CN104733725A - Application and modified preparation method of manganese and lithium rich solid solution material - Google Patents
Application and modified preparation method of manganese and lithium rich solid solution material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 90
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 71
- 239000011572 manganese Substances 0.000 title claims abstract description 44
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 30
- 239000006104 solid solution Substances 0.000 title claims abstract description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- 229910001171 0.5LiNi0.5Mn0.5O2 Inorganic materials 0.000 claims abstract description 8
- 239000011343 solid material Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims description 24
- 229910016757 Ni0.5Mn1.5(OH)4 Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000008247 solid mixture Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 238000002715 modification method Methods 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 8
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 8
- 239000011702 manganese sulphate Substances 0.000 claims description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 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 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims 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 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims 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 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 8
- 239000010405 anode material Substances 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 229910016759 Ni0.5Mn1.5O4 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 ethyl carbonate ester Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101001111742 Homo sapiens Rhombotin-2 Proteins 0.000 description 1
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 102100023876 Rhombotin-2 Human genes 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 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
- 239000013590 bulk material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 1
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to application and a modified preparation method of a manganese and lithium rich solid solution material which is a 0.5Li2MnO3.0.5LiNi0.5Mn0.5O2 manganese and lithium rich solid material used as a anode material of a lithium-ion battery. The preparation method includes the steps of 1), forming a precursor; 2), forming the solid solution material with lithium; 3), evenly depositing lithium titanate on the surface of the material. The 0.5Li2MnO3.0.5LiNi0.5Mn0.5O2 manganese and lithium rich solid material good in performance is obtained by selecting proper process parameters, the material is then evenly wrapped with the nano lithium titanate on the surface, and first coulomb efficiency, rate capability and cycling stability of the material are improved.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to the rich lithium solid-solution material of a kind of rich manganese, its purposes and modification method for preparing.
Background technology
Electric automobile field has the anode material for lithium-ion batteries of application prospect to mainly contain LiFePO4, LiMn2O4 etc.Although the LiFePO4 cost price with olivine structural is low, good rate capability, but due to its energy density low (being generally less than 120Wh/Kg), process the problems such as consistency is poor, poor performance at low temperatures, limit its industrialization level and application prospect; The LiMn2O4 simultaneously with spinel structure has the three-dimensional deintercalation channel design being applicable to very much lithium ion turnover, the advantages such as cost is low, good rate capability, but because its specific capacity is low, the defects such as high temperature cyclic performance difference, have impact on the large-scale application of such material.Therefore people are actively finding new lithium ion power battery cathode material, Li2MnO3 and layered oxide LMO2 (M=Ni, Co, Mn) the rich manganese anode material of the rich lithium formed (being called for short LNMO) is a kind of α-NaFeO2 type solid-solution material, have that specific capacity is high, operating voltage is high, the advantage such as energy density high (>250Wh/Kg), fail safe are better, be considered to one of follow-on lithium ion power battery cathode material of most application prospect, become the study hotspot of current anode material for lithium-ion batteries; But people also find under study for action, although LNMO has higher specific discharge capacity and energy density, but also also exist first that coulombic efficiency is low, high rate performance is poor, the problems such as capacity attenuation, so need by reaching the requirement of electric automobile to performances such as lithium ion battery high magnification, high-energy-density and long-lives to the modification of this kind of material.
In order to overcome the problems such as high rate performance difference that the rich manganese solid solution battery material of rich lithium occurs in the application and capacity attenuation, current industry mainly to be adulterated or/and Surface coating carries out by material body for above way to solve the problem, and the kind of Surface coating material and the performance of battery material are closely-related, employing has the quick conductive nano lithium titanate of lithium ion and carries out finishing to LNMO.
