CN103367733A - Lithium ion battery cathode material and preparation method thereof and lithium ion battery - Google Patents
Lithium ion battery cathode material and preparation method thereof and lithium ion battery Download PDFInfo
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- CN103367733A CN103367733A CN2013102871784A CN201310287178A CN103367733A CN 103367733 A CN103367733 A CN 103367733A CN 2013102871784 A CN2013102871784 A CN 2013102871784A CN 201310287178 A CN201310287178 A CN 201310287178A CN 103367733 A CN103367733 A CN 103367733A
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- lithium
- anode material
- manganese
- nickel
- ion batteries
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 54
- 239000010406 cathode material Substances 0.000 title abstract 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 136
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 125
- 239000010405 anode material Substances 0.000 claims description 197
- 239000011572 manganese Substances 0.000 claims description 154
- 239000013049 sediment Substances 0.000 claims description 103
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 93
- 239000007864 aqueous solution Substances 0.000 claims description 79
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 44
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 37
- 239000003153 chemical reaction reagent Substances 0.000 claims description 34
- 238000001556 precipitation Methods 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 30
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 29
- 229910003002 lithium salt Inorganic materials 0.000 claims description 26
- 229910013716 LiNi Inorganic materials 0.000 claims description 25
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 150000002696 manganese Chemical class 0.000 claims description 16
- 150000002815 nickel Chemical class 0.000 claims description 16
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 15
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 15
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 11
- 239000001099 ammonium carbonate Substances 0.000 claims description 11
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 10
- 229940099596 manganese sulfate Drugs 0.000 claims description 9
- 239000011702 manganese sulphate Substances 0.000 claims description 9
- 235000007079 manganese sulphate Nutrition 0.000 claims description 9
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- 239000011565 manganese chloride Substances 0.000 claims description 7
- 235000002867 manganese chloride Nutrition 0.000 claims description 7
- 229940099607 manganese chloride Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- 229940078494 nickel acetate Drugs 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- 229910017246 Ni0.8Co0.1Mn0.1 Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910015118 LiMO Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910001170 xLi2MnO3-(1−x)LiMO2 Inorganic materials 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 11
- 230000014759 maintenance of location Effects 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 27
- 229910001437 manganese ion Inorganic materials 0.000 description 27
- 229910001453 nickel ion Inorganic materials 0.000 description 27
- -1 lithium salts lithium carbonate Chemical class 0.000 description 25
- 238000000975 co-precipitation Methods 0.000 description 20
- 229910012409 LiNi0.4Mn1.6O4 Inorganic materials 0.000 description 17
- 230000032683 aging Effects 0.000 description 17
- 239000002244 precipitate Substances 0.000 description 17
- 229910001429 cobalt ion Inorganic materials 0.000 description 16
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 16
- 239000011656 manganese carbonate Substances 0.000 description 14
- 235000006748 manganese carbonate Nutrition 0.000 description 14
- 229940093474 manganese carbonate Drugs 0.000 description 14
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 14
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 14
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 14
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000007599 discharging Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 7
- UORLFMNCHYTQSD-UHFFFAOYSA-N manganese(2+) tetranitrate Chemical class [Mn++].[Mn++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O UORLFMNCHYTQSD-UHFFFAOYSA-N 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- AZMQGJINSTTZTP-UHFFFAOYSA-J manganese(2+);disulfate Chemical compound [Mn+2].[Mn+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AZMQGJINSTTZTP-UHFFFAOYSA-J 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910013554 LiNi0.05Mn1.95O4 Inorganic materials 0.000 description 5
- HAZNKDJFOOUKJY-UHFFFAOYSA-N [Ni++].[Ni++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical class [Ni++].[Ni++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HAZNKDJFOOUKJY-UHFFFAOYSA-N 0.000 description 5
- SGDPVQRGBHPKIH-UHFFFAOYSA-L [Ni].Cl[Ni]Cl Chemical compound [Ni].Cl[Ni]Cl SGDPVQRGBHPKIH-UHFFFAOYSA-L 0.000 description 5
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 5
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 4
- WGLWCANOKOJRDY-UHFFFAOYSA-J manganese(2+);tetraacetate Chemical class [Mn+2].[Mn+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O WGLWCANOKOJRDY-UHFFFAOYSA-J 0.000 description 4
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- JEMUNLMELOOTDQ-UHFFFAOYSA-J [Cl-].[Cl-].[Cl-].[Cl-].[Mn++].[Mn++] Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Mn++].[Mn++] JEMUNLMELOOTDQ-UHFFFAOYSA-J 0.000 description 3
- AHZXJMJKTLUFMC-UHFFFAOYSA-J cobalt(2+) tetraacetate Chemical compound [Co+2].[Co+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O AHZXJMJKTLUFMC-UHFFFAOYSA-J 0.000 description 3
- GHGNQWNTEPHORR-UHFFFAOYSA-L cobalt;dichlorocobalt Chemical compound [Co].Cl[Co]Cl GHGNQWNTEPHORR-UHFFFAOYSA-L 0.000 description 3
- AKWULMNJVXIMRR-UHFFFAOYSA-J nickel(2+);tetraacetate Chemical compound [Ni+2].[Ni+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O AKWULMNJVXIMRR-UHFFFAOYSA-J 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium ion battery cathode material and a preparation method thereof and a lithium ion battery; and the lithium ion battery cathode material has a structure of covering LiNiyMn2-yO4 outside lithium-rich cathode material, wherein y is more than 0 and less than or equal to 0.5. The lithium ion battery cathode material not only has the outstanding advantages of high specific capacity and high voltage of the lithium-rich cathode material, but also has the advantages of high voltage, high capacity retention ratio, good cycling stability and rate capability and long service life of LiNiyMn2-yO4. Compared with single lithium-rich cathode material, the lithium ion battery cathode material which is formed by covering the LiNiyMn2-yO4 outside the lithium-rich cathode material overcomes the defects that the single lithium-rich cathode material is low in first time coulomb efficiency and poor in rate capability; the electrochemical performance of the lithium ion battery cathode material is improved. Furthermore, the lithium ion battery cathode material is simple in preparation technology and low in cost, thus being very suitable for large-scale industrial production.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of anode material for lithium-ion batteries and preparation method thereof, battery.
Background technology
Along with the progress of science and technology, improve day by day to the requirement of energy storage device in the fields such as electronic product (mobile phone, digital product, notebook computer etc.), electric automobile, Medical Devices and space flight and aviation, conventional positive electrode for example, LiCoO
2, LiMn
2O
4, LiFePO
4Deng more and more can not satisfy high power capacity, the high-energy-density of people to lithium ion battery, have extended cycle life, self discharge is little, the demand of memory-less effect, environmentally safe.Stratiform lithium-rich anode material xLi
2MnO
3(1-x) LiMO
2(M=Mn, Ni, Co, Ni
0.5Mn
0.5, Cr, Ni
1/3Co
1/3Mn
1/3, Fe...) be a kind of α-NaFeO
2The type solid-solution material is by the Li of stratiform
2MnO
3And LiMO
2(M=Mn, Ni, Co, Ni
0.5Mn
0.5, Cr, Ni
1/3Co
1/3Mn
1/3, Fe...) form, its have height ratio capacity (200～300mAh/g) and high-tension outstanding advantages, probably become the positive electrode of high-performance lithium ion battery of future generation, become the focus of domestic and international research.But lithium-rich anode material still exists and has the i.e. enclosed pasture inefficiency first of larger irreversible capacity loss in the first charge-discharge process, and the problem such as high rate performance is poor, cycle performance is poor, has limited its commercial applications.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in the prior art, a kind of anode material for lithium-ion batteries and preparation method thereof, battery are provided, this anode material for lithium-ion batteries has height ratio capacity and the high-tension advantage of its kernel lithium-rich anode material, also has its shell LiNi simultaneously
yMn
2-yO
4The high voltage of (0＜y≤0.5), capability retention height, good cycling stability, good rate capability, long advantage of life-span.
The technical scheme that solution the technology of the present invention problem adopts provides a kind of anode material for lithium-ion batteries, and its structure is for to be coated with LiNi at lithium-rich anode material
yMn
2-yO
4, wherein, 0＜y≤0.5.Wherein, lithium-rich anode material is layer structure, LiNi
yMn
2-yO
4Be spinel structure.
Preferably, the structure of described anode material for lithium-ion batteries is for to be coated with LiNi at described lithium-rich anode material
yMn
2-yO
4, wherein, y=0.4 or 0.5.
Preferably, described lithium-rich anode material is xLi
2MnO
3(1-x) LiMO
2, and 0.1≤x≤0.9, wherein,
M is Ni
0.5Mn
0.5, Ni
1/3Co
1/3Mn
1/3, Ni
0.5Co
0.3Mn
0.2, Ni
0.4Co
0.4Mn
0.2, Ni
0.8Co
0.1Mn
0.1, Ni
0.6Co
0.2Mn
0.2, Ni
0.7Co
0.15Mn
0.15In any one.
