CN201710632461 A CN 201710632461A CN 107394172 A CN107394172 A CN 107394172A
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- CN
- China
- Prior art keywords
- lithium
- tungstate
- positive electrode
- raw material
- ion battery
- Prior art date
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- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 321
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 296
- 239000011572 manganese Substances 0.000 title claims abstract description 211
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 209
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 208
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 163
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 90
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 73
- 150000002641 lithium Chemical class 0.000 claims abstract description 52
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 35
- 239000010941 cobalt Substances 0.000 claims abstract description 35
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010405 anode material Substances 0.000 claims abstract description 34
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 33
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 230000004907 flux Effects 0.000 claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000008139 complexing agent Substances 0.000 claims abstract description 20
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims abstract description 20
- 150000003657 tungsten Chemical class 0.000 claims abstract description 6
- 229910013191 LiMO2 Inorganic materials 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 24
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 230000008595 infiltration Effects 0.000 claims description 16
- 238000001764 infiltration Methods 0.000 claims description 16
- 229910052721 tungsten Inorganic materials 0.000 claims description 16
- 239000010937 tungsten Substances 0.000 claims description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 14
- 238000002604 ultrasonography Methods 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 9
- 150000004703 alkoxides Chemical class 0.000 claims description 8
- 239000008236 heating water Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical class CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical group O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 37
- 239000003643 water by type Substances 0.000 description 20
- 239000006182 cathode active material Substances 0.000 description 16
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 16
- 235000015165 citric acid Nutrition 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000007774 positive electrode material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 8
- 239000001099 ammonium carbonate Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910001346 0.5Li2MnO3 Inorganic materials 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 238000007605 air drying Methods 0.000 description 6
- -1 LiCoO2 Chemical class 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- HYFPVPNWNRFTMP-UHFFFAOYSA-N formic acid;manganese Chemical compound [Mn].OC=O HYFPVPNWNRFTMP-UHFFFAOYSA-N 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- QQGWBRJQPRTJDA-UHFFFAOYSA-N [Li].CC(O)=O Chemical compound [Li].CC(O)=O QQGWBRJQPRTJDA-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- WIDQNNDDTXUPAN-UHFFFAOYSA-I tungsten(v) chloride Chemical compound Cl[W](Cl)(Cl)(Cl)Cl WIDQNNDDTXUPAN-UHFFFAOYSA-I 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
- H01M4/362—Composites
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention particularly discloses a kind of tungstate lithium to be modified lithium-rich manganese-based layered lithium ion battery positive electrode, and its chemical general formula is (xLi2MnO3·(1‑x)LiMO2)/yLi2WO4；Wherein, 0.1≤x≤0.9,0.001≤y≤0.4, M Mn, Co and Ni；It includes following raw material components：Manganese raw material, nickel raw material, cobalt raw material, lithium salts, tungsten salt, complexing agent, reducing agent and liquid flux；And disclose the preparation method that tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode.The present invention utilizes the satisfactory electrical conductivity of tungstate lithium, have greatly improved to the high rate performance of anode material for lithium-ion batteries, improve its electrochemical stability simultaneously, significantly improve the cyclical stability of anode material for lithium-ion batteries so that tungstate lithium of the invention coats the discharge platform of lithium-rich manganese-based layered lithium ion battery positive electrode and capacity attenuation slows down.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion
Cell positive material and preparation method thereof.
Background technology
As economic rapid development and the continuous acceleration of process of industrialization, the mankind are increasing to the demand of the energy.Due to
The excessive exploitation of the resource such as coal and oil so that traditional energy increasingly depleted.Moreover, in the combustion process of fossil fuel, meeting
Substantial amounts of pernicious gas and dust are produced, environmental pollution is extremely serious.Grave danger is brought to environment for the survival of mankind.
As can be seen here, the green energy resource of Sustainable Development is imperative.
Develop free of contamination sustainable green energy resource to be expected to alleviate environmental pollution, new energy includes wind energy, water energy, solar energy
With geothermal energy etc., but the effect of these energy is in intermittent, wants to be more reasonably utilized these energy, it is necessary to use
One matched device stores them, is discharged again when needing to use.Secondary cell, Ke Yishi
Existing electric energy and chemical transformation of energy, in the more than ten years in past, chargeable lithium ion battery as important energy storage device because it
It is suitable energy storage device with good charge-discharge performance and good cycle performance.
At present, anode material for lithium-ion batteries is mainly embedding lithium type complex metal oxide, such as LiCoO2、LiMn2O4With
LiFePO4Deng.But because the cost of Co elements is high, shortage of resources, and have certain pollution so that LiCoO2It can not advise greatly
The application of mould.And LiMn2O4And LiFePO4Advantage be that cost is low, rich content, certain competitiveness be present；But
LiMn2O4Specific discharge capacity it is low, 1C is about 120mA/g.LiFePO4Energy density it is relatively low.Therefore people have been look for pacifying
Entirely, environmentally friendly, energy density is high, the electrode material of new generation of good cycle.
By continuous exploration of the people for existing positive electrode, find in the LiMnO to stratiform2It is doped modified
During, if the amount of control metallic element and Li elements, the composite oxides with high-energy-density can be synthesized, are referred to as
Lithium-rich anode material.Lithium-rich anode material is due to high reversible specific capacity, typically in 200mAh/g-300mAh/g, have compared with
Good cyclical stability and heat endurance and higher operating voltage.It is considered as current commercialized LiCoO2Most
Have a promising substitute, but its cycle efficieny is low first, high rate performance and cyclical stability are very poor, limit its business
Change.Therefore, the cyclical stability for improving such positive electrode is urgent problem to be solved.
The content of the invention
For problems of the prior art, it is an object of the invention to provide a kind of tungstate lithium to be modified lithium-rich manganese-based layer
Shape anode material for lithium-ion batteries and preparation method thereof.
In order to achieve the above object, the present invention is achieved using following technical scheme.
(1) a kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that its chemistry is logical
Formula is (xLi2MnO3·(1-x)LiMO2)/yLi2WO4；Wherein, 0.1≤x≤0.9,0.001≤y≤0.4, M Mn, Co and Ni.
(2) a kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that including following
Raw material components：Manganese raw material, nickel raw material, cobalt raw material, lithium salts, tungsten salt, complexing agent, reducing agent and liquid flux.
Preferably, the manganese raw material is manganese metal, Mn oxide, inorganic salts containing manganese, organic salt containing manganese or alkoxide containing manganese.
It is further preferred that the manganese raw material is manganese nitrate, manganese sulfate, formic acid manganese, manganese acetate or manganese acetate.
Preferably, the nickel raw material is metallic nickel, nickel oxide, nickeliferous inorganic salts, nickeliferous organic salt or nickeliferous alkoxide.
It is further preferred that the nickel raw material is nickel acetate, nickel nitrate, nickel sulfate, nickel formate or nickel acetate.
Preferably, the cobalt raw material is metallic cobalt, cobalt/cobalt oxide, inorganic salts containing cobalt, organic salt containing cobalt or alkoxide containing cobalt.
It is further preferred that the cobalt raw material is cobalt acetate, cobalt nitrate, cobaltous sulfate, cobaltous formate or cobalt acetate.
Preferably, the lithium salts is oxidate for lithium, inorganic salts containing lithium, organic salt containing lithium or containing lithium alkoxide.
It is further preferred that the lithium salts is lithium nitrate, lithium acetate, lithium formate, lithium hydroxide or lithium carbonate.
Preferably, the tungsten salt is tungsten oxide, tungstenic organic salt, tungstenic inorganic salts or tungstenic alkoxide.