Summary of the invention
The object of the present invention is to provide the rich lithium solid-solution material of a kind of rich manganese, its purposes and modification method for preparing, solve the rich multiplying power of manganese solid solution material of rich lithium and the problem of cycle performance difference, pass through coprecipitation, form predecessor, then lithium is accompanied to synthesize solid-solution material, then at material surface uniform deposition lithium titanate.Concrete technical scheme is as follows:
The rich lithium solid-solution material of a kind of rich manganese, it is a kind of 0.5Li
2mnO
30.5LiNi0.5Mn0.5O
2the rich lithium solid-solution material of rich manganese.
The purposes of the rich lithium solid-solution material of above-mentioned rich manganese, as cell positive material.
Further, as lithium ion power battery cathode material.
The modification method for preparing of the rich lithium solid-solution material of above-mentioned rich manganese, comprises the steps:
(1) predecessor is formed;
(2) lithium is accompanied to synthesize solid-solution material;
(3) at material surface uniform deposition lithium titanate.
Further, by coprecipitation in step (1), form predecessor Ni0.5Mn1.5 (OH)
4.
Further, step (1) comprises the steps:
(1-1) mixture aqueous solution of nickel presoma and manganese presoma is prepared in the mole ratio Ni ︰ Mn=1 ︰ 3 of material;
(1-2) in mixture aqueous solution, add alkaline solution pH value regulator, pH value is controlled at 10-12;
(1-3) stir;
(1-4) centrifugal;
(1-5) pure water cleaning obtains nickel manganese presoma Ni0.5Mn1.5 (OH)
4.
Further, step (2) comprises the steps:
(2-1) in amount of substance ratio Li ︰ Ni ︰ Mn=, (lithium source and nickel manganese presoma batch mixing are obtained solid mixture by 6.3 ~ 6.6) ︰ 1 ︰ 3;
(2-2) form powder, obtain powder mixture;
(2-3) under an oxygen-containing atmosphere, 500-600 DEG C is heated to the programming rate of 1-5 DEG C/min;
(2-4) heat preservation sintering 5-10h, obtains pretreated nickel manganese presoma.
Further, step (2) also comprises the steps: the pretreated nickel manganese presoma of gained under an oxygen-containing atmosphere, is heated to 800-1000 DEG C with the programming rate of 0.5-10 DEG C/min, and calcining 8-24h, Temperature fall, to room temperature, namely obtains 0.5Li
2mnO
30.5LiNi0.5Mn0.5O
2material.
Further, step (3) comprises the steps:
(3-1) the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 dispersion of materials obtained is in appropriate ethanolic solution;
(3-2) appropriate titanium source and lithium source Li:Ti=(0.8:1) is added;
(3-3) when stir at 50-80 DEG C, solvent evaporated;
(3-4) powder is collected;
(3-5) 700-800 DEG C is heated to the programming rate of 3-10 DEG C/min;
(3-6) 2-10h is calcined;
(3-7) Temperature fall is to room temperature, namely obtains nano lithium titanate Surface coating 0.5Li
2mnO
30.5LiNi0.5Mn0.5O
2material.
Further, solid phase reaction atmosphere is oxygen-containing atmosphere is air atmosphere or pure oxygen atmosphere; And/or solid material mixed method is wet ball grinding, described wet ball grinding comprises: mixed with the ratio of solid mixture in 1 ︰ (1-2) mL/g by ethanol, with the rotating speed ball milling 2-16h of 300-500r/min; And/or described nickel presoma is one or more in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride; And/or described manganese presoma is one or more in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride; And/or described titanium source presoma is one or more in butyl titanate, manganese sulfate, titanium tetrachloride; And/or described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithia; And/or described alkaline pH adjuster is NaOH solution or KOH solution or LiOH solution.
Compared with currently available technology, the present invention obtains the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material of function admirable by choosing suitable technological parameter, then uniform nano lithium titanate Surface coating is carried out to this material, thus improve the coulombic efficiency first of this material, high rate performance and cyclical stability.Technical problem to be solved by this invention is, for the problem that coulombic efficiency is first low He specific capacity is low, cycle performance is poor of existing 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material.Principle of the present invention is chemistry based on lithium titanate and physical characteristic, because lithium titanate is spinel structure, has three-dimensional lithium ion tunnel, is very suitable for the fast transferring of lithium ion, serve the effect promoting material high rate performance; Simultaneously due to the coated protective effect served bulk material on surface, the contact between material and electrolyte can be reduced, reduce the generation of side reaction, improve coulombic efficiency and cyclical stability.