Preferably, described LiNi
yMn
2-yO
4Account for 2%～20% of described anode material for lithium-ion batteries quality.
The present invention also provides a kind of preparation method of anode material for lithium-ion batteries, may further comprise the steps:
(1) prepares the mixed aqueous solution of the first slaine of each described metallic element according to the coefficient proportioning between each metallic element except lithium in the molecular formula of lithium-rich anode material, add again the first precipitation reagent that contains hydroxyl or carbonate, obtain the first sediment;
(2) according to amount of substance ratio Ni: the Mn=y:(2-y) mixed aqueous solution of preparation the second nickel salt and the second manganese salt, and mix with described the first sediment in the described step (1), then add the second precipitation reagent that contains hydroxyl or carbonate, obtain the first sediment that the second sediment coats;
(3) be coated with LiNi according to described lithium-rich anode material
yMn
2-yO
4Whole compound in proportioning between lithium and all the other metallic elements, 0＜y≤0.5 wherein, the first sediment that the first lithium salts and described the second sediment are coated mixes afterwards that calcination obtains described anode material for lithium-ion batteries.
Preferably, described the first slaine in the described step (1) is the first manganese salt, the first nickel salt or the first cobalt salt, described step (1) is specially: adding described described the first precipitation reagent that contains hydroxyl or carbonate in the mixed aqueous solution of the mixed aqueous solution of the first manganese salt, the first nickel salt or the first nickel salt, the first cobalt salt, the first manganese salt obtains described the first sediment, and the molar ratio between the manganese in described the first sediment and the molar ratio between the nickel or manganese, nickel and the cobalt satisfies the molecular formula xLi of described lithium-rich anode material
2MnO
3(1-x) LiMO
2The coefficient proportioning of middle respective metal element, and 0.1≤x≤0.9, wherein,
M is Ni
0.5Mn
0.5, Ni
1/3Co
1/3Mn
1/3, Ni
0.5Co
0.3Mn
0.2, Ni
0.4Co
0.4Mn
0.2, Ni
0.8Co
0.1Mn
0.1, Ni
0.6Co
0.2Mn
0.2, Ni
0.7Co
0.15Mn
0.15In any one.
Preferably, the calcination temperature in the described step (3) is 700 ℃～1000 ℃.
Preferably, the described calcination process in the described step (3) is specially:
Be heated to 400～600 ℃ with 0.5～10 ℃/min programming rate, heating 1～15h; In this temperature range, heat, can be so that the first sediment and lithium salts that the second sediment coats all generate oxide, thereby so that each component in the product in conjunction with closely, is easy to next step reaction;
Be heated to 750～950 ℃ with 0.5～10 ℃/min programming rate again, heating 2～24h; In this temperature range, heat, can be so that the complete in crystal formation of the anode material for lithium-ion batteries that obtains;
Then be cooled to room temperature.
Preferably, described the first precipitation reagent is one or more in sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical, the ammonium carbonate solution;
And/or described the second nickel salt is one or more in nickel nitrate, nickel acetate, nickelous sulfate, the nickel chloride;
And/or described the second manganese salt is one or more in manganese nitrate, manganese acetate, manganese sulfate, the manganese chloride;
And/or described the second precipitation reagent is one or more in sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical, the ammonium carbonate solution;
And/or described the first lithium salts is one or more in lithium carbonate, lithium hydroxide, lithium acetate, the lithium nitrate.
Preferably, described the first nickel salt is one or more in nickel nitrate, nickel acetate, nickelous sulfate, the nickel chloride;
And/or described the first cobalt salt is one or more in cobalt nitrate, cobalt acetate, cobaltous sulfate, the cobalt chloride;
And/or described the first manganese salt is one or more in manganese nitrate, manganese acetate, manganese sulfate, the manganese chloride.
The present invention also provides a kind of preparation method of anode material for lithium-ion batteries, may further comprise the steps:
According to amount of substance ratio Ni: the Mn=y:(2-y) mixed aqueous solution of preparation the 3rd nickel salt and the 3rd manganese salt, and mix with lithium-rich anode material, then add the 3rd precipitation reagent that contains hydroxyl or carbonate, obtain the described lithium-rich anode material that the 3rd sediment coats; Satisfy LiNi according to the nickel in the lithium in the second lithium salts and the 3rd sediment and the proportioning of manganese
yMn
2-yO
4Coefficient proportioning in the molecular formula, 0＜y≤0.5 wherein, the described lithium-rich anode material that described the 3rd sediment is coated mixes with the second lithium salts afterwards that calcination obtains described anode material for lithium-ion batteries.
Preferably, described the 3rd nickel salt is one or more in nickel nitrate, nickel acetate, nickelous sulfate, the nickel chloride;
And/or described the 3rd manganese salt is one or more in manganese nitrate, manganese acetate, manganese sulfate, the manganese chloride;
And/or described the 3rd precipitation reagent is one or more in sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical, the ammonium carbonate solution.
And/or described the second lithium salts is one or more in lithium carbonate, lithium hydroxide, lithium acetate, the lithium nitrate.
The present invention also provides a kind of lithium ion battery, and its positive pole comprises above-mentioned positive electrode.
The structure of the anode material for lithium-ion batteries among the present invention is for to be coated with LiNi at lithium-rich anode material
yMn
2-yO
4, wherein, 0＜y≤0.5.This positive electrode not only has height ratio capacity and the high-tension outstanding advantages of lithium-rich anode material, but also has simultaneously LiNi
yMn
2-yO
4The long advantage of high voltage, capability retention height, good cycling stability, good rate capability, life-span.Be coated with LiNi at lithium-rich anode material
yMn
2-yO
4Anode material for lithium-ion batteries with respect to single lithium-rich anode material, overcome the shortcoming that first coulombic efficiency is low, high rate performance is poor, cycle performance is poor of single lithium-rich anode material, the chemical property of this anode material for lithium-ion batteries has obtained modification.And the preparation technology of this anode material for lithium-ion batteries is simple, and cost is low, is highly suitable for large-scale industrial production.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the anode material for lithium-ion batteries of the embodiment of the invention 1 preparation;
Fig. 2 is the first charge-discharge specific capacity resolution chart of the lithium ion battery made of the anode material for lithium-ion batteries of the embodiment of the invention 1 preparation;
Fig. 3 is the charge-discharge performance resolution chart of the lithium ion battery made of the embodiment of the invention 1 preparation anode material for lithium-ion batteries;
Fig. 4 is the high rate performance resolution chart of the lithium ion battery made of the embodiment of the invention 1 preparation anode material for lithium-ion batteries.
Embodiment
For making those skilled in the art understand better technical scheme of the present invention, below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
Embodiment 1
Present embodiment provides a kind of anode material for lithium-ion batteries, and the structure of this material is at lithium-rich anode material 0.1Li
2MnO
30.9LiNi
0.5Mn
0.5O
2Be coated with LiNi
0.5Mn
1.5O
4, and this structure is nucleocapsid structure, wherein, and lithium-rich anode material 0.1Li
2MnO
30.9LiNi
0.5Mn
0.5O
2Be the nuclear of this nucleocapsid structure, LiNi
0.5Mn
1.5O
4Be the shell of this nucleocapsid structure, LiNi
0.5Mn
1.5O
4Account for 18% of anode material for lithium-ion batteries quality.
The preparation method of the anode material for lithium-ion batteries in the present embodiment may further comprise the steps:
(1) according to the molecular formula 0.1Li of lithium-rich anode material
2MnO
30.9LiNi
0.5Mn
0.5O
2In coefficient proportioning Ni: Mn=9: the mixed aqueous solution of 11 preparation the first nickel salt nickel nitrates and the first manganese salt manganese nitrates, and the molar ratio of the nickel ion in this mixed aqueous solution and manganese ion is 9: 11.In this mixed aqueous solution, add the first precipitation reagent aqueous sodium carbonate again, and the aqueous sodium carbonate excessive 4% that adds precipitates fully to guarantee nickel ion and manganese ion in the solution, leave standstill again, ageing is after 16 hours, centrifugal, the washing 5 times, obtain the first sediment, comprise the co-precipitation of nickelous carbonate and manganese carbonate in this first sediment.
(2) prepare the mixed aqueous solution of the second nickel salt nickel nitrate and the second manganese salt manganese sulfate according to amount of substance ratio Ni:Mn=1:3, the mixed aqueous solution of this nickel nitrate and manganese sulfate is mixed with the first sediment, be uniformly dispersed by ultrasonic, under stirring, to wherein dripping the second precipitation reagent aqueous sodium carbonate, and the aqueous sodium carbonate excessive 2% that adds precipitates fully to guarantee nickel ion and manganese ion in the solution, leave standstill again, after the ageing 6 hours, centrifugal, wash 3 times, lower dry 8 hours at 110 ℃, obtain the first sediment that the second sediment coats, comprise the co-precipitation of nickelous carbonate and manganese carbonate in this second sediment.