It is further preferred that the tungsten salt is ammonium metatungstate, ammonium tungstate, tungsten pentachloride, tungsten hexachloride.
Preferably, the complexing agent includes alcamines complexing agent, hydroxycarboxylic acid complexing agent, organic phosphate complexing agent
Or polyacrylic complexing agent.
It is further preferred that the complexing agent is citric acid, acetylacetone,2,4-pentanedione, ethylenediamine tetra-acetic acid, sucrose or glucose.
Preferably, the reducing agent includes inorganic acids reducing agent, organic acid reducing agent or alcohols reducing agent.
It is further preferred that the reducing agent is citric acid.
Preferably, the liquid flux is deionized water, ethylene glycol ethyl ether or ethanol.
Preferably, in the lithium salts, manganese raw material, nickel raw material and cobalt raw material, when manganese raw material is bivalent manganese raw material, nickel raw material is
When nickelous raw material, cobalt raw material are divalence cobalt raw material, wherein, Li+、Mn2+、Ni2+With Co2+Mol ratio be (1.1~1.9)：
(0.3997~0.9333)：(0.2997~0.0333)：(0.2997~0.0333).
Preferably, the chemical general formula of the lithium-rich manganese-based layered lithium ion battery positive electrode of the tungstate lithium modification is
(xLi2MnO3·(1-x)LiMO2)/yLi2WO4, wherein, M is manganese, cobalt and nickel；The mole of the complexing agent with it is described
(xLi2MnO3·(1-x)LiMO2)/yLi2WO4The ratio between middle M mole is 1:1~2:1.
(3) a kind of tungstate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, and its feature exists
In comprising the following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared：By manganese raw material, nickel raw material, cobalt raw material and lithium salts
It is dissolved in successively in liquid flux, adds complexing agent, heating water bath, stirring reaction 3-5h under the conditions of 50-80 DEG C, obtains presoma
Colloidal sol, then the precursor sol is heat-treated, obtains lithium-rich manganese-based layered lithium ion battery positive electrode；Wherein,
The heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere, 3- is calcined under the conditions of 350-550 DEG C first
5h, then 12-24h is calcined under the conditions of 800-950 DEG C；
Step 2, tungstate lithium presoma is prepared：Tungsten source and reducing agent are dissolved in liquid flux, water-bath under the conditions of 50-70 DEG C
Heating, 2-3h is stirred, adds lithium salts, continued to stir 1-2h, obtain tungstate lithium colloidal sol；
Step 3, prepare tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode：By the lithium-rich manganese-based stratiform
Anode material for lithium-ion batteries mixes with the tungstate lithium colloidal sol, be stirred successively, ultrasonic infiltration, negative pressure impregnation, heat treatment,
Produce tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode.
Preferably, in step 3, when the ultrasound is permeated, the frequency of ultrasonic wave is 40KHz, and the time of ultrasound infiltration is 20-
40min。
Preferably, in step 3, the condition of the negative pressure impregnation is (- 0.05) MPa- (- 0.08) MPa.
Preferably, in step 3, the heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere,
4-8h is calcined under the conditions of 600-750 DEG C.
(4) a kind of tungstate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, and its feature exists
In comprising the following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared：Manganese raw material, nickel raw material, cobalt raw material is molten successively
In liquid flux, complexing agent, lithium salts are added, heating water bath, stirring reaction 3-5h under the conditions of 50-70 DEG C, obtain presoma
Colloidal sol, then the precursor sol is heat-treated, obtains lithium-rich manganese-based layered lithium ion battery positive electrode；Wherein,
The heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere, 3- is calcined under the conditions of 350-550 DEG C first
5h, then 12-24h is calcined under the conditions of 800-950 DEG C；
Step 2, tungstate lithium presoma is prepared：Tungsten source and reducing agent are dissolved in liquid flux, water-bath under the conditions of 50-70 DEG C
Heating, 2-3h is stirred, adds lithium salts, continued to stir 1-2h, form colloidal sol, then be heat-treated, obtain tungstate lithium presoma；
Step 3, prepare tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode：By the lithium-rich manganese-based stratiform
Anode material for lithium-ion batteries is well mixed with the tungstate lithium presoma, grinding, then is heat-treated, and produces tungstate lithium modification
Lithium-rich manganese-based layered lithium ion battery positive electrode.
Preferably, in step 3, the time of the grinding is 2-5h.
Preferably, in step 2 and step 3, the heat treatment is carried out according to following operation：In Muffle furnace, air atmosphere
Under, 4-8h is calcined under the conditions of 600-750 DEG C.
(5) a kind of tungstate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, and its feature exists
In comprising the following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared：First by manganese raw material, nickel raw material, cobalt raw material according to
It is secondary to be dissolved in liquid flux, obtain raw material mixed liquor；Then sodium carbonate and sodium acid carbonate are dissolved in liquid flux respectively, respectively
Sodium carbonate liquor and sodium bicarbonate solution；Raw material mixed liquor, sodium carbonate liquor and the sodium bicarbonate solution are added dropwise simultaneously again
Into deionized water, and the heating water bath under the conditions of 50-70 DEG C, stirring reaction 6-7h, it is aged, is filtered, is dried successively afterwards
It is dry, obtain carbonate precursor；Then the carbonate precursor is mixed with lithium salts, grinds, be finally heat-treated, obtained
Lithium-rich manganese-based layered lithium ion battery positive electrode；
Step 2, tungstate lithium presoma is prepared：Tungsten source and reducing agent are dissolved in liquid flux, water-bath under the conditions of 50-70 DEG C
Heating, 2-3h is stirred, adds lithium salts, continued to stir 1-2h, form colloidal sol, then be heat-treated, obtain tungstate lithium presoma；
Step 3, prepare tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode：By the lithium-rich manganese-based stratiform
Anode material for lithium-ion batteries is well mixed with the tungstate lithium presoma, grinding, then is heat-treated, and produces tungstate lithium modification
Lithium-rich manganese-based layered lithium ion battery positive electrode.
Preferably, in step 1, the pH of the deionized water is 8-10.
Preferably, in step 1, the time of the ageing is 10-12h.
Preferably, in step 1, the heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere, 800-
12-24h is calcined under the conditions of 950 DEG C.
Preferably, in step 3, the time of the grinding is 2-5h.
Preferably, in step 2 and step 3, the heat treatment is carried out according to following operation：In Muffle furnace, air atmosphere
Under, 4-8h is calcined under the conditions of 600-750 DEG C.
(6) a kind of tungstate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, and its feature exists
In comprising the following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared：First by manganese raw material, nickel raw material, cobalt raw material according to
It is secondary to be dissolved in liquid flux, obtain raw material mixed liquor；Then sodium carbonate and sodium acid carbonate are dissolved in liquid flux respectively, respectively
Sodium carbonate liquor and sodium bicarbonate solution；Raw material mixed liquor, sodium carbonate liquor and the sodium bicarbonate solution are added dropwise simultaneously again
Into deionized water, and the heating water bath under the conditions of 50-70 DEG C, stirring reaction 6-7h, it is aged, is filtered, is dried successively afterwards
It is dry, obtain carbonate precursor；Then the carbonate precursor is mixed with lithium salts, grinds, be finally heat-treated, obtained
Lithium-rich manganese-based layered lithium ion battery positive electrode；
Step 2, tungstate lithium presoma is prepared：Tungsten source and reducing agent are dissolved in liquid flux, water-bath under the conditions of 50-70 DEG C
Heating, 2-3h is stirred, adds lithium salts, continued to stir 1-2h, obtain tungstate lithium colloidal sol；
Step 3, prepare tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode：By the lithium-rich manganese-based stratiform
Anode material for lithium-ion batteries mixes with the tungstate lithium colloidal sol, be stirred successively, ultrasonic infiltration, negative pressure impregnation, heat treatment,
Produce tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode.