Accompanying drawing explanation
Fig. 1 is the coated 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material discharging cycle performance of nano lithium titanate prepared by embodiment 1;
Fig. 2 is that the coated 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material of nano lithium titanate prepared by embodiment 1 discharges under different charge-discharge magnification, compares with not coated material.
Embodiment
Describe the present invention with reference to the accompanying drawings below, it is a kind of preferred embodiment in numerous embodiments of the present invention.
In a typical embodiment, the preparation of rich manganese rich lithium 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material and surface modifying method, comprising:
1) coprecipitation prepares nickel manganese presoma Ni0.5Mn1.5 (OH) 4, the mixture aqueous solution of nickel presoma and manganese presoma is prepared in the mole ratio Ni ︰ Mn=1 ︰ 3 of material, alkaline solution pH value regulator is added in mixture aqueous solution, pH value is controlled at 10-12, after stirring certain hour, obtain nickel manganese presoma Ni0.5Mn1.5 (OH) 4 through centrifugal, pure water cleaning.
2) nickel manganese mixed hydroxides presoma Ni0.5Mn1.5 (OH) 4 pre-treatment step, it comprises any one in following two kinds of processes: in amount of substance ratio Li ︰ Ni ︰ Mn=, (lithium source and nickel manganese presoma batch mixing are obtained solid mixture by 6.3 ~ 6.6) ︰ 1 ︰ 3, powder, obtains powder mixture; Under an oxygen-containing atmosphere, be heated to 500-600 DEG C with the programming rate of 1-5 DEG C/min, heat preservation sintering 5-10h, obtain pretreated nickel manganese presoma.
3) synthesis in solid state step, by step 2) the pretreated nickel manganese presoma of gained under an oxygen-containing atmosphere, be heated to 800-1000 DEG C with the programming rate of 0.5-10 DEG C/min, calcining 8-24h, Temperature fall, to room temperature, namely obtains 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material.
4) surface treatment step, just step 3) in the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 dispersion of materials that obtains in appropriate ethanolic solution, then appropriate titanium source and lithium source Li:Ti=(0.8:1) is added, then when stir at 50-80 DEG C, solvent evaporated, then powder is collected, 700-800 DEG C is heated to the programming rate of 3-10 DEG C/min, calcining 2-10h, Temperature fall, to room temperature, namely obtains nano lithium titanate Surface coating 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material.
Preferred solid phase reaction atmosphere is oxygen-containing atmosphere is air atmosphere or pure oxygen atmosphere; Preferred solid material mixed method is wet ball grinding, and described wet ball grinding comprises: mixed with the ratio of solid mixture in 1 ︰ (1-2) mL/g by ethanol, with the rotating speed ball milling 2-16h of 300-500r/min; Preferably, described nickel presoma is one or more in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride; Preferably, described manganese presoma is one or more in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride; Preferably, described titanium source presoma is one or more in butyl titanate, manganese sulfate, titanium tetrachloride; Preferably, described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithia; Preferably, described alkaline pH adjuster is NaOH solution or KOH solution or LiOH solution.
Embodiment 1
In another exemplary embodiments, the preparation method of the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material providing a kind of nano lithium titanate coated, comprising:
Nickel manganese presoma Ni0.5Mn1.5 (OH) 4 prepares nickel nitrate and manganese nitrate mixture aqueous solution in amount of substance ratio Ni ︰ Mn=1 ︰ 3 is prepared in step 1. co-precipitation, under stirring, to the NaOH solution of mixed solution and dripping 2M, the pH value of mixed solution is controlled about 10.5, to ensure Ni2+, Mn2+ precipitation completely, after leaving standstill 2h, suction filtration, washing three times, 110 DEG C dry 12h obtain presoma Ni0.5Mn1.5 (OH) 4.