(3) the first sediment that the second sediment is coated mixes with the first lithium salts lithium carbonate that (structure according to anode material for lithium-ion batteries is at lithium-rich anode material 0.1Li
2MnO
30.9LiNi
0.5Mn
0.5O
2Be coated with LiNi
0.5Mn
1.5O
4In the element Relationship of Coefficients, lithium is excessive 2%～6%, lithium is slightly excessive to be in order to compensate at high temperature on a small quantity volatilization of lithium carbonate), add planetary ball mill, add a certain amount of ethanol again, the amount ratio of ethanol and above-mentioned solid is 1.1mL/g, with the rotating speed ball milling 4h of 300r/min, batch mixing is even.Then under air atmosphere, carry out sintering by temperature programmed control:
Be heated to 450 ℃ with 3 ℃/min programming rate, heating 6h;
Be heated to 850 ℃ with 5 ℃/min programming rate, heating 12h;
Then naturally be cooled to room temperature, namely obtain at lithium-rich anode material 0.1Li
2MnO
30.9LiNi
0.5Mn
0.5O
2Be coated with LiNi
0.5Mn
1.5O
4Anode material for lithium-ion batteries.Wherein, kernel 0.1Li
2MnO
30.9LiNi
0.5Mn
0.5O
2Be layer structure, shell LiNi
0.5Mn
1.5O
4Be spinel structure.Generated the kernel 0.1Li of anode material for lithium-ion batteries by step (1)
2MnO
30.9LiNi
0.5Mn
0.5O
2Presoma the first sediment, generated the shell LiNi of this anode material for lithium-ion batteries by step (2)
0.5Mn
1.5O
4Presoma the second sediment, by step (3) so that the first sediment can react with the first lithium salts lithium carbonate, the second sediment that is coated on simultaneously the first sediment outside also reacts with the first lithium salts lithium carbonate, like this kernel 0.1Li of anode material for lithium-ion batteries
2MnO
30.9LiNi
0.5Mn
0.5O
2With shell LiNi
0.5Mn
1.5O
4Generate simultaneously, and exist lattice energy between kernel and the shell and combine closely, energy savings so greatly, the preparation method in the present embodiment is with respect to preparing respectively 0.1Li
2MnO
30.9LiNi
0.5Mn
0.5O
2With LiNi
0.5Mn
1.5O
4Method greatly saved energy.The kernel 0.1Li of the anode material for lithium-ion batteries that obtains by this preparation method
2MnO
30.9LiNi
0.5Mn
0.5O
2With shell LiNi
0.5Mn
1.5O
4Structure all very complete, and the boundary of kernel and shell is obviously, kernel and shell can distinguish the chemical property of independently bringing into play separately, thereby have improved the chemical property of whole anode material for lithium-ion batteries.
Present embodiment also provides a kind of lithium ion battery, and its positive pole contains above-mentioned anode material for lithium-ion batteries.
Positive electrode LiNi
0.5Mn
1.5O
4Have spinel structure, the lithium ion battery of being made by this material changes mainly there is 4.7V in " lithium battery " in charge and discharge process platform, corresponding Ni into
2+/ Ni
4+Oxidation-reduction process.Positive electrode LiNi
0.5Mn
1.5O
4Theoretical specific capacity be 146.7mAh/g, this theoretical specific capacity compares LiCoO
2, LiMn
2O
4, LiFePO
4Equal height.X.Y.Feng etc. (X.Y.Feng, C.Shen,, X.Fang etc., Synthesis of LiNi
0.5Mn
1.5O
4By solid-state reaction with improved electrochemical performance, Journal of Alloys and Compounds, 509(2011) 3623-3626) adopt two step solid phase methods to synthesize LiNi
0.5Mn
1.5O
4Material, first discharge specific capacity are 140mAh/g, and 100 specific capacities that circulate are 135mAh/g, and capability retention is 96.4%, has preferably cyclical stability, and during discharging current 10C, specific discharge capacity is 113mAh/g, and high rate performance is better.
Present embodiment provides a kind of anode material for lithium-ion batteries, and the structure of this positive electrode is at lithium-rich anode material 0.1Li
2MnO
30.9LiNi
0.5Mn
0.5O
2Be coated with LiNi
0.5Mn
1.5O
4Nucleocapsid structure, this positive electrode not only has 0.1Li like this
2MnO
30.9LiNi
0.5Mn
0.5O
2Height ratio capacity and high-tension outstanding advantages, but also have simultaneously LiNi
0.5Mn
1.5O
4The long advantage of high voltage, capability retention height, good cycling stability, good rate capability, life-span.At 0.1Li
2MnO
30.9LiNi
0.5Mn
0.5O
2Be coated with LiNi
0.5Mn
1.5O
4Anode material for lithium-ion batteries with respect to single 0.1Li
2MnO
30.9LiNi
0.5Mn
0.5O
2, overcome single lithium-rich anode material 0.1Li
2MnO
30.9LiNi
0.5Mn
0.5O
2The shortcoming that first coulombic efficiency is low, high rate performance is poor, cycle performance is poor, the chemical property of this anode material for lithium-ion batteries has obtained modification.And the preparation technology of this anode material for lithium-ion batteries is simple, and cost is low, is highly suitable for large-scale industrial production.
As shown in Figure 1, the anode material for lithium-ion batteries that present embodiment makes is spheric granules, and has nucleocapsid structure, and the particle diameter of this spheric granules is 10～15um.
The preparation method of battery pole piece:
With this positive electrode and conductive agent acetylene black, binding agent PVDF(Kynoar) mix at 8: 1: 1 according to mass ratio, use the NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into slurry, evenly be coated on the aluminium foil, put into baking oven, 80～120 ℃ of lower oven dry 1 hour, take out and be washed into pole piece, 85 ℃ of vacuumize 12 hours, carry out compressing tablet, 85 ℃ of vacuumize 12 hours makes the experimental cell pole piece.Take the lithium sheet as to electrode, electrolyte is the LiPF of 1.5mol/L
6EC(ethyl carbonate ester)+the DMC(dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, is assembled into CR2025 type button cell in being full of the glove box of argon gas atmosphere.
As shown in Figure 2, this button cell is carried out the test of first charge-discharge specific capacity: the charging/discharging voltage scope is 4.8～2.0V, be 0.1C(1C=220mA/g at charging and discharging currents) condition under, the first charge-discharge specific capacity is respectively 265.173mAh/g, 232.04mAh/g, and coulombic efficiency is 87.51% first.
As shown in Figure 3, this button cell is carried out the charge-discharge performance test: be at charging and discharging currents under the condition of 0.2C, first discharge specific capacity is 222.448mAh/g, and 60 specific capacities that circulate are 211.425mAh/g, capability retention is 95%, and cyclical stability is better.
As shown in Figure 4, this button cell is carried out the high rate performance test: the charging/discharging voltage scope is 4.8～2.0V, and charging current is 0.1C, and discharging current is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, each multiplying power circulation 5 times.Wherein, 1C=220mA/g.The high rate performance test result shows that still more than 105mAh, high rate performance is better for the 5C specific discharge capacity.
Present embodiment provides a kind of anode material for lithium-ion batteries, and the structure of this material is at lithium-rich anode material 0.3Li
2MnO
30.7LiNi
1/3Co
1/3Mn
1/3O
2Be coated with LiNi
0.1Mn
1.9O
4, and this structure is nucleocapsid structure, wherein, and lithium-rich anode material 0.3Li
2MnO
30.7LiNi
1/3Co
1/3Mn
1/3O
2Be the nuclear of this nucleocapsid structure, LiNi
0.1Mn
1.9O
4Be the shell of this nucleocapsid structure, LiNi
0.1Mn
1.9O
4Account for 16% of anode material for lithium-ion batteries quality.
The preparation method of the anode material for lithium-ion batteries in the present embodiment may further comprise the steps:
(1) according to the molecular formula 0.3Li of lithium-rich anode material
2MnO
30.7LiNi
1/3Co
1/3Mn
1/3O
2In coefficient proportioning Ni: Co: Mn=7: the mixed aqueous solution of 7: 16 preparations the first nickel salt nickel acetate, the first cobalt salt cobalt acetate and the first manganese salt manganese acetates, and the molar ratio in this mixed aqueous solution is nickel ion: cobalt ions: manganese ion=7: 7: 16.In this mixed aqueous solution, add the first precipitation reagent aqueous sodium carbonate again, and the aqueous sodium carbonate excessive 5% that adds precipitates fully to guarantee nickel ion, cobalt ions, manganese ion in the solution, leave standstill again, ageing is after 12 hours, centrifugal, the washing 3 times, obtain the first sediment, comprise the co-precipitation of nickelous carbonate, cobalt carbonate and manganese carbonate in this first sediment.