Preferably, in step 1, the pH of the deionized water is 8-10.
Preferably, in step 1, the time of the ageing is 10-12h.
Preferably, in step 1, the heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere, 800-
12-24h is calcined under the conditions of 950 DEG C.
Preferably, in step 3, when the ultrasound is permeated, the frequency of ultrasonic wave is 40KHz, and the time of ultrasound infiltration is 20-
40min。
Preferably, in step 3, the condition of the negative pressure impregnation is (- 0.05) MPa- (- 0.08) MPa.
Preferably, in step 3, the heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere,
4-8h is calcined under the conditions of 600-750 DEG C.
(7) a kind of tungstate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, and its feature exists
In comprising the following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared：By manganese raw material, nickel raw material, cobalt raw material and lithium salts
It is dissolved in successively in liquid flux, adds complexing agent, stirring and dissolving, hydro-thermal reaction is carried out after dissolving, after hydro-thermal reaction terminates
Solid precursor is obtained, the solid precursor is heat-treated, obtains lithium-rich manganese-based layered lithium ion battery positive electrode；
Step 2, tungstate lithium presoma is prepared：Tungsten source and reducing agent are dissolved in liquid flux, water-bath under the conditions of 50-70 DEG C
Heating, 2-3h is stirred, adds lithium salts, continued to stir 1-2h, form colloidal sol, obtain tungstate lithium presoma；
Step 3, prepare tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode：By the lithium-rich manganese-based stratiform
Anode material for lithium-ion batteries mixes with the tungstate lithium presoma, be stirred successively, ultrasonic infiltration, negative pressure impregnation, Re Chu
Reason, produce tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode.
Preferably, in step 1, the temperature of the hydro-thermal reaction is 150-220 DEG C, and the time of hydro-thermal reaction is 10-15h.
Preferably, in step 1, the heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere, first
3-5h is calcined under the conditions of 350-550 DEG C, then 12-24h is calcined under the conditions of 800-950 DEG C.
Preferably, in step 3, when the ultrasound is permeated, the frequency of ultrasonic wave is 40KHz, and the time of ultrasound infiltration is 20-
40min。
Preferably, in step 3, the condition of the negative pressure impregnation is (- 0.05) MPa- (- 0.08) MPa.
Preferably, in step 3, the heat treatment is carried out according to following operation：In Muffle furnace, under air atmosphere,
4-8h is calcined under the conditions of 600-750 DEG C.
(8) a kind of tungstate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, and its feature exists
In comprising the following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared：By manganese raw material, nickel raw material, cobalt raw material and lithium salts
It is dissolved in successively in formaldehyde, adds resorcinol, stirring and dissolving carries out hydro-thermal reaction after dissolving, hydro-thermal reaction obtains after terminating
Solid precursor, the solid precursor is heat-treated, obtains lithium-rich manganese-based layered lithium ion battery positive electrode；Its
In, the mol ratio of resorcinol and formaldehyde is 1:2；
Step 2, tungstate lithium presoma is prepared：Tungsten source and reducing agent are dissolved in liquid flux, water-bath under the conditions of 50-70 DEG C
Heating, 2-3h is stirred, adds lithium salts, continued to stir 1-2h, form colloidal sol, then be heat-treated, obtain tungstate lithium presoma
Powder；
Step 3, prepare tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode：By the lithium-rich manganese-based stratiform
Anode material for lithium-ion batteries is well mixed with the tungstate lithium precursor powder, grinding, then is heat-treated, and produces tungstate lithium
Modified lithium-rich manganese-based layered lithium ion battery positive electrode.
Preferably, in step 1, the temperature of the hydro-thermal reaction is 150-220 DEG C, and the time of hydro-thermal reaction is 10-15h.
Preferably, in step 1, step 2 and step 3, the heat treatment is carried out according to following operation：It is empty in Muffle furnace
Under gas atmosphere, 4-8h is calcined under the conditions of 600-750 DEG C.
Preferably, in step 3, the time of the grinding is 2-5h.
Compared with prior art, beneficial effects of the present invention are：
A kind of tungstate lithium provided by the invention is modified lithium-rich manganese-based layered lithium ion battery positive electrode, utilizes tungstate lithium
Satisfactory electrical conductivity, have greatly improved to the high rate performance of anode material for lithium-ion batteries, while it is electrochemically stable to improve its
Property, significantly improve the cyclical stability of anode material for lithium-ion batteries so that tungstate lithium of the invention is modified lithium-rich manganese-based layer
The discharge platform and capacity attenuation of shape anode material for lithium-ion batteries slow down.
Brief description of the drawings
The present invention is described in further details with specific embodiment below in conjunction with the accompanying drawings.
Fig. 1 is that the tungstate lithium of embodiment 1 is modified the X-ray diffraction of lithium-rich manganese-based layered lithium ion battery positive electrode
(XRD) spectrogram；Wherein, a be tungstate lithium diffraction maximum, b be lithium-rich manganese-based layered lithium ion battery positive electrode diffraction maximum, c
The X-ray diffraction spectrogram of lithium-rich manganese-based layered lithium ion battery positive electrode is modified for tungstate lithium；Abscissa is X-ray diffraction
The θ of measurement angle 2, unit for °, ordinate be material the diffraction sealing strength in this angle of diffraction, unit a.u.；
Fig. 2 is that the tungstate lithium of embodiment 4 is modified the scanning electron microscopy of lithium-rich manganese-based layered lithium ion battery positive electrode
Mirror figure, multiplication factor are 50,000 times；
Fig. 3 is that the tungstate lithium of embodiment 4 is modified lithium-rich manganese-based layered lithium ion battery positive electrode and unmodified rich lithium
Charging and discharging curve comparison diagram of the manganese basic unit shape anode material for lithium-ion batteries in the case where charging and discharging currents density is 100mA/g；In figure,
A is charging and discharging curve of the unmodified lithium-rich manganese-based layered lithium ion battery positive electrode when circulating the number of turns and being the 1st circle；B is
Charging and discharging curve of the unmodified lithium-rich manganese-based layered lithium ion battery positive electrode when circulating the number of turns and being the 200th circle；C is tungsten
Sour lithium is modified charging and discharging curve of the lithium-rich manganese-based layered lithium ion battery positive electrode when circulating the number of turns and being the 1st circle；D is wolframic acid
Lithium is modified charging and discharging curve of the lithium-rich manganese-based layered lithium ion battery positive electrode when circulating the number of turns and being the 200th circle；Abscissa
For the specific capacity of material, unit mAh/g, ordinate is voltage, unit V；
Fig. 4 is that the tungstate lithium of embodiment 1 is modified lithium-rich manganese-based layered cathode active material under different discharge current densities
Circulation figure；In figure, a is unmodified lithium-rich manganese-based layered lithium ion battery positive electrode in different discharge current densities
Under circulation figure, b is that tungstate lithium is modified times of lithium-rich manganese-based layered cathode active material under different discharge current densities
Rate circulation figure；Abscissa for circulation the number of turns, ordinate be material specific capacity, unit mAh/g；
Fig. 5 be tungstate lithium prepared by embodiment 1 be modified lithium-rich manganese-based layered lithium ion battery positive electrode with it is unmodified
The long circulating performance comparison figure of lithium-rich manganese-based layered lithium ion battery positive electrode；Abscissa is the circulation number of turns, and ordinate is material
The specific capacity of material, unit mAh/g.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
It will be appreciated that the following example is merely to illustrate the present invention, and it is not construed as limiting the scope of the present invention.