Step 2. nickel manganese presoma Ni0.5Mn1.5 (OH) 4 preliminary treatment, in amount of substance ratio Li ︰ Ni ︰ Mn=4.1 ︰ 1 ︰ 3 by lithium carbonate (both amount of substance ratios are 1 ︰ 1), presoma Ni0.5Mn1.5 (OH) 4 batch mixing obtains solid mixture, and wherein Li is excessive is a little a small amount of volatilization loss in order to make up lithium in subsequent high temperature process; And be that 1.2mL/g adds ball mill in the ratio of ethanol and solid mixture, with the rotating speed ball milling 13h of 400r/min, obtain powder mixture.Powder mixture is taken out dry, then under pure oxygen atmosphere, be heated to 500 DEG C with the programming rate of 3 DEG C/min, heat preservation sintering 5h, obtain pretreated nickel manganese presoma.
Step 3. synthesis in solid state, in air atmosphere, is heated to 800 DEG C with the programming rate of 10 DEG C/min, calcining 8h; Last Temperature fall, to room temperature, namely obtains 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material.
Step 4. surface treatment step, just step 3) in the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 dispersion of materials that obtains in appropriate ethanolic solution, then titanium sulfate and lithium acetate Li:Ti=(0.8:1) that weight ratio is 1% is added, then when stir at 80 DEG C, solvent evaporated, then powder is collected, 800 DEG C are heated to the programming rate of 5 DEG C/min, calcining 2h, Temperature fall, to room temperature, namely obtains nano lithium titanate Surface coating 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material.
Can continue with prepared 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material preparation experiment battery pole piece and test battery.The process of preparation experiment battery pole piece is: mixed according to mass ratio 8 ︰ 1 ︰ 1 with conductive agent acetylene black, PVDF by 0.5Li2MnO30.5LiNi0.5Mn0.5O2 positive electrode, with NMP, this mixture is modulated into slurry, evenly be coated on aluminium foil, put into baking oven to dry, taking-up is washed into pole piece, vacuumize 12h at 90 DEG C, carries out compressing tablet, then continues vacuumize 12h and obtains experimental cell pole piece.The process of assembling battery and test is: with the pole piece of above-mentioned preparation for positive pole, be to electrode with lithium sheet, the solution of electrolyte to be concentration the be LiPF6 of 1mol/L, its solvent is EC (ethyl carbonate ester)+DMC (dimethyl carbonate), wherein the volume ratio of EC (ethyl carbonate ester) and DMC (dimethyl carbonate) is 1 ︰ 1, barrier film is celgard2400 film, in the glove box being full of argon gas atmosphere, be assembled into CR2025 type button cell, discharge and recharge by voltage be 2.0-4.8V.Charge and discharge cycles is set to: the 1-5 time charging and discharging currents is 0.1C, and the 6-45 time charging and discharging currents is 0.2C (1C=250mA/g).High rate performance test setting: charging current is 0.1C, and discharging current is respectively 0.1C, 0.2C, 0.5C, 1C, each circulation 3 times.
The discharge cycles test data of material prepared by the present embodiment is in table 1.
As shown in Figure 1, the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material discharging cycle performance that the nano lithium titanate prepared of the present embodiment is coated is good.
As shown in Figure 2, the coated 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material of the nano lithium titanate prepared of the present embodiment cycle performance that discharges under different charge-discharge magnification is good, compares with not coated material.
Embodiment 2
The preparation method of the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material that the present embodiment provides a kind of nano lithium titanate coated:
Step 1. co-precipitation is prepared nickel manganese presoma Ni0.5Mn1.5 (OH) 4 and is prepared nickel nitrate and nickel acetate (both amount of substance ratios are 1 ︰ 1) in mole ratio Ni ︰ Mn=1 ︰ 3, the mixture aqueous solution of manganese sulfate, under vigorous stirring state, be the KOH solution of 2M to mixed solution and dripping molar concentration, the pH value of mixed solution is controlled about 10, to ensure Ni2+, Mn2+ precipitation completely, after leaving standstill 2h, suction filtration, washing three times, 110 DEG C dry 12h obtain presoma Ni0.5Mn1.5 (OH) 4.