(2) prepare the mixed aqueous solution of the second nickel salt nickel chloride and the second manganese salt manganese sulfate according to amount of substance ratio Ni:Mn:=1:19, the mixed aqueous solution of this nickel chloride and manganese sulfate is mixed with the first sediment, be uniformly dispersed by ultrasonic, under stirring, to wherein dripping the second precipitation reagent aqueous sodium carbonate, and the aqueous sodium carbonate excessive 5% that adds precipitates fully to guarantee nickel ion and manganese ion in the solution, leave standstill again, after the ageing 12 hours, centrifugal, wash 3 times, lower dry 8 hours at 110 ℃, obtain the first sediment that the second sediment coats, comprise the co-precipitation of nickelous carbonate and manganese carbonate in this second sediment.
(3) the first sediment that the second sediment is coated mixes with the first lithium salts lithium acetate that (structure according to anode material for lithium-ion batteries is at lithium-rich anode material 0.3Li
2MnO
30.7LiNi
1/3Co
1/3Mn
1/3O
2Be coated with LiNi
0.1Mn
1.9O
4In the element Relationship of Coefficients, lithium is excessive 2%, lithium is slightly excessive to be in order to compensate at high temperature on a small quantity volatilization of lithium acetate), add planetary ball mill, add a certain amount of ethanol again, the amount ratio of ethanol and above-mentioned solid is 1.5mL/g, with the rotating speed ball milling 8h of 350r/min, batch mixing is even.Then under air atmosphere, carry out sintering by temperature programmed control:
Be heated to 600 ℃ with 5 ℃/min programming rate, heating 8h;
Be heated to 950 ℃ with 4 ℃/min programming rate, heating 10h;
Then naturally be cooled to room temperature, namely obtain at lithium-rich anode material 0.3Li
2MnO
30.7LiNi
1/3Co
1/3Mn
1/3O
2Be coated with LiNi
0.1Mn
1.9O
4Anode material for lithium-ion batteries.Wherein, 0.3Li
2MnO
30.7LiNi
1/3Co
1/3Mn
1/3O
2Be layer structure, LiNi
0.1Mn
1.9O
4Be spinel structure.
Present embodiment provides a kind of anode material for lithium-ion batteries, and this positive electrode is at lithium-rich anode material 0.3Li
2MnO
30.7LiNi
1/3Co
1/3Mn
1/3O
2Be coated with LiNi
0.1Mn
1.9O
4Nucleocapsid structure, this positive electrode not only has 0.3Li like this
2MnO
30.7LiNi
1/3Co
1/3Mn
1/3O
2Height ratio capacity and high-tension outstanding advantages, but also have simultaneously LiNi
0.1Mn
1.9O
4The long advantage of high voltage, capability retention height, good cycling stability, good rate capability, life-span.At 0.3Li
2MnO
30.7LiNi
1/3Co
1/3Mn
1/3O
2Be coated with LiNi
0.1Mn
1.9O
4Anode material for lithium-ion batteries with respect to single 0.3Li
2MnO
30.7LiNi
1/3Co
1/3Mn
1/3O
2, overcome single lithium-rich anode material 0.3Li
2MnO
30.7LiNi
1/3Co
1/3Mn
1/3O
2The shortcoming that first coulombic efficiency is low, high rate performance is poor, cycle performance is poor, the chemical property of this anode material for lithium-ion batteries has obtained modification.And the preparation technology of this anode material for lithium-ion batteries is simple, and cost is low, is highly suitable for large-scale industrial production.
According to the method for preparing button cell among the embodiment 1, the anode material for lithium-ion batteries that uses present embodiment to make is made button cell, and this battery is carried out charge-discharge performance test: charging and discharging currents is 0.2C, first discharge specific capacity is 246.681mAh/g, coulombic efficiency is 79.52% first, 60 capability retentions that circulate are 94.8%, and cyclical stability is better.
Embodiment 3
Present embodiment provides a kind of anode material for lithium-ion batteries, and the structure of this material is at lithium-rich anode material 0.4Li
2MnO
30.6LiNi
0.5Co
0.3Mn
0.2O
2Be coated with LiNi
0.4Mn
1.6O
4, and this structure is nucleocapsid structure, wherein, and lithium-rich anode material 0.4Li
2MnO
30.6LiNi
0.5Co
0.3Mn
0.2O
2Be the nuclear of this nucleocapsid structure, LiNi
0.4Mn
1.6O
4Be the shell of this nucleocapsid structure, LiNi
0.4Mn
1.6O
4Account for 2% of anode material for lithium-ion batteries quality.
The preparation method of the anode material for lithium-ion batteries in the present embodiment may further comprise the steps:
(1) according to the molecular formula 0.4Li of lithium-rich anode material
2MnO
30.6LiNi
0.5Co
0.3Mn
0.2O
2In coefficient proportioning Ni: Co: Mn=15: the mixed aqueous solution of 9: 26 preparations the first nickel salt nickelous sulfate, the first cobalt salt cobaltous sulfate and the first manganese salt manganese sulfates, and the molar ratio in this mixed aqueous solution is nickel ion: cobalt ions: manganese ion=15: 9: 26.In this mixed aqueous solution, add the first precipitation reagent wet chemical again, and the wet chemical excessive 5% that adds precipitates fully to guarantee nickel ion, cobalt ions, manganese ion in the solution, leave standstill again, ageing is after 20 hours, centrifugal, the washing 5 times, obtain the first sediment, comprise the co-precipitation of nickelous carbonate, cobalt carbonate and manganese carbonate in this first sediment.
(2) prepare the mixed aqueous solution of the second nickel salt nickel acetate and the second manganese salt manganese chloride according to amount of substance ratio Ni:Mn:=1:4, the mixed aqueous solution of this nickel acetate and manganese chloride is mixed with the first sediment, be uniformly dispersed by ultrasonic, under stirring, to wherein dripping the second precipitation reagent wet chemical, and the wet chemical excessive 3% that adds precipitates fully to guarantee nickel ion and manganese ion in the solution, leave standstill again, after the ageing 24 hours, centrifugal, wash 3 times, lower dry 8 hours at 110 ℃, obtain the first sediment that the second sediment coats, comprise the co-precipitation of nickelous carbonate and manganese carbonate in this second sediment.
(3) the first sediment that the second sediment is coated mixes with the first lithium salts lithium hydroxide that (structure according to anode material for lithium-ion batteries is at lithium-rich anode material 0.4Li
2MnO
30.6LiNi
0.5Co
0.3Mn
0.2O
2Be coated with LiNi
0.4Mn
1.6O
4In the element Relationship of Coefficients, lithium is excessive 3%, lithium is slightly excessive to be in order to compensate at high temperature on a small quantity volatilization of lithium hydroxide), add mortar, hand-ground, batch mixing is even.Then under air atmosphere, carry out sintering by temperature programmed control:
Be heated to 500 ℃ with 6 ℃/min programming rate, heating 10h;
Be heated to 900 ℃ with 0.5 ℃/min programming rate, heating 15h;
Then naturally be cooled to room temperature, namely obtain at lithium-rich anode material 0.4Li
2MnO
30.6LiNi
0.5Co
0.3Mn
0.2O
2Be coated with LiNi
0.4Mn
1.6O
4Anode material for lithium-ion batteries.
According to the method for preparing button cell among the embodiment 1, the anode material for lithium-ion batteries that uses present embodiment to make is made button cell, and this battery is carried out charge-discharge performance test: charging and discharging currents is 0.2C, first discharge specific capacity is 220.417mAh/g, coulombic efficiency is 81.24% first, 60 capability retentions that circulate are 96.9%, and cyclical stability is better.
Present embodiment provides a kind of anode material for lithium-ion batteries, and the structure of this material is at lithium-rich anode material 0.5Li
2MnO
30.5LiNi
0.4Co
0.4Mn
0.2O
2Be coated with LiNi
0.5Mn
1.5O
4, and this structure is nucleocapsid structure, wherein, and lithium-rich anode material 0.5Li
2MnO
30.5LiNi
0.4Co
0.4Mn
0.2O
2Be the nuclear of this nucleocapsid structure, LiNi
0.5Mn
1.5O
4Be the shell of this nucleocapsid structure, LiNi
0.5Mn
1.5O
4Account for 7% of anode material for lithium-ion batteries quality.
The preparation method of the anode material for lithium-ion batteries in the present embodiment may further comprise the steps:
(1) according to the molecular formula 0.5Li of lithium-rich anode material
2MnO
30.5LiNi
0.4Co
0.4Mn
0.2O
2In coefficient proportioning Ni: Co: Mn=1: the mixed aqueous solution of 1: 3 preparation the first nickel salt nickel chloride, the first cobalt salt cobalt chloride and the first manganese salt manganese chloride, and the molar ratio in this mixed aqueous solution is nickel ion: cobalt ions: manganese ion=1: 1: 3.In this mixed aqueous solution, add the first precipitation reagent aqueous sodium carbonate again, and the aqueous sodium carbonate excessive 2.5% that adds precipitates fully to guarantee nickel ion, cobalt ions, manganese ion in the solution, leave standstill again, ageing is after 6 hours, centrifugal, the washing 5 times, obtain the first sediment, comprise the co-precipitation of nickelous carbonate, cobalt carbonate and manganese carbonate in this first sediment.