Embodiment 1
A kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, and its preparation method comprises the following steps：
(1) by formic acid manganese 0.067mol, cobaltous formate 0.0167mol, nickel formate 0.0167mol, lithium formate 0.15mol successively
30mL ethanol is dissolved in, 0.1mol acetylacetone,2,4-pentanediones are added after abundant dissolving, under 80 DEG C of water bath conditions, 3h is stirred, before obtaining
Body colloidal sol is driven, 100 DEG C are incubated 24h in air；Calcined again in Muffle furnace, 5h is specially calcined at 450 DEG C, then 900
12h is calcined at DEG C, obtains powdered lithium-rich manganese-based layered lithium ion battery positive electrode, its chemical formula is：0.5Li2MnO3·
0.5LiMn1/3Ni1/3Co1/3O2。
(2) citric acid for weighing 0.00046mol is dissolved in 20mL deionized waters, adds 0.0000255mol ammonium metatungstates,
Under 70 DEG C of water bath conditions, 2h is stirred, adds 0.000611mol lithium hydroxides, continued to stir 2h, obtain tungstate lithium colloidal sol.
(3) the lithium-rich manganese-based layered lithium ion battery positive electrode obtained in 1.6g steps (1) is weighed, is immersed in tungstate lithium
In colloidal sol, stirring, and the ultrasound infiltration 20min under 40KHz ultrasonic frequency, then negative pressure is soaked under conditions of -0.05MPa
Stain, drying, obtain tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor；Obtained tungstate lithium is changed again
The lithium-rich manganese-based layered lithium ion battery positive electrode material precursor of property is finally calcined in Muffle furnace in 70 DEG C of air drying 24h,
5h specially is calcined under the conditions of 650 DEG C, tungstate lithium is produced and is modified lithium-rich manganese-based layered lithium ion battery positive electrode, it is powder
Last shape, chemical formula are：(0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2)/0.05Li2WO4。
Embodiment 2
A kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, and its preparation method comprises the following steps：
(1) it is manganese acetate 0.333moL, cobalt nitrate 0.083moL, nickel nitrate 0.083moL, lithium nitrate 0.75mol is molten successively
In 20mL deionized waters, 0.5mol citric acids are added, are 7 with ammoniacal liquor regulation pH value, under 50 DEG C of water bath conditions, stirring
5h, precursor sol is formed, 100 DEG C are incubated 24h in air；Calcined again in Muffle furnace, be specially：First in 450 DEG C of conditions
Lower calcining 5h, 12h is calcined at being then 900 DEG C in temperature；Powdered lithium-rich manganese-based layered lithium ion battery positive electrode is obtained,
Its chemical formula is：0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2。
(2) citric acid for weighing 0.0000573mol is dissolved in 20mL deionized waters, adds 0.00000318mol wolframic acids
Ammonium, under 70 DEG C of water bath conditions, 2h is stirred, add the addition of 0.000764mol lithium nitrates, continued to stir 2h, obtain tungstate lithium
Colloidal sol.
(3) the lithium-rich manganese-based layered lithium ion battery positive electrode prepared in 10g (1) is weighed, is added to tungstate lithium colloidal sol
In, stirring, and the ultrasound infiltration 20min under 40KHz ultrasonic frequency, then the negative pressure impregnation under conditions of -0.05MPa, dry
It is dry, obtain tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor；Tungstate lithium is modified lithium-rich manganese-based layer
Shape precursor of lithium ionic cell positive material is finally calcined, specially 650 in 70 DEG C of air drying 24h in Muffle furnace
5h is calcined under the conditions of DEG C, 0.91g tungstate lithiums is obtained and is modified lithium-rich manganese-based layered lithium ion battery positive electrode, its to be powdered,
Chemical formula is：(0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2)/0.001Li2WO4。
Embodiment 3
A kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, and its preparation method comprises the following steps：
(1) lithium nitrate 1.2moL, manganese sulfate 0.533moL, nickel sulfate 0.133moL, cobaltous sulfate 0.133moL are weighed respectively
It is dissolved in 30ml ethylene glycol ethyl ethers, 0.1moL EDTA complexes is added after abundant dissolving, in 70 DEG C of water bath conditions
Lower stirring 3h, precursor sol is obtained, 100 DEG C are incubated 24h in air；Calcine in Muffle furnace, specially forged at 450 DEG C again
5h is burnt, then 12h is calcined at 900 DEG C, obtains lithium-rich manganese-based layered lithium ion battery positive electrode, its chemical formula is：
0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2。
(2) citric acid for weighing 0.00138mol is dissolved in 20mL deionized waters, adds 0.0000764mol ammonium metatungstates,
Under 70 DEG C of water bath conditions, 2h is stirred, adds 0.00183mol lithium hydroxides, continued to stir 1h, obtain tungstate lithium colloidal sol.
(3) the lithium-rich manganese-based layered lithium ion battery positive electrode obtained in 12g (1) is weighed, is immersed in tungstate lithium colloidal sol
In, stirring, and the ultrasound infiltration 20min under 40KHz ultrasonic frequency, then the negative pressure impregnation under conditions of -0.08MPa, dry
It is dry, obtain tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor；Obtained tungstate lithium is modified again rich
Li Meng basic units shape precursor of lithium ionic cell positive material is finally calcined, specifically in 70 DEG C of air drying 12h in Muffle furnace
To calcine 5h under the conditions of 650 DEG C, produce tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode, it is powder
Shape, chemical formula are：(0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2)/0.02Li2WO4。
Embodiment 4
A kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, and its preparation method comprises the following steps：
(1) lithium nitrate 0.019moL, manganese nitrate 0.00933moL, nickel nitrate 0.00033moL, cobalt nitrate are weighed respectively
0.00033moL is dissolved in 30ml deionized waters, is added the complexing of 0.1moL glucose, is stirred 3h under 70 DEG C of water bath conditions, obtain
To precursor sol, 100 DEG C of insulation 24-36h in air；Calcined again in Muffle furnace, 5h is specially calcined at 450 DEG C, so
12h is calcined at 900 DEG C afterwards, obtains lithium-rich manganese-based layered lithium ion battery positive electrode, to be powdered, chemical formula is for it：
0.9Li2MnO3·0.1LiMn1/3Ni1/3Co1/3O2。
(2) citric acid for weighing 0.00161mol is dissolved in 25mL deionized waters, adds 0.000178mol tungsten hexachlorides,
Under 70 DEG C of water bath conditions, 2h is stirred, then 0.00214mol lithium hydroxides are added, continues stirring reaction 1h, obtains tungstate lithium
Colloidal sol, drying, obtains tungstate lithium precursor powder.