Step 2. nickel manganese presoma Ni0.5Mn1.5 (OH) 4 preliminary treatment, by step 1) drying of gained presoma Ni0.5Mn1.5 (OH) 4, sinter in air atmosphere, 600 DEG C are heated to the programming rate of 10 DEG C/min, heat preservation sintering 2h, obtain Ni, Mn oxide Ni0.5Mn1.5O4, then in amount of substance ratio Li ︰ Ni ︰ Mn=4.15 ︰ 1 ︰ 3, lithium carbonate and this Ni, Mn oxide batch mixing are obtained solid mixture, wherein Li is excessive is a little a small amount of volatilization loss in order to make up lithium in subsequent high temperature process; And be that 1mL/g adds ball mill in the ratio of ethanol and solid mixture, with the rotating speed ball milling 10h of 500r/min, obtain powder mixture.
Step 3. synthesis in solid state
Powder mixture step 2 obtained takes out dry, then sinters under pure oxygen atmosphere, is heated to 950 DEG C with the programming rate of 1 DEG C/min, calcining 12h; Last Temperature fall, to room temperature, namely obtains 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material.
Step 4. surface treatment step, just step 3) in the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 dispersion of materials that obtains in appropriate ethanolic solution, then titanium sulfate and lithium acetate Li:Ti=(0.8:1) that weight ratio is 2% is added, then when stir at 60 DEG C, solvent evaporated, then powder is collected, 700 DEG C are heated to the programming rate of 3 DEG C/min, calcining 5h, Temperature fall, to room temperature, namely obtains nano lithium titanate Surface coating 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material.
The battery pole piece assembled with the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material that prepared nano lithium titanate is coated and test battery.Prepare pole piece identical with the method in embodiment 1 with method of testing.
The discharge cycles test data of material prepared by the present embodiment is in table 1.
Embodiment 3
The preparation method of the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material that the present embodiment provides a kind of nano lithium titanate coated, comprising:
Step 1. co-precipitation is prepared nickel manganese presoma Ni0.5Mn1.5 (OH) 4 and is prepared nickelous sulfate in amount of substance ratio Ni ︰ Mn=1 ︰ 3, the mixture aqueous solution of manganese chloride and manganese sulfate (both amount of substance ratios are 1 ︰ 1), under stirring, to the LiOH solution that mixed solution and dripping molar concentration is 2M, the pH value of mixed solution is controlled about 10.1, to ensure Ni2+, Mn2+ precipitation completely, after leaving standstill 2h, suction filtration, washing three times, 110 DEG C dry 12h obtain presoma Ni0.5Mn1.5 (OH) 4.
Step 2. nickel manganese presoma Ni0.5Mn1.5 (OH) 4 preliminary treatment, in amount of substance ratio Li ︰ Ni ︰ Mn=4.20 ︰ 1 ︰ 3, lithium acetate and presoma Ni0.5Mn1.5 (OH) 4 batch mixing are obtained solid mixture, wherein Li is excessive is a little a small amount of volatilization loss in order to make up lithium in subsequent high temperature process; And be that 1.3mL/g adds ball mill in the ratio of ethanol and solid mixture, with the rotating speed ball milling 16h of 300r/min, obtain powder mixture.Powder mixture is taken out dry, then in air atmosphere, be heated to 550 DEG C with the programming rate of 4 DEG C/min, heat preservation sintering 8h, obtain pretreated nickel manganese presoma.
Step 3. synthesis in solid state; In air atmosphere, be heated to 850 DEG C with the programming rate of 6 DEG C/min, calcining 24h; Last Temperature fall, to room temperature, namely obtains 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material.