(2) prepare the mixed aqueous solution of the second nickel salt nickelous sulfate and the second manganese salt manganese nitrate according to amount of substance ratio Ni:Mn:=1:3, the mixed aqueous solution of this nickelous sulfate and manganese nitrate is mixed with the first sediment, be uniformly dispersed by ultrasonic, under stirring, to wherein dripping the second precipitation reagent aqueous sodium carbonate, and the aqueous sodium carbonate excessive 2.5% that adds precipitates fully to guarantee nickel ion and manganese ion in the solution, leave standstill again, after the ageing 12 hours, centrifugal, wash 3 times, lower dry 8 hours at 110 ℃, obtain the first sediment that the second sediment coats, comprise the co-precipitation of nickelous carbonate and manganese carbonate in this second sediment.
(3) the first sediment that the second sediment is coated mixes with the first lithium salts lithium carbonate that (structure according to anode material for lithium-ion batteries is at lithium-rich anode material 0.5Li
2MnO
30.5LiNi
0.4Co
0.4Mn
0.2O
2Be coated with LiNi
0.5Mn
1.5O
4In the element Relationship of Coefficients, lithium is excessive 2%, lithium is slightly excessive to be in order to compensate at high temperature on a small quantity volatilization of lithium carbonate), add in the beaker, add again a certain amount of ethanol, magnetic agitation, batch mixing is even.Then under air atmosphere, carry out sintering by temperature programmed control:
Be heated to 600 ℃ with 10 ℃/min programming rate, heating 15h;
Be heated to 850 ℃ with 5 ℃/min programming rate, heating 24h;
Then naturally be cooled to room temperature, namely obtain at lithium-rich anode material 0.5Li
2MnO
30.5LiNi
0.4Co
0.4Mn
0.2O
2Be coated with LiNi
0.5Mn
1.5O
4Anode material for lithium-ion batteries.
According to the method for preparing button cell among the embodiment 1, the anode material for lithium-ion batteries that uses present embodiment to make is made button cell, and this battery is carried out charge-discharge performance test: charging and discharging currents is 0.2C, first discharge specific capacity is 257.325mAh/g, coulombic efficiency is 86% first, 60 capability retentions that circulate are 93.2%, and cyclical stability is better.
Embodiment 5
Present embodiment provides a kind of anode material for lithium-ion batteries, and the structure of this material is at lithium-rich anode material 0.9Li
2MnO
30.1LiNi
0.8Co
0.1Mn
0.1O
2Be coated with LiNi
0.05Mn
1.95O
4, and this structure is nucleocapsid structure, wherein, and lithium-rich anode material 0.9Li
2MnO
30.1LiNi
0.8Co
0.1Mn
0.1O
2Be the nuclear of this nucleocapsid structure, LiNi
0.05Mn
1.95O
4Be the shell of this nucleocapsid structure, LiNi
0.05Mn
1.95O
4Account for 20% of anode material for lithium-ion batteries quality.
The preparation method of the anode material for lithium-ion batteries in the present embodiment may further comprise the steps:
(1) according to the molecular formula 0.9Li of lithium-rich anode material
2MnO
30.1LiNi
0.8Co
0.1Mn
0.1O
2In coefficient proportioning Ni: Co: Mn=8: the mixed aqueous solution of 1: 91 preparation the first nickel salt nickel nitrate, the first cobalt salt cobalt acetate and the first manganese salt manganese sulfate, and the molar ratio in this mixed aqueous solution is nickel ion: cobalt ions: manganese ion=8: 1: 91.In this mixed aqueous solution, add the first precipitation reagent sodium hydrate aqueous solution again, and the sodium hydrate aqueous solution excessive 4% that adds precipitates fully to guarantee nickel ion, cobalt ions, manganese ion in the solution, leave standstill again, ageing is after 20 hours, centrifugal, the washing 5 times, obtain the first sediment, comprise the co-precipitation of nickel hydroxide, cobalt hydroxide and manganous hydroxide in this first sediment.
(2) prepare the mixed aqueous solution of the second nickel salt nickelous sulfate and the second manganese salt manganese sulfate according to amount of substance ratio Ni:Mn:=1:39, the mixed aqueous solution of this nickelous sulfate and manganese sulfate is mixed with the first sediment, be uniformly dispersed by ultrasonic, under stirring, to wherein dripping the second precipitation reagent sodium hydrate aqueous solution, and the hydrocarbon aqueous solution of sodium oxide excessive 3% that adds precipitates fully to guarantee nickel ion and manganese ion in the solution, leave standstill again, after the ageing 20 hours, centrifugal, wash 3 times, lower dry 8 hours at 110 ℃, obtain the first sediment that the second sediment coats, comprise the co-precipitation of nickel hydroxide and manganous hydroxide in this second sediment.
(3) the first sediment that the second sediment is coated mixes with the first lithium salts lithium nitrate that (structure according to anode material for lithium-ion batteries is at lithium-rich anode material 0.9Li
2MnO
30.1LiNi
0.8Co
0.1Mn
0.1O
2Be coated with LiNi
0.05Mn
1.95O
4In the element Relationship of Coefficients, lithium is excessive 2%, lithium is slightly excessive to be in order to compensate at high temperature on a small quantity volatilization of lithium nitrate), add planetary ball mill, add a certain amount of ethanol again, the amount ratio of ethanol and above-mentioned solid is 1.5mL/g, with the rotating speed ball milling 8h of 350r/min, batch mixing is even.Then under air atmosphere, carry out sintering by temperature programmed control:
Be heated to 500 ℃ with 0.5 ℃/min programming rate, heating 4h;
Be heated to 750 ℃ with 5 ℃/min programming rate, heating 2h;
Then naturally be cooled to room temperature, namely obtain at lithium-rich anode material 0.9Li
2MnO
30.1LiNi
0.8Co
0.1Mn
0.1O
2Be coated with LiNi
0.05Mn
1.95O
4Anode material for lithium-ion batteries.
Present embodiment provides a kind of anode material for lithium-ion batteries, and the structure of this material is at lithium-rich anode material 0.6Li
2MnO
30.4LiNi
0.6Co
0.2Mn
0.2O
2Be coated with LiNi
0.4Mn
1.6O
4, and this structure is nucleocapsid structure, wherein, and lithium-rich anode material 0.6Li
2MnO
30.4LiNi
0.6Co
0.2Mn
0.2O
2Be the nuclear of this nucleocapsid structure, LiNi
0.4Mn
1.6O
4Be the shell of this nucleocapsid structure, LiNi
0.4Mn
1.6O
4Account for 11% of anode material for lithium-ion batteries quality.
The preparation method of the anode material for lithium-ion batteries in the present embodiment may further comprise the steps:
(1) according to the molecular formula 0.6Li of lithium-rich anode material
2MnO
30.4LiNi
0.6Co
0.2Mn
0.2O
2In coefficient proportioning Ni: Co: Mn=6: the mixed aqueous solution of 2: 17 preparations the first nickel salt nickelous sulfate, the first cobalt salt cobalt chloride and the first manganese salt manganese nitrates, and the molar ratio in this mixed aqueous solution is nickel ion: cobalt ions: manganese ion=6: 2: 17.In this mixed aqueous solution, add the first precipitation reagent potassium hydroxide aqueous solution again, and the potassium hydroxide aqueous solution excessive 5% that adds precipitates fully to guarantee nickel ion, cobalt ions, manganese ion in the solution, leave standstill again, ageing is after 12 hours, centrifugal, the washing 3 times, obtain the first sediment, comprise the co-precipitation of hydrogen-oxygen nickel, hydrogen-oxygen cobalt and hydrogen-oxygen manganese in this first sediment.
(2) prepare the mixed aqueous solution of the second nickel salt nickel nitrate and the second manganese salt manganese acetate according to amount of substance ratio Ni:Mn:=1:4, the mixed aqueous solution of this nickel nitrate and manganese acetate is mixed with the first sediment, be uniformly dispersed by ultrasonic, under stirring, to wherein dripping the second precipitation reagent ammonium carbonate solution, and the ammonium carbonate solution excessive 5% that adds precipitates fully to guarantee nickel ion and manganese ion in the solution, leave standstill again, after the ageing 12 hours, centrifugal, wash 3 times, lower dry 8 hours at 110 ℃, obtain the first sediment that the second sediment coats, comprise the co-precipitation of nickelous carbonate and manganese carbonate in this second sediment.