(3) the lithium-rich manganese-based layered lithium ion battery positive electrode prepared in 7g (1) is weighed, with the wolframic acid obtained in (2)
Lithium powder is well mixed, and grinds 2h, then is heat-treated, and is specially：In Muffle furnace, temperature calcines 5h under the conditions of being 650 DEG C,
Produce tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode, chemical formula is：(0.9Li2MnO3·0.1LiMn1/ 3Ni1/3Co1/3O2)/0.04Li2WO4。
Embodiment 5
A kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, and its preparation method comprises the following steps：
(1) 0.00933moL manganese acetates, 0.00033moL acetic acid brill, 0.00033moL nickel acetates are dissolved in 30mL and gone successively
In ionized water, 50 DEG C of stirring in water bath, raw material mixed liquor is obtained；0.01moL sodium carbonate is dissolved in 40mL deionized waters and forms sodium carbonate
The aqueous solution；0.01moL ammonium hydrogen carbonate is dissolved in 40mL deionized waters and forms ammonium bicarbonate aqueous solution；Again by raw material mixed liquor, carbon
Acid sodium aqueous solution and ammonium bicarbonate aqueous solution these three solution three-phase cocurrents, make it using identical flow velocity while instill pH as 9
Deionized water solution in, pH value of solution is controlled in course of reaction, under 50 DEG C of water bath conditions, after stirring reaction 7h, precipitation 12h,
Then washed 3-5 times with deionized water filter water in a manner of suction filtration, then dry moisture removal, obtain carbonate precursor；Incited somebody to action
Filter obtained powdered carbonate precursor to mix with 1.9moL lithium carbonate, grind, be placed in being heat-treated in Muffle furnace, specifically
To be calcined 15h at 900 DEG C, powdered lithium-rich manganese-based anode material is obtained, its chemical formula is：0.9Li2MnO3·
0.1LiMn1/3Ni1/3Co1/3O2。
(2) citric acid for weighing 0.00275mol is dissolved in 20mL deionized waters, and it is phosphoric to add 0.000306mol
Tungsten, under 70 DEG C of water bath conditions, 3h is stirred, adds 0.00367mol lithium hydroxides, continued to react 2h, it is molten to obtain tungstate lithium
Glue.
(3) the lithium-rich manganese-based layered lithium ion battery positive electrode obtained in 1g (1) is weighed, is added to tungstate lithium colloidal sol
In, stirring, and the ultrasound infiltration 40min under 40KHz ultrasonic frequency, then the negative pressure impregnation under conditions of -0.05MPa, dry
It is dry, obtain tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor；Obtained tungstate lithium is modified again rich
Li Meng basic units shape precursor of lithium ionic cell positive material is finally calcined in Muffle furnace in 70 DEG C of air drying 12h, is specially
5h is calcined under the conditions of 650 DEG C, powdered tungstate lithium is produced and is modified lithium-rich manganese-based layered lithium ion battery positive electrode.Chemical formula
For：(0.9Li2MnO3·0.1LiMn1/3Ni1/3Co1/3O2)/0.4Li2WO4。
Embodiment 6
A kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, and its preparation method comprises the following steps：
(1) by 0.3267moL formic acid manganese, 0.1867moL formic acid bores, 0.1867moL nickel formates be dissolved in successively 50mL go from
In sub- water, 50 DEG C of stirring in water bath, raw material mixed liquor is obtained；It is water-soluble that 0.7moL sodium carbonate is dissolved in 40mL deionized waters formation sodium carbonate
Liquid；0.7moL ammonium hydrogen carbonate is dissolved in 40mL deionized waters and forms ammonium bicarbonate aqueous solution；Again by raw material mixed liquor, sodium carbonate
Solution and ammonium bicarbonate aqueous solution these three solution three-phase cocurrents, make it using identical flow velocity 5mL/h while instill pH as 10
Deionized water solution in, while under 50 DEG C of water bath conditions, after being stirred vigorously 7h, precipitation 12h, then used in a manner of suction filtration
Deionization is washed 3-5 times, then is dried moisture removal and obtained carbonate precursor；The powdered carbonate precursor that will be filtrated to get
Ground with 0.84moL lithium carbonate, be placed in being heat-treated in Muffle furnace, be specially calcined 15h at 900 DEG C, obtain powdered
Lithium-rich manganese-based manganese-based anode material, chemical formula are：0.2Li2MnO3·0.8LiMn1/3Ni1/3Co1/3O2。
(2) citric acid for weighing 0.00103mol is dissolved in 20mL deionized waters, and adds 0.0000573mol ammonium tungstates,
Under 70 DEG C of water bath conditions, 2h is stirred, then adds 0.00138mol lithium nitrates, continue stirring reaction 1h, form colloidal sol, most
Colloidal sol is placed in Muffle furnace afterwards, 8h is calcined under the conditions of 600 DEG C, obtains powdered tungstate lithium presoma.
(3) take the lithium-rich manganese-based layered lithium ion battery positive electrode prepared in 6g (1), with obtained in (2) it is powdered
Ammonium tungstate presoma is well mixed, grinding, then is calcined in Muffle furnace, is specially calcined 5h under the conditions of 650 DEG C, is produced wolframic acid
Lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, and, to be powdered, chemical formula is for it：(0.2Li2MnO3·
0.8LiMn1/3Ni1/3Co1/3O2)/0.03Li2WO4。
Embodiment 7
A kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, and its preparation method comprises the following steps：
(1) 0.4moL manganese acetates, 0.05moL acetic acid being bored, 0.05moL nickel acetates are dissolved in 90mL deionized waters successively,
50 DEG C of stirring in water bath, obtain raw material mixed liquor；0.5moL sodium carbonate is dissolved in 30mL deionized waters and forms aqueous sodium carbonate；
0.5moL ammonium hydrogen carbonate is dissolved in 30mL deionized waters and forms ammonium bicarbonate aqueous solution；By above-mentioned three kinds of solution three-phase cocurrent, make
It instills pH using identical flow velocity simultaneously, and under 50 DEG C of water bath conditions, after stirring 7h, and precipitation
12h, then it is washed with deionized water 3-5 times in a manner of suction filtration, then dries moisture removal and obtain carbonate precursor；It will filter
The powdered carbonate precursor arrived mixes with 0.85moL lithium carbonate, grinds 2h；Finally it is placed in Muffle furnace, in 900 DEG C of bars
15h is calcined under part, obtains powdered lithium-rich manganese-based manganese-based anode material, chemical formula is：0.7Li2MnO3·0.3LiMn1/3Ni1/ 3Co1/3O2。
(2) citric acid for weighing 0.00429mol is dissolved in 20mL deionized waters, and adds 0.0000238moL metatungstic acids
Ammonium, under 70 DEG C of water bath conditions, 2h is stirred, adds 0.00573moL lithium hydroxides, continues stirring reaction 2h, obtains tungstate lithium
Colloidal sol.
(3) the lithium-rich manganese-based layered lithium ion battery positive electrode in 5g (1), the tungstate lithium colloidal sol being added in (2) are taken
In, stirring, and the ultrasound infiltration 30min under 40KHz ultrasonic frequency, then the negative pressure impregnation under conditions of -0.08MPa, dry
It is dry, obtain a kind of tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor；The tungstate lithium that will finally obtain
Modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor is in 70 DEG C of air drying 12-24h, 650 DEG C of bars of Muffle furnace
5h is calcined under part, powdered tungstate lithium is produced and is modified lithium-rich manganese-based layered lithium ion battery positive electrode, chemical formula is：
(0.7Li2MnO3·0.3LiMn1/3Ni1/3Co1/3O2)/0.15Li2WO4。
Embodiment 8
A kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, and its preparation method comprises the following steps：
(1) it is manganese nitrate 0.04moL, cobalt nitrate 0.024moL, nickel nitrate 0.024moL, lithium nitrate 0.104moL is molten successively
Then solution adds resorcinol, stirring and dissolving in formaldehyde；Wherein, the addition of resorcinol is according to n (resorcinol)：n
(formaldehyde) is 1:2 calculate；It is transferred to until completely dissolved in the liner hydrothermal reaction kettle of polytetrafluoroethylene (PTFE), then in reaction temperature
To carry out 12h hydro-thermal reaction at 180 DEG C, after question response terminates, solid precursor is obtained, by solid precursor at 850 DEG C
12h is calcined, obtains powdered lithium-rich manganese-based anode material, chemical formula is：0.1Li2MnO3·0.9LiMn1/3Ni1/3Co1/3O2。
(2) citric acid and 0.000172moL ammonium tungstates for weighing 0.0309moL are dissolved in 20mL deionized waters, in 70 DEG C
Under water bath condition, 2h is stirred, adds 0.0413moL lithium hydroxides, continued to react 1h, obtain tungstate lithium colloidal sol.