Step 4. surface treatment step, just step 3) in the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 dispersion of materials that obtains in appropriate ethanolic solution, then butyl titanate and lithium acetate Li:Ti=(0.8:1) that weight ratio is 1% is added, then when stir at 80 DEG C, solvent evaporated, then powder is collected, 750 DEG C are heated to the programming rate of 3 DEG C/min, calcining 3h, Temperature fall, to room temperature, namely obtains nano lithium titanate Surface coating 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material.
The battery pole piece assembled with the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material that prepared nano lithium titanate is coated and test battery.Prepare pole piece identical with the method in embodiment 1 with method of testing.
The discharge cycles test data of material prepared by the present embodiment is in table 1.
Embodiment 4
The preparation method of the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material that the present embodiment provides a kind of nano lithium titanate coated,
Nickel manganese presoma Ni0.5Mn1.5 (OH) 4 prepares nickel acetate and manganese acetate mixture aqueous solution in amount of substance ratio Ni ︰ Mn=1 ︰ 3 is prepared in step 1. co-precipitation, under stirring, be the NaOH solution of 2M to mixed solution and dripping molar concentration, the pH value of mixed solution is controlled about 10.4, to ensure Ni2+, Mn2+ precipitation completely, after leaving standstill 2h, suction filtration, washing three times, 110 DEG C dry 12h obtain presoma Ni0.5Mn1.5 (OH) 4.
Step 2. nickel manganese presoma Ni0.5Mn1.5 (OH) 4 preliminary treatment, by step 1) drying of gained presoma Ni0.5Mn1.5 (OH) 4, sinter under pure oxygen atmosphere, 500 DEG C are heated to the programming rate of 2 DEG C/min, heat preservation sintering 12h, obtain Ni, Mn oxide Ni0.5Mn1.5O4, then in amount of substance ratio Li ︰ Ni ︰ Mn=4.05 ︰ 1 ︰ 3, lithium hydroxide and this Ni, Mn oxide batch mixing are obtained solid mixture; And be that 1.5mL/g adds ball mill in the ratio of ethanol and solid mixture, with the rotating speed ball milling 6h of 500r/min, obtain powder mixture.
Step 3. synthesis in solid state; Powder mixture step 2 obtained takes out dry, then sinters under pure oxygen atmosphere, is heated to 900 DEG C with the programming rate of 8 DEG C/min, calcining 4h; Last Temperature fall, to room temperature, namely obtains 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material.
Step 4. surface treatment step, just step 3) in the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 dispersion of materials that obtains in appropriate ethanolic solution, then butyl titanate and lithium acetate Li:Ti=(0.8:1) that weight ratio is 2% is added, then when stir at 70 DEG C, solvent evaporated, then powder is collected, 750 DEG C are heated to the programming rate of 5 DEG C/min, calcining 3h, Temperature fall, to room temperature, namely obtains nano lithium titanate Surface coating 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material.
The battery pole piece assembled with the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material that prepared nano lithium titanate is coated and test battery.Prepare pole piece identical with the method in embodiment 1 with method of testing.The discharge cycles test data of material prepared by the present embodiment is in table 1.
The coated 0.5Li2MnO30.5LiNi0.5Mn0.5O2 material of table one nano lithium titanate compares under different embodiment.
Above by reference to the accompanying drawings to invention has been exemplary description; obvious specific implementation of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or directly apply to other occasion, all within protection scope of the present invention without improving.
Claims (10)
1. the rich lithium solid-solution material of rich manganese, it is characterized in that, it is a kind of 0.5Li
2mnO
30.5LiNi0.5Mn0.5O
2the rich lithium solid-solution material of rich manganese.
2. the purposes of the rich lithium solid-solution material of rich manganese as claimed in claim 1, is characterized in that, as cell positive material.
3. the purposes of the rich lithium solid-solution material of rich manganese as claimed in claim 2, is characterized in that, as lithium ion power battery cathode material.