(3) the first sediment that the second sediment is coated mixes with the first lithium salts lithium hydroxide that (structure according to anode material for lithium-ion batteries is at lithium-rich anode material 0.6Li
2MnO
30.4LiNi
0.6Co
0.2Mn
0.2O
2Be coated with LiNi
0.4Mn
1.6O
4In the element Relationship of Coefficients, lithium is excessive 2%, lithium is slightly excessive to be in order to compensate at high temperature on a small quantity volatilization of lithium hydroxide), add planetary ball mill, add a certain amount of ethanol again, the amount ratio of ethanol and above-mentioned solid is 1.5mL/g, with the rotating speed ball milling 8h of 350r/min, batch mixing is even.Then under air atmosphere, carry out sintering by temperature programmed control:
Be heated to 550 ℃ with 8 ℃/min programming rate, heating 1h;
Be heated to 800 ℃ with 8 ℃/min programming rate, heating 8h;
Then naturally be cooled to room temperature, namely obtain at lithium-rich anode material 0.6Li
2MnO
30.4LiNi
0.6Co
0.2Mn
0.2O
2Be coated with LiNi
0.4Mn
1.6O
4Anode material for lithium-ion batteries.
Embodiment 7
Present embodiment provides a kind of anode material for lithium-ion batteries, and the structure of this material is at lithium-rich anode material 0.7Li
2MnO
30.3LiNi
0.7Co
0.15Mn
0.15O
2Be coated with LiNi
0.5Mn
1.5O
4, and this structure is nucleocapsid structure, wherein, and lithium-rich anode material 0.7Li
2MnO
30.3LiNi
0.7Co
0.15Mn
0.15O
2Be the nuclear of this nucleocapsid structure, LiNi
0.5Mn
1.5O
4Be the shell of this nucleocapsid structure, LiNi
0.5Mn
1.5O
4Account for 10% of anode material for lithium-ion batteries quality.
The preparation method of the anode material for lithium-ion batteries in the present embodiment may further comprise the steps:
(1) according to the molecular formula 0.7Li of lithium-rich anode material
2MnO
30.3LiNi
0.7Co
0.15Mn
0.15O
2In coefficient proportioning Ni: the mixed aqueous solution of Co: Mn=42:9:149 the first nickel salt nickel chloride, the first cobalt salt cobaltous sulfate and the first manganese salt manganese nitrate, and the molar ratio in this mixed aqueous solution is nickel ion: cobalt ions: manganese ion=42:9:149.In this mixed aqueous solution, add the first precipitation reagent ammonium carbonate solution again, and the ammonium carbonate solution excessive 5% that adds precipitates fully to guarantee nickel ion, cobalt ions, manganese ion in the solution, leave standstill again, ageing is after 12 hours, centrifugal, the washing 3 times, obtain the first sediment, comprise the co-precipitation of nickelous carbonate, cobalt carbonate and manganese carbonate in this first sediment.
(2) prepare the mixed aqueous solution of the second nickel salt nickelous sulfate and the second manganese salt manganese nitrate according to amount of substance ratio Ni:Mn:=1:3, the mixed aqueous solution of this nickelous sulfate and manganese nitrate is mixed with the first sediment, be uniformly dispersed by ultrasonic, under stirring, to wherein dripping the second precipitation reagent potassium hydroxide aqueous solution, and the potassium hydroxide aqueous solution excessive 5% that adds precipitates fully to guarantee nickel ion and manganese ion in the solution, leave standstill again, after the ageing 12 hours, centrifugal, wash 3 times, lower dry 8 hours at 110 ℃, obtain the first sediment that the second sediment coats, comprise the co-precipitation of nickel hydroxide and manganous hydroxide in this second sediment.
(3) the first sediment that the second sediment is coated mixes with the first lithium salts lithium carbonate that (structure according to anode material for lithium-ion batteries is at lithium-rich anode material 0.7Li
2MnO
30.3LiNi
0.7Co
0.15Mn
0.15O
2Be coated with LiNi
0.5Mn
1.5O
4In the element Relationship of Coefficients, lithium is excessive 2%, lithium is slightly excessive to be in order to compensate at high temperature on a small quantity volatilization of lithium carbonate), add planetary ball mill, add a certain amount of ethanol again, the amount ratio of ethanol and above-mentioned solid is 1.5mL/g, with the rotating speed ball milling 8h of 350r/min, batch mixing is even.Then under air atmosphere, carry out sintering by temperature programmed control:
Be heated to 400 ℃ with 4 ℃/min programming rate, heating 12h;
Be heated to 900 ℃ with 10 ℃/min programming rate, heating 19h;
Then naturally be cooled to room temperature, namely obtain at lithium-rich anode material 0.7Li
2MnO
30.3LiNi
0.7Co
0.15Mn
0.15O
2Be coated with LiNi
0.5Mn
1.5O
4Anode material for lithium-ion batteries.
Present embodiment provides a kind of anode material for lithium-ion batteries, and the structure of this material is at lithium-rich anode material 0.1Li
2MnO
30.9LiNi
1/3Co
1/3Mn
1/3O
2Be coated with LiNi
0.4Mn
1.6O
4, and this structure is nucleocapsid structure, wherein, and lithium-rich anode material 0.1Li
2MnO
30.9LiNi
1/3Co
1/3Mn
1/3O
2Be the nuclear of this nucleocapsid structure, LiNi
0.4Mn
1.6O
4Be the shell of this nucleocapsid structure, LiNi
0.4Mn
1.6O
4Account for 12% of anode material for lithium-ion batteries quality.
Present embodiment provides a kind of preparation method of anode material for lithium-ion batteries, may further comprise the steps:
(1) according to the molecular formula 0.1Li of lithium-rich anode material
2MnO
30.9LiNi
1/3Co
1/3Mn
1/3O
2In coefficient proportioning Ni: Mn: Co=3: the mixed aqueous solution of 3: 4 preparations the first nickel salt nickel acetate, the first cobalt salt cobalt acetate and the first manganese salt manganese acetates, and the molar ratio in this mixed aqueous solution is nickel ion: cobalt ions: manganese ion=3: 3: 4.In this mixed aqueous solution, add the first precipitation reagent aqueous sodium carbonate again, and the aqueous sodium carbonate excessive 5% that adds precipitates fully to guarantee nickel ion, cobalt ions, manganese ion in the solution, leave standstill again, ageing is after 12 hours, centrifugal, the washing 3 times, obtain the first sediment, comprise the co-precipitation of nickelous carbonate, cobalt carbonate and manganese carbonate in this first sediment.
(2) the first sediment is mixed (according to the molecular formula 0.1Li of lithium-rich anode material with the first lithium salts lithium acetate
2MnO
30.9LiNi
1/3Co
1/3Mn
1/3O
2In the element Relationship of Coefficients, lithium is excessive 2%, lithium is slightly excessive to be in order to compensate at high temperature on a small quantity volatilization of lithium acetate), add planetary ball mill, add a certain amount of ethanol again, the amount ratio of ethanol and above-mentioned solid is 1.5mL/g, with the rotating speed ball milling 8h of 350r/min, batch mixing is even.Then under air atmosphere, carry out sintering by temperature programmed control:
Be heated to 600 ℃ with 5 ℃/min programming rate, heating 8h;
Be heated to 950 ℃ with 4 ℃/min programming rate, heating 10h;
Then naturally be cooled to room temperature, namely obtain at lithium-rich anode material 0.1Li
2MnO
30.9LiNi
1/3Co
1/3Mn
1/3O
2
(3) according to amount of substance ratio Ni: Mn=1: the mixed aqueous solution of 4 preparation the 3rd nickel salt nickel nitrates and the 3rd manganese salt manganese acetate, and mix with lithium-rich anode material, then add the 3rd precipitation reagent NaOH, obtain the described lithium-rich anode material 0.1Li that the 3rd sediment coats
2MnO
30.9LiNi
1/3Co
1/3Mn
1/3O
2, wherein, the 3rd sediment comprises the co-precipitation of nickel hydroxide and manganous hydroxide, the described lithium-rich anode material that described the 3rd sediment is coated mixes rear calcination with the second lithium salts lithium carbonate:
Be heated to 600 ℃ with 5 ℃/min programming rate, heating 8h;
Be heated to 950 ℃ with 4 ℃/min programming rate, heating 10h;
Then naturally be cooled to room temperature, obtain 0.1Li
2MnO
30.9LiNi
1/3Co
1/3Mn
1/3O
2Be coated with LiNi
0.4Mn
1.6O
4Anode material for lithium-ion batteries.
The preparation method of the anode material for lithium-ion batteries in the present embodiment prepares lithium-rich anode material first by step (1) and step (2), and then makes anode material for lithium-ion batteries by step (3).By this preparation method obtain at lithium-rich anode material 0.1Li
2MnO
30.9LiNi
1/3Co
1/3Mn
1/3O
2Be coated with LiNi
0.4Mn
1.6O
4The kernel 0.1Li of anode material for lithium-ion batteries
2MnO
30.9LiNi
1/3Co
1/3Mn
1/3O
2With shell LiNi
0.4Mn
1.6O
4Boundary more obvious, the kernel 0.1Li of anode material for lithium-ion batteries
2MnO
30.9LiNi
1/3Co
1/3Mn
1/3O
2With shell LiNi
0.4Mn
1.6O
4Chemical property more independent.