(3) the lithium-rich manganese-based layered lithium ion battery positive electrode in 3g (1) is taken, is added in tungstate lithium colloidal sol, is stirred,
And the ultrasound infiltration 20min under 40KHz ultrasonic frequency, then the negative pressure impregnation under conditions of -0.05MPa, drying, obtain one
Kind tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode material precursor；Then obtained tungstate lithium is modified rich lithium manganese
Basic unit's shape precursor of lithium ionic cell positive material is in 70 DEG C of air drying 12-24h, last 650 DEG C of conditions in Muffle furnace
Lower calcining 5h, produce powdered tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode.Chemical formula is：
(0.1Li2MnO3·0.9LiMn1/3Ni1/3Co1/3O2)/0.18Li2WO4。
Embodiment 9
A kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, and its preparation method comprises the following steps：
(1) stoichiometrically by manganese sulfate 0.032moL, cobaltous sulfate 0.018moL, nickel sulfate 0.018moL and acetic acid
Lithium 0.078moL is dissolved in formaldehyde successively, then adds resorcinol, stirring and dissolving；Wherein, the addition of resorcinol is pressed
According to n (resorcinol)：N (formaldehyde) is 1:2 calculate；The liner hydrothermal reaction kettle of polytetrafluoroethylene (PTFE) is transferred to until completely dissolved
In, 15h hydro-thermal reaction is carried out at being then 150 DEG C in reaction temperature, after reaction terminates, solid precursor is obtained, by solid
Presoma is placed in Muffle furnace, and calcines 12h at 850 DEG C, obtains powdered lithium-rich manganese-based anode material, and chemical formula is：
0.1Li2MnO3·0.9LiMn1/3Ni1/3Co1/3O2。
(2) citric acid for weighing 0.00143moL is dissolved in 20mL deionized waters, and 0.0000769moL ammonium tungstates are added,
Under 60 DEG C of water bath conditions, 2h is stirred, then adds 0.00191moL lithium nitrates, stirring forms colloidal sol, thermally treated to obtain
Tungstate lithium precursor powder.
(3) the ammonium tungstate presoma obtained in the lithium-rich manganese-based layered lithium ion battery positive electrode in 5g (1) and (2) is taken
It is well mixed, 3h is ground, is placed in Muffle furnace, 5h is calcined under the conditions of 650 DEG C, tungstate lithium is obtained and is modified lithium-rich manganese-based stratiform
Anode material for lithium-ion batteries, to be powdered, chemical formula is for it：(0.1Li2MnO3·0.9LiMn1/3Ni1/3Co1/3O2)/
0.05Li2WO4。
Embodiment 10
A kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, and its preparation method comprises the following steps：
(1) lithium nitrate 0.019moL, manganese nitrate 0.00933moL, nickel nitrate 0.00033moL, cobalt nitrate are weighed respectively
0.00033moL is dissolved in 30ml deionized waters, adds the complexing of 0.1moL sucrose, stirs 5h under 80 DEG C of water bath conditions, in air
100 DEG C of insulation 36h, are subsequently placed in Muffle furnace, calcine 5h under the conditions of 450 DEG C first, then calcine 12h at 900 DEG C；
To powdered lithium-rich manganese-based layered lithium ion battery positive electrode, its chemical formula is：0.9Li2MnO3·0.1LiMn1/3Ni1/ 3Co1/3O2。
(2) citric acid and 0.000255mol tungsten hexachlorides for weighing 0.0023mol are dissolved in 20mL deionized waters, in 70
Under DEG C water bath condition, 3h is stirred, adds 0.00306mol lithium nitrates, continues stirring reaction 1h, forms colloidal sol, then it is thermally treated
Obtain powdered tungstate lithium presoma.
(3) the powdered tungstate lithium obtained in the lithium-rich manganese-based layered lithium ion battery positive electrode in 2g (1) and (2) is taken
Presoma is well mixed, and grinds 5h；Finally it is placed in Muffle furnace and calcines 4h under the conditions of 750 DEG C, produces tungstate lithium and be modified rich lithium
Manganese basic unit shape anode material for lithium-ion batteries, chemical formula are：(0.9Li2MnO3·0.1LiMn1/3Ni1/3Co1/3O2)/
0.2Li2WO4。
The tungstate lithium that the various embodiments described above are prepared is modified lithium-rich manganese-based layered lithium ion battery positive electrode and carried out
The detection of chemical property, testing result are as follows：
Fig. 1 is that tungstate lithium prepared by embodiment 1 is modified lithium-rich manganese-based layered lithium ion battery positive electrode X-ray diffraction
(XRD) spectrogram.The diffraction that tungstate lithium corresponds to diffraction maximum and the lithium-rich manganese-based stratified lithium ion anode material of raw material is labelled with figure
Peak.By the diffraction maximum that tungstate lithium position is marked in figure with being understood after the contrast of tungstate lithium standard card, the material synthesized by the present invention
Exist in the diffraction maximum of corresponding crystal face and sharply, coincide with the diffraction maximum of tungstate lithium standard card.Illustrate to have synthesized pure phase tungsten
Sour lithium, without impurity, this patent has synthesized target substance and purity is high.In addition, the lithium-rich manganese-based Layered Lithium of raw material will be marked
The positive electrode contrast unmodified with pure sample of the diffraction maximum position of ion positive electrode finds, the test result of modified material with
The test result of unmodified positive electrode is similar, maintains original tripartite's layer structure, whole collection of illustrative plates is except original richness
Outside the diffraction maximum of lithium manganese base stratified lithium ion anode material, the diffraction maximum corresponding to wolframic acid lithium material have also appeared.This can be pushed away
Disconnected to draw, the present invention has synthesized tungstate lithium and has been modified the structure of lithium-rich manganese-based stratified lithium ion anode material, and does not change original
The layer structure of positive electrode, it is to occur new tungstate lithium phase in the composite, maintains the intrinsic performance of raw material.
The XRD testing results of other embodiment are identical with the testing result of embodiment 1, show that tungstate lithium is modified rich lithium manganese
Basic unit's shape anode material for lithium-ion batteries does not change the intrinsic structure of lithium-rich manganese-based layered lithium ion battery positive electrode, protects
Its proper property is held.
Fig. 2 is the scanning electron that tungstate lithium prepared by embodiment 4 is modified lithium-rich manganese-based layered lithium ion battery positive electrode
Microscope figure, figure are figure picture of the modified material in 50,000 times of multiplication factors.As seen from the figure, the tungstate lithium that prepared by embodiment 5 changes
The grain diameter of the lithium-rich manganese-based layered cathode active material of property is increased slightly in 200-400nm, modified particle size, and
It is modified to have obvious agglomeration, without obvious corner angle.This is probably because tungstate lithium modification is lived in lithium-rich manganese-based layered cathode
The surface of property material.
The ESEM characterization result of other embodiment is consistent with the result of embodiment 5, shows that tungstate lithium is preferable
Modification on lithium-rich manganese-based layered lithium ion battery positive electrode.