4. the modification method for preparing of the rich lithium solid-solution material of rich manganese as claimed in claim 1, is characterized in that, comprise the steps:
(1) predecessor is formed;
(2) lithium is accompanied to synthesize solid-solution material;
(3) at material surface uniform deposition lithium titanate.
5. the modification method for preparing of the rich lithium solid-solution material of rich manganese as claimed in claim 4, is characterized in that, by coprecipitation in step (1), form predecessor Ni0.5Mn1.5 (OH)
4.
6. the modification method for preparing of the rich lithium solid-solution material of rich manganese as described in claim 4 or 5, it is characterized in that, step (1) comprises the steps:
(1-1) mixture aqueous solution of nickel presoma and manganese presoma is prepared in the mole ratio Ni ︰ Mn=1 ︰ 3 of material;
(1-2) in mixture aqueous solution, add alkaline solution pH value regulator, pH value is controlled at 10-12;
(1-3) stir;
(1-4) centrifugal;
(1-5) pure water cleaning obtains nickel manganese presoma Ni0.5Mn1.5 (OH)
4.
7. the modification method for preparing of the rich lithium solid-solution material of rich manganese according to any one of claim 4-6, it is characterized in that, step (2) comprises the steps:
(2-1) in amount of substance ratio Li ︰ Ni ︰ Mn=, (lithium source and nickel manganese presoma batch mixing are obtained solid mixture by 6.3 ~ 6.6) ︰ 1 ︰ 3;
(2-2) form powder, obtain powder mixture;
(2-3) under an oxygen-containing atmosphere, 500-600 DEG C is heated to the programming rate of 1-5 DEG C/min;
(2-4) heat preservation sintering 5-10h, obtains pretreated nickel manganese presoma.
8. the modification method for preparing of the rich lithium solid-solution material of rich manganese according to any one of claim 4-7, it is characterized in that, step (2) also comprises the steps: the pretreated nickel manganese presoma of gained under an oxygen-containing atmosphere, 800-1000 DEG C is heated to the programming rate of 0.5-10 DEG C/min, calcining 8-24h, Temperature fall, to room temperature, namely obtains 0.5Li
2mnO
30.5LiNi0.5Mn0.5O
2material.
9. the modification method for preparing of the rich lithium solid-solution material of rich manganese according to any one of claim 4-8, it is characterized in that, step (3) comprises the steps:
(3-1) the 0.5Li2MnO30.5LiNi0.5Mn0.5O2 dispersion of materials obtained is in appropriate ethanolic solution;
(3-2) appropriate titanium source and lithium source Li:Ti=(0.8:1) is added;
(3-3) when stir at 50-80 DEG C, solvent evaporated;
(3-4) powder is collected;
(3-5) 700-800 DEG C is heated to the programming rate of 3-10 DEG C/min;
(3-6) 2-10h is calcined;
(3-7) Temperature fall is to room temperature, namely obtains nano lithium titanate Surface coating 0.5Li
2mnO
30.5LiNi0.5Mn0.5O
2material.
10. the modification method for preparing of the rich lithium solid-solution material of rich manganese according to any one of claim 4-9, it is characterized in that, solid phase reaction atmosphere is oxygen-containing atmosphere is air atmosphere or pure oxygen atmosphere; And/or solid material mixed method is wet ball grinding, described wet ball grinding comprises: mixed with the ratio of solid mixture in 1 ︰ (1-2) mL/g by ethanol, with the rotating speed ball milling 2-16h of 300-500r/min; And/or described nickel presoma is one or more in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride; And/or described manganese presoma is one or more in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride; And/or described titanium source presoma is one or more in butyl titanate, manganese sulfate, titanium tetrachloride; And/or described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, lithia; And/or described alkaline pH adjuster is NaOH solution or KOH solution or LiOH solution.
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| CN111740085A (en) * | 2020-06-19 | 2020-10-02 | 贵州梅岭电源有限公司 | Coating modification method of lithium-rich manganese-based positive electrode material |
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Application publication date: 20150624 |