According to the method for preparing button cell among the embodiment 1, the anode material for lithium-ion batteries that uses present embodiment to make is made button cell, and this battery is carried out charge-discharge performance test: charging and discharging currents is 0.2C, first discharge specific capacity is 242.352mAh/g, coulombic efficiency is 80.2% first, 60 capability retentions that circulate are 97.1%, and cyclical stability is better.
Embodiment 9
Present embodiment provides a kind of anode material for lithium-ion batteries, and the structure of this material is at lithium-rich anode material 0.9Li
2MnO
30.1LiNi
0.5Mn
0.5O
2Be coated with LiNi
0.5Mn
1.5O
4, and this structure is nucleocapsid structure, wherein, and lithium-rich anode material 0.9Li
2MnO
30.1LiNi
0.5Mn
0.5O
2Be the nuclear of this nucleocapsid structure, LiNi
0.5Mn
1.5O
4Be the shell of this nucleocapsid structure, LiNi
0.5Mn
1.5O
4Account for 2% of anode material for lithium-ion batteries quality.
Present embodiment provides a kind of preparation method of anode material for lithium-ion batteries, may further comprise the steps:
(1) according to the molecular formula 0.9Li of lithium-rich anode material
2MnO
30.1LiNi
0.5Mn
0.5O
2In coefficient proportioning Ni: Mn=1: the mixed aqueous solution of 19 preparation the first nickel salt nickel chlorides and the first manganese salt manganese chlorides, and the molar ratio in this mixed aqueous solution is nickel ion: manganese ion=1: 19.In this mixed aqueous solution, add the first precipitation reagent aqueous sodium carbonate again, and the aqueous sodium carbonate excessive 2.5% that adds precipitates fully to guarantee the nickel ion manganese ion in the solution, leave standstill again, ageing is after 6 hours, centrifugal, the washing 5 times, obtain the first sediment, comprise the co-precipitation of nickelous carbonate, manganese carbonate in this first sediment.
(2) the first sediment is mixed (according to the molecular formula 0.9Li of lithium-rich anode material with the first lithium salts lithium carbonate
2MnO
30.1LiNi
0.5Mn
0.5O
2In the element Relationship of Coefficients, lithium is excessive 2%, lithium is slightly excessive to be in order to compensate at high temperature on a small quantity volatilization of lithium carbonate), add in the beaker, add again a certain amount of ethanol, magnetic agitation, batch mixing is even.Then under air atmosphere, carry out sintering by temperature programmed control:
Be heated to 600 ℃ with 10 ℃/min programming rate, heating 15h;
Be heated to 850 ℃ with 5 ℃/min programming rate, heating 24h;
Then naturally be cooled to room temperature, namely obtain lithium-rich anode material 0.9Li
2MnO
30.1LiNi
0.5Mn
0.5O
2
(3) according to amount of substance ratio Ni: Mn=1: the mixed aqueous solution of 3 preparation the 3rd nickel salt nickelous sulfates and the 3rd manganese salt manganese nitrates, and with lithium-rich anode material 0.9Li
2MnO
30.1LiNi
0.5Mn
0.5O
2Mix, then add the 3rd precipitation reagent potash, obtain the described lithium-rich anode material that the 3rd sediment coats, wherein the 3rd sediment comprises the co-precipitation of nickelous carbonate and manganese carbonate, and the described lithium-rich anode material that described the 3rd sediment is coated mixes rear calcination with the second lithium salts lithium hydroxide:
Be heated to 600 ℃ with 10 ℃/min programming rate, heating 15h;
Be heated to 850 ℃ with 5 ℃/min programming rate, heating 24h;
Then naturally be cooled to room temperature, obtain 0.9Li
2MnO
30.1LiNi
0.5Mn
0.5O
2Be coated with LiNi
0.5Mn
1.5O
4Anode material for lithium-ion batteries.
Present embodiment provides a kind of anode material for lithium-ion batteries, and the structure of this material is at lithium-rich anode material 0.5Li
2MnO
30.5LiNi
0.6Co
0.2Mn
0.2O
2Be coated with LiNi
0.5Mn
1.5O
4, and this structure is nucleocapsid structure, wherein, and lithium-rich anode material 0.5Li
2MnO
30.5LiNi
0.6Co
0.2Mn
0.2O
2Be the nuclear of this nucleocapsid structure, LiNi
0.5Mn
1.5O
4Be the shell of this nucleocapsid structure, LiNi
0.5Mn
1.5O
4Account for 20% of anode material for lithium-ion batteries quality.
Present embodiment provides a kind of preparation method of anode material for lithium-ion batteries, may further comprise the steps:
(1) according to the molecular formula 0.5Li of lithium-rich anode material
2MnO
30.5LiNi
0.6Co
0.2Mn
0.2O
2In coefficient proportioning Ni: Co: Mn=3: the mixed aqueous solution of 1: 6 preparation the first nickel salt nickelous sulfate, the first cobalt salt cobalt chloride and the first manganese salt manganese nitrate, and the molar ratio in this mixed aqueous solution is nickel ion: cobalt ions: manganese ion=3: 1: 6.In this mixed aqueous solution, add the first precipitation reagent potassium hydroxide aqueous solution again, and the potassium hydroxide aqueous solution excessive 5% that adds precipitates fully to guarantee nickel ion, cobalt ions, manganese ion in the solution, leave standstill again, ageing is after 12 hours, centrifugal, the washing 3 times, obtain the first sediment, comprise the co-precipitation of hydrogen-oxygen nickel, hydrogen-oxygen cobalt and hydrogen-oxygen manganese in this first sediment.
(2) the first sediment is mixed (according to the molecular formula 0.5Li of lithium-rich anode material with the first lithium salts lithium hydroxide
2MnO
30.5LiNi
0.6Co
0.2Mn
0.2O
2In the element Relationship of Coefficients, lithium is excessive 2%, lithium is slightly excessive to be in order to compensate at high temperature on a small quantity volatilization of lithium hydroxide), add planetary ball mill, add a certain amount of ethanol again, the amount ratio of ethanol and above-mentioned solid is 1.5mL/g, with the rotating speed ball milling 8h of 350r/min, batch mixing is even.Then under air atmosphere, carry out sintering by temperature programmed control:
Be heated to 550 ℃ with 8 ℃/min programming rate, heating 1h;
Be heated to 800 ℃ with 8 ℃/min programming rate, heating 8h;
Then naturally be cooled to room temperature, namely obtain at lithium-rich anode material 0.5Li
2MnO
30.5LiNi
0.6Co
0.2Mn
0.2O
2
(3) according to amount of substance ratio Ni: Mn=1: the mixed aqueous solution of 3 preparation the 3rd nickel salt nickel chlorides and the 3rd manganese salt manganese sulfates, and with lithium-rich anode material 0.5Li
2MnO
30.5LiNi
0.6Co
0.2Mn
0.2O
2Mix, then add the 3rd precipitation reagent ammonium carbonate, obtain the described lithium-rich anode material that the 3rd sediment coats, wherein the 3rd sediment comprises the co-precipitation of nickelous carbonate and manganese carbonate, and the described lithium-rich anode material that described the 3rd sediment is coated mixes rear calcination with the second lithium salts lithium nitrate:
Be heated to 550 ℃ with 8 ℃/min programming rate, heating 1h;
Be heated to 800 ℃ with 8 ℃/min programming rate, heating 8h;
Then naturally be cooled to room temperature, obtain 0.5Li
2MnO
30.5LiNi
0.6Co
0.2Mn
0.2O
2Be coated with LiNi
0.5Mn
1.5O
4Anode material for lithium-ion batteries.
Be understandable that above execution mode only is the illustrative embodiments that adopts for principle of the present invention is described, yet the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement also are considered as protection scope of the present invention.
Claims (13)
1. an anode material for lithium-ion batteries is characterized in that, its structure is for to be coated with LiNi at lithium-rich anode material
yMn
2-yO
4, wherein, 0＜y≤0.5.
2. anode material for lithium-ion batteries according to claim 1 is characterized in that, its structure is for to be coated with LiNi at described lithium-rich anode material
yMn
2-yO
4, wherein, y=0.4 or 0.5.
3. described anode material for lithium-ion batteries according to claim 1 is characterized in that described lithium-rich anode material is xLi
2MnO
3(1-x) LiMO
2, and 0.1≤x≤0.9, wherein,
M is Ni
0.5Mn
0.5, Ni
1/3Co
1/3Mn
1/3, Ni
0.5Co
0.3Mn
0.2, Ni
0.4Co
0.4Mn
0.2, Ni
0.8Co
0.1Mn
0.1, Ni
0.6Co
0.2Mn
0.2, Ni
0.7Co
0.15Mn
0.15In any one.