Fig. 3 is that tungstate lithium prepared by embodiment 4 is modified lithium-rich manganese-based layered cathode active material and unmodified rich lithium manganese
The circulation number of turns under basic unit's shape positive electrode active materials are 100mA/g in charging and discharging currents density is the 1st circle and the 200th charge and discharge enclosed
Electric curve comparison figure.In figure, curve represents the charge data of circulation into the curve of ascendant trend respectively, and curve is into downward trend
Curve represents the discharge data of circulation respectively.As seen from the figure, tungstate lithium is can be seen that from the initial charge curve of two kinds of materials to change
Property lithium-rich manganese-based layered cathode active material and unmodified lithium-rich manganese-based layered cathode active material charging curve basic one
Cause, be all made up of obvious two parts, a part is the LiMn that 3.7V starts1/3Ni1/3Co1/3O2Short characteristics of ramps
Platform, another part are the Li in 4.5V2MnO3Long platform.Two kinds of curves are sufficiently close in the charging and discharging curve of the 1st circle, tungsten
Sour lithium is modified lithium-rich manganese-based layered cathode active material, and discharge platform slightly improves first, and as discharge and recharge is carried out, electric discharge is flat
Platform decay is slow, and platform is gentle and more square；The specific discharge capacity of material is slightly improved simultaneously.Unmodified lithium-rich manganese-based stratiform is just
Pole active material first discharge specific capacity is 251mAh/g, and tungstate lithium is modified lithium-rich manganese-based layered cathode active material capacity and is
258mAh/g；With the progress of circulation, when the 200th encloses, the capacity of unmodified lithium-rich manganese-based layered cathode active material declines
Subtract more seriously, decay to 108mAh/g from 251mAh/g, capacity attenuation rate is 56.97%, and discharge platform flex point declines from 3.4V
Reduce to 2.5V；And the specific discharge capacity that tungstate lithium is modified lithium-rich manganese-based layered cathode active material still has 140mAh/g, capacity declines
Lapse rate is 42.63%, and platform flex point decays to 3.0V from 3.5V；Modified platform and capacity improve compared to first lap more
Substantially.Testing result is also shown that compared with unmodified lithium-rich manganese-based layered cathode active material tungstate lithium is modified lithium-rich manganese-based
Layered cathode active material is after the circulation number of turns is more than 200 circles, the lifting of its effect on specific discharge capacity and platform decay
It is more notable.It follows that lithium-rich manganese-based layered lithium ion battery positive electrode can be effectively improved after modified tungstate lithium
Discharge platform and specific discharge capacity decay.
The charge-discharge performance testing result of other embodiment is suitable with the result of embodiment 4, and, when 200 enclose, discharge ratio for it
Capacity all maintains 150mAh/g or so substantially, and discharge platform and specific discharge capacity decay are slowed by.
Fig. 4 is that the lithium-rich manganese-based layered cathode active material of tungstate lithium modification prepared by embodiment 1 is close in different discharge currents
Circulation figure under degree.As seen from the figure, in the cyclic process that current density is 20mA/g, unmodified lithium-rich manganese-based stratiform
The capacity attenuation of anode material for lithium-ion batteries is very fast, and the modified decay to capacity of tungstate lithium is significantly improved.Whole circulation
Find out in figure, modified tungstate lithium is advantageous to the raising to the specific discharge capacity of material, and the improvement under high current density is more bright
It is aobvious.Unmodified lithium-rich manganese-based layered cathode active material specific capacity under 400mA/g discharge current density is 22.1mAh/
G, and the lithium-rich manganese-based layered cathode active material of tungstate lithium modification still has putting for 63.4mAh/g under 1000mA/g current density
Electric specific capacity.Therefore draw a conclusion：Multiplying power after the lithium-rich manganese-based layered cathode active material of tungstate lithium modification is obviously improved, big
Improvement under current density is particularly evident.
The circulation test result of other embodiment is suitable with the test result of embodiment 1, equally shows electric discharge
Specific capacity improves, and discharge platform decay slows down, powerful feature.
Fig. 5 be tungstate lithium prepared by embodiment 1 be modified lithium-rich manganese-based layered lithium ion battery positive electrode with it is unmodified
The long circulating performance comparison figure of lithium-rich manganese-based layered lithium ion battery positive electrode.It can be seen that tungstate lithium is modified
The cycle performance of anode material for lithium-ion batteries obtain larger improvement, slow down to later stage capacity attenuation speed；In circulating ring
Number for 100 circle when, its specific capacity can also be maintained at 175mAh/g, and the specific capacity of unmodified anode material for lithium-ion batteries
Then decay to 148mAh/g.
The long circulating performance test results of other embodiment and the result of embodiment 1 are substantially suitable, are 100 in the circulation number of turns
During circle, specific capacity is held in more than 160mAh/g.
The present invention improves the appearance of lithium-rich manganese-based layered lithium ion battery positive electrode using the satisfactory electrical conductivity of tungstate lithium
Amount and platform decay and high rate performance, obtain platform and slow, the powerful electrode material of specific discharge capacity decay.
Although the present invention is described in detail with a general description of the specific embodiments in this specification,
But on the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.
Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed model
Enclose.
Claims (10)
1. a kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that its chemical general formula is
(xLi2MnO3·(1-x)LiMO2)/yLi2WO4；Wherein, 0.1≤x≤0.9,0.001≤y≤0.4, M Mn, Co and Ni.
2. a kind of tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that including following raw material group
Point：Manganese raw material, nickel raw material, cobalt raw material, lithium salts, tungsten salt, complexing agent, reducing agent and liquid flux.
3. tungstate lithium according to claim 2 is modified lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that
The manganese raw material is manganese metal, Mn oxide, inorganic salts containing manganese, organic salt containing manganese or alkoxide containing manganese；The nickel raw material is metal
Nickel, nickel oxide, nickeliferous inorganic salts, nickeliferous organic salt or nickeliferous alkoxide；The cobalt raw material is metallic cobalt, cobalt/cobalt oxide, containing cobalt
Inorganic salts, organic salt containing cobalt or alkoxide containing cobalt；The lithium salts is oxidate for lithium, inorganic salts containing lithium, organic salt containing lithium or alcohol containing lithium
Salt；The tungsten salt is tungsten oxide, tungstenic organic salt, tungstenic inorganic salts or tungstenic alkoxide；The complexing agent includes alcamines network
Mixture, hydroxycarboxylic acid complexing agent, organic phosphate complexing agent or polyacrylic complexing agent；The reducing agent includes inorganic
Acids reducing agent, organic acid reducing agent or alcohols reducing agent；The liquid flux is deionized water, ethanol or ethylene glycol ethyl ethers
Ether.
4. tungstate lithium according to claim 2 is modified lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that
In the lithium salts, manganese raw material, nickel raw material and cobalt raw material, when manganese raw material is bivalent manganese raw material, nickel raw material is that nickelous raw material, cobalt are former
Expect for divalence cobalt raw material when, wherein, Li+、Mn2+、Ni2+With Co2+Mol ratio be (1.1~1.9)：(0.3997~0.9333)：
(0.2997~0.0333)：(0.2997~0.0333).
5. a kind of tungstate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that including
Following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared：By manganese raw material, nickel raw material, cobalt raw material and lithium salts successively
It is dissolved in liquid flux, adds complexing agent, heating water bath, stirring reaction 3-5h under the conditions of 50-80 DEG C, it is molten obtains presoma
Glue, then the precursor sol is heat-treated, obtains lithium-rich manganese-based layered lithium ion battery positive electrode；Wherein, institute
Heat treatment is stated to carry out according to following operation：In Muffle furnace, under air atmosphere, 3-5h is calcined under the conditions of 350-550 DEG C first,
12-24h is calcined under the conditions of 800-950 DEG C again；
Step 2, tungstate lithium presoma is prepared：Tungsten source and reducing agent are dissolved in liquid flux, under the conditions of 50-70 DEG C water-bath add
Heat, 2-3h is stirred, adds lithium salts, continued to stir 1-2h, obtain tungstate lithium colloidal sol；
Step 3, prepare tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode：By the lithium-rich manganese-based Layered Lithium from
Sub- cell positive material mixes with the tungstate lithium colloidal sol, be stirred successively, ultrasonic infiltration, negative pressure impregnation, heat treatment, produce
Tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode；Wherein, the time of the ultrasound infiltration is 20-40min；Institute
Heat treatment is stated to carry out according to following operation：In Muffle furnace, under air atmosphere, 4-8h is calcined under the conditions of 600-750 DEG C.