4. described anode material for lithium-ion batteries according to claim 1 is characterized in that described LiNi
yMn
2-yO
4Account for 2%～20% of described anode material for lithium-ion batteries quality.
5. the preparation method of an anode material for lithium-ion batteries is characterized in that, may further comprise the steps:
(1) prepares the mixed aqueous solution of the first slaine of each described metallic element according to the coefficient proportioning between each metallic element except lithium in the molecular formula of lithium-rich anode material, add again the first precipitation reagent that contains hydroxyl or carbonate, obtain the first sediment;
(2) according to amount of substance ratio Ni: the Mn=y:(2-y) mixed aqueous solution of preparation the second nickel salt and the second manganese salt, and mix with described the first sediment in the described step (1), then add the second precipitation reagent that contains hydroxyl or carbonate, obtain the first sediment that the second sediment coats;
(3) be coated with LiNi according to described lithium-rich anode material
yMn
2-yO
4Whole compound in proportioning between lithium and all the other metallic elements, 0＜y≤0.5 wherein, the first sediment that the first lithium salts and described the second sediment are coated mixes afterwards that calcination obtains the described anode material for lithium-ion batteries of claim 1.
6. the preparation method of described anode material for lithium-ion batteries according to claim 5, it is characterized in that, described the first slaine in the described step (1) is the first manganese salt, the first nickel salt or the first cobalt salt, described step (1) is specially: to the first manganese salt, the mixed aqueous solution of the first nickel salt or the first nickel salt, the first cobalt salt, add described described the first precipitation reagent that contains hydroxyl or carbonate in the mixed aqueous solution of the first manganese salt and obtain described the first sediment, and the manganese in described the first sediment and the molar ratio between the nickel or manganese, molar ratio between nickel and the cobalt satisfies the molecular formula xLi of described lithium-rich anode material
2MnO
3(1-x) LiMO
2The coefficient proportioning of middle respective metal element, and 0.1≤x≤0.9, wherein,
M is Ni
0.5Mn
0.5, Ni
1/3Co
1/3Mn
1/3, Ni
0.5Co
0.3Mn
0.2, Ni
0.4Co
0.4Mn
0.2, Ni
0.8Co
0.1Mn
0.1, Ni
0.6Co
0.2Mn
0.2, Ni
0.7Co
0.15Mn
0.15In any one.
7. the preparation method of described anode material for lithium-ion batteries according to claim 5 is characterized in that the calcination temperature in the described step (3) is 700 ℃～1000 ℃.
8. the preparation method of described anode material for lithium-ion batteries according to claim 5 is characterized in that the described calcination process in the described step (3) is specially:
Be heated to 400～600 ℃ with 0.5～10 ℃/min programming rate, heating 1～15h;
Be heated to 750～950 ℃ with 0.5～10 ℃/min programming rate again, heating 2～24h;
Then be cooled to room temperature.
9. the preparation method of described anode material for lithium-ion batteries according to claim 5 is characterized in that,
Described the first precipitation reagent is one or more in sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical, the ammonium carbonate solution;
And/or described the second nickel salt is one or more in nickel nitrate, nickel acetate, nickelous sulfate, the nickel chloride;
And/or described the second manganese salt is one or more in manganese nitrate, manganese acetate, manganese sulfate, the manganese chloride;
And/or described the second precipitation reagent is one or more in sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical, the ammonium carbonate solution;
And/or described the first lithium salts is one or more in lithium carbonate, lithium hydroxide, lithium acetate, the lithium nitrate.
10. the preparation method of described anode material for lithium-ion batteries according to claim 5 is characterized in that,
Described the first nickel salt is one or more in nickel nitrate, nickel acetate, nickelous sulfate, the nickel chloride;
And/or described the first cobalt salt is one or more in cobalt nitrate, cobalt acetate, cobaltous sulfate, the cobalt chloride;
And/or described the first manganese salt is one or more in manganese nitrate, manganese acetate, manganese sulfate, the manganese chloride.
11. the preparation method of an anode material for lithium-ion batteries is characterized in that, may further comprise the steps:
According to amount of substance ratio Ni: the Mn=y:(2-y) mixed aqueous solution of preparation the 3rd nickel salt and the 3rd manganese salt, and mix with lithium-rich anode material, then add the 3rd precipitation reagent that contains hydroxyl or carbonate, obtain the described lithium-rich anode material that the 3rd sediment coats; Satisfy LiNi according to the nickel in the lithium in the second lithium salts and the 3rd sediment and the proportioning of manganese
yMn
2-yO
4Coefficient proportioning in the molecular formula, 0＜y≤0.5 wherein, the described lithium-rich anode material that described the 3rd sediment is coated mixes with the second lithium salts afterwards that calcination obtains the described anode material for lithium-ion batteries of claim 1.
12. the preparation method of described anode material for lithium-ion batteries is characterized in that according to claim 11,
Described the 3rd nickel salt is one or more in nickel nitrate, nickel acetate, nickelous sulfate, the nickel chloride;
And/or described the 3rd manganese salt is one or more in manganese nitrate, manganese acetate, manganese sulfate, the manganese chloride;
And/or described the 3rd precipitation reagent is one or more in sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical, the ammonium carbonate solution.
And/or described the second lithium salts is one or more in lithium carbonate, lithium hydroxide, lithium acetate, the lithium nitrate.
13. a lithium ion battery is characterized in that its positive pole comprises the positive electrode in one of claim 1～4.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103996838A (en) * | 2014-05-09 | 2014-08-20 | 上海大学 | Lithium zirconate-cladded lithium-rich positive material for lithium ion battery and preparation method thereof |
| CN104966819A (en) * | 2015-05-06 | 2015-10-07 | 合肥国轩高科动力能源股份公司 | High energy density lithium-ion battery positive electrode material and preparation method thereof |
| CN105161679A (en) * | 2015-06-30 | 2015-12-16 | 中国人民解放军国防科学技术大学 | Lithium-rich cathode material and preparation method and application thereof |
| CN107528056A (en) * | 2017-08-28 | 2017-12-29 | 四川富骅新能源科技有限公司 | Positive electrode and preparation method thereof, lithium ion battery |
| CN107706393A (en) * | 2017-10-19 | 2018-02-16 | 厦门高容新能源科技有限公司 | A kind of high power capacity solid lithium ion battery and preparation method thereof |
| CN109546115A (en) * | 2018-11-19 | 2019-03-29 | 安徽安凯汽车股份有限公司 | A kind of NCA ternary battery of nickelic rich lithium manganese base solid solution positive electrode |
| CN114300673A (en) * | 2021-12-15 | 2022-04-08 | 惠州锂威新能源科技有限公司 | Lithium ion positive electrode composite material and preparation method thereof |
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| CN102394295A (en) * | 2011-11-23 | 2012-03-28 | 东莞新能源科技有限公司 | Lithium ion battery and its positive material |
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| CN103996838A (en) * | 2014-05-09 | 2014-08-20 | 上海大学 | Lithium zirconate-cladded lithium-rich positive material for lithium ion battery and preparation method thereof |
| CN104966819A (en) * | 2015-05-06 | 2015-10-07 | 合肥国轩高科动力能源股份公司 | High energy density lithium-ion battery positive electrode material and preparation method thereof |
| CN104966819B (en) * | 2015-05-06 | 2017-08-25 | 合肥国轩高科动力能源有限公司 | High-energy-density lithium ion battery positive electrode material and preparation method thereof |
| CN105161679A (en) * | 2015-06-30 | 2015-12-16 | 中国人民解放军国防科学技术大学 | Lithium-rich cathode material and preparation method and application thereof |
| CN105161679B (en) * | 2015-06-30 | 2018-01-16 | 中国人民解放军国防科学技术大学 | Lithium-rich anode material and its preparation method and application |
| CN107528056A (en) * | 2017-08-28 | 2017-12-29 | 四川富骅新能源科技有限公司 | Positive electrode and preparation method thereof, lithium ion battery |
| CN107528056B (en) * | 2017-08-28 | 2020-06-02 | 四川富骅新能源科技有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN107706393A (en) * | 2017-10-19 | 2018-02-16 | 厦门高容新能源科技有限公司 | A kind of high power capacity solid lithium ion battery and preparation method thereof |
| CN107706393B (en) * | 2017-10-19 | 2020-02-07 | 厦门高容新能源科技有限公司 | High-capacity solid lithium ion battery and preparation method thereof |
| CN109546115A (en) * | 2018-11-19 | 2019-03-29 | 安徽安凯汽车股份有限公司 | A kind of NCA ternary battery of nickelic rich lithium manganese base solid solution positive electrode |
| CN114300673A (en) * | 2021-12-15 | 2022-04-08 | 惠州锂威新能源科技有限公司 | Lithium ion positive electrode composite material and preparation method thereof |
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