6. a kind of tungstate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that including
Following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared：Manganese raw material, nickel raw material, cobalt raw material are dissolved in liquid successively
In body solvent, complexing agent, lithium salts are added, heating water bath, stirring reaction 3-5h under the conditions of 50-70 DEG C, obtain precursor sol,
Then the precursor sol is heat-treated, obtains lithium-rich manganese-based layered lithium ion battery positive electrode；Wherein, the heat
Processing is carried out according to following operation：In Muffle furnace, under air atmosphere, 3-5h is calcined under the conditions of 350-550 DEG C first, then
12-24h is calcined under the conditions of 800-950 DEG C；
Step 2, tungstate lithium presoma is prepared：Tungsten source and reducing agent are dissolved in liquid flux, under the conditions of 50-70 DEG C water-bath add
Heat, 2-3h is stirred, adds lithium salts, continued to stir 1-2h, form colloidal sol, then be heat-treated, obtain tungstate lithium presoma；Its
In, the heat treatment refers to calcine 4-8h under the conditions of 600-750 DEG C；
Step 3, prepare tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode：By the lithium-rich manganese-based Layered Lithium from
Sub- cell positive material is well mixed with the tungstate lithium presoma, grinding, then is heat-treated, and is produced tungstate lithium and is modified rich lithium
Manganese basic unit shape anode material for lithium-ion batteries；Wherein, the heat treatment refers to calcine 4-8h under the conditions of 600-750 DEG C.
7. a kind of tungstate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that including
Following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared：It is first that manganese raw material, nickel raw material, cobalt raw material is molten successively
In liquid flux, raw material mixed liquor is obtained；Then sodium carbonate and sodium acid carbonate are dissolved in liquid flux respectively, obtain carbonic acid respectively
Sodium solution and sodium bicarbonate solution；Raw material mixed liquor, sodium carbonate liquor and the sodium bicarbonate solution are added dropwise to simultaneously again
In ionized water, and the heating water bath under the conditions of 50-70 DEG C, stirring reaction 6-7h, it is aged, is filtered, is dried successively afterwards, obtained
To carbonate precursor；Then the carbonate precursor is mixed with lithium salts, grinds, be finally heat-treated, obtain rich lithium
Manganese basic unit shape anode material for lithium-ion batteries；
Step 2, tungstate lithium presoma is prepared：Tungsten source and reducing agent are dissolved in liquid flux, under the conditions of 50-70 DEG C water-bath add
Heat, 2-3h is stirred, adds lithium salts, continued to stir 1-2h, form colloidal sol, then be heat-treated, obtain tungstate lithium presoma；Its
In, the heat treatment refers to calcine 4-8h under the conditions of 600-750 DEG C；
Step 3, prepare tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode：By the lithium-rich manganese-based Layered Lithium from
Sub- cell positive material is well mixed with the tungstate lithium presoma, grinding, then is heat-treated, and is produced tungstate lithium and is modified rich lithium
Manganese basic unit shape anode material for lithium-ion batteries；Wherein, the heat treatment refers to calcine 4-8h under the conditions of 600-750 DEG C.
8. a kind of tungstate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that including
Following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared：It is first that manganese raw material, nickel raw material, cobalt raw material is molten successively
In liquid flux, raw material mixed liquor is obtained；Then sodium carbonate and sodium acid carbonate are dissolved in liquid flux respectively, obtain carbonic acid respectively
Sodium solution and sodium bicarbonate solution；Raw material mixed liquor, sodium carbonate liquor and the sodium bicarbonate solution are added dropwise to simultaneously again
In ionized water, and the heating water bath under the conditions of 50-70 DEG C, stirring reaction 6-7h, it is aged, is filtered, is dried successively afterwards, obtained
To carbonate precursor；Then the carbonate precursor is mixed with lithium salts, grinds, be finally heat-treated, obtain rich lithium
Manganese basic unit shape anode material for lithium-ion batteries；Wherein, the heat treatment refers to calcine 4-8h under the conditions of 600-750 DEG C；
Step 2, tungstate lithium presoma is prepared：Tungsten source and reducing agent are dissolved in liquid flux, under the conditions of 50-70 DEG C water-bath add
Heat, 2-3h is stirred, adds lithium salts, continued to stir 1-2h, obtain tungstate lithium colloidal sol；
Step 3, prepare tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode：By the lithium-rich manganese-based Layered Lithium from
Sub- cell positive material mixes with the tungstate lithium colloidal sol, be stirred successively, ultrasonic infiltration, negative pressure impregnation, heat treatment, produce
Tungstate lithium is modified lithium-rich manganese-based layered lithium ion battery positive electrode；Wherein, the heat treatment refers under the conditions of 600-750 DEG C
Calcine 4-8h.
9. a kind of tungstate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that including
Following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared：By manganese raw material, nickel raw material, cobalt raw material and lithium salts successively
It is dissolved in liquid flux, adds complexing agent, stirring and dissolving, carry out hydro-thermal reaction after dissolving, hydro-thermal reaction must be consolidated after terminating
Body presoma, the solid precursor is heat-treated, obtains lithium-rich manganese-based layered lithium ion battery positive electrode；
Step 2, tungstate lithium presoma is prepared：Tungsten source and reducing agent are dissolved in liquid flux, under the conditions of 50-70 DEG C water-bath add
Heat, 2-3h is stirred, adds lithium salts, continued to stir 1-2h, form colloidal sol, obtain tungstate lithium presoma；
Step 3, prepare tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode：By the lithium-rich manganese-based Layered Lithium from
Sub- cell positive material mixes with the tungstate lithium presoma, be stirred successively, ultrasonic infiltration, negative pressure impregnation, heat treatment, i.e.,
Obtain tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode.
10. a kind of tungstate lithium is modified the preparation method of lithium-rich manganese-based layered lithium ion battery positive electrode, it is characterised in that including
Following steps：
Step 1, lithium-rich manganese-based layered lithium ion battery positive electrode is prepared：By manganese raw material, nickel raw material, cobalt raw material and lithium salts successively
It is dissolved in formaldehyde, adds resorcinol, stirring and dissolving carries out hydro-thermal reaction after dissolving, hydro-thermal reaction obtains solid after terminating
Presoma, the solid precursor is heat-treated, obtains lithium-rich manganese-based layered lithium ion battery positive electrode；Wherein,
The mol ratio of benzenediol and formaldehyde is 1:2；
Step 2, tungstate lithium presoma is prepared：Tungsten source and reducing agent are dissolved in liquid flux, under the conditions of 50-70 DEG C water-bath add
Heat, 2-3h is stirred, adds lithium salts, continued to stir 1-2h, form colloidal sol, then be heat-treated, obtain tungstate lithium precursor
End；
Step 3, prepare tungstate lithium and be modified lithium-rich manganese-based layered lithium ion battery positive electrode：By the lithium-rich manganese-based Layered Lithium from
Sub- cell positive material is well mixed with the tungstate lithium precursor powder, grinding, then is heat-treated, and produces tungstate lithium modification
Lithium-rich manganese-based layered lithium ion battery positive electrode.
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