CN103066273B - A kind of Ti4+, Al3+, Fe3+, F-codope composite lithium-rich anode material and preparation method - Google Patents
A kind of Ti4+, Al3+, Fe3+, F-codope composite lithium-rich anode material and preparation method Download PDFInfo
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Abstract
A kind of Ti4+, Al3+, Fe3+, F‑Codope composite lithium-rich anode material xLi layer by layer2MnO3.(1‑x)LiMn0.5Ni0.5O2(0≤x≤0.5), it is characterised in that stoichiometric equation is xLi2MnO3.(1‑x)Li1‑n‑y(Mn0.5Ni0.5)1‑m‑npAlm TinFepO2‑yFyWherein: 0≤x≤0.5；0.01≤m≤0.05；0.01≤n≤0.05；0.01≤p≤0.05；0.01≤y≤0.06；By the stoichiometric proportion according to above-mentioned molecular formula by soluble lithium compounds, soluble manganese salt, soluble nickel salt, butyl titanate, Al (NO3)3·9H2O, soluble ferric iron salt and lithium fluoride join in deionized water, and the tartaric acid that amount is all metal ions total amount 2.5 4.0 times adding material stirs to being completely dissolved；Solution through concentration, gel, be dried, grind, decompose, prepare after tabletting, calcining step, the positive electrode prepared has circulation volume holding capacity and the multiplying power property of excellence.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and manufacture field.
Background technology
Lithium ion battery have volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, have extended cycle life, the high absolute advantage of power density, have in portable power source market, the whole world and exceed 30,000,000,000 dollar/year shares and exceed well over the market share of other batteries, it is the electrochmical power source [Wu Yuping most with market development prospect, Wan Chunrong, Jiang Changyin, lithium rechargeable battery, Beijing: Chemical Industry Press, 2002.].But since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time between 100-180mAh/g, positive electrode specific capacity is low has become as the bottleneck promoting lithium ion battery specific energy.If wanting to be effectively improved the energy density of lithium ion battery, it is necessary to from the standpoint of the voltage difference improved between positive and negative pole material and exploitation height ratio capacity electrode material two.
The positive electrode of the most commercial most commonly used practicality of lithium ion battery is LiCoO2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and actual specific capacity is between 130-140mAh/g, and cobalt is strategic materials, expensive and have bigger toxicity.The most in recent years, the research worker of countries in the world is devoted to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, up till now, the most tens of kinds of the lithium ion cell positive filtered out, but really have potential commercial applications prospect or the positive electrode that is already present on market the fewest.Such as lithium manganate having spinel structure LiMn2O4, its cost is relatively low, is easier preparation, and security performance is relatively good, but capacity is relatively low, and theoretical capacity is 148mAh/g, and actual capacity is at 100-120mAh/g, and this material capacity circulation holding capacity is the best, and under high temperature, capacity attenuation is quickly, Mn3+John-Teller effect and dissolving in the electrolyte annoying research worker for a long time.The LiNiO of layer structure2And LiMnO2Although having bigger theoretical specific capacity, respectively 275mAh/g and 285mAh/g, but they preparing extremely difficult, poor heat stability, cyclicity is very poor, and capacity attenuation is quickly.And current the most business-like LiFePO4 LiFePO4Low cost, Heat stability is good, environmental friendliness, but its theoretical capacity about only has 170mAh/g, and actual capacity is at about 140mAh/g.
In recent years, research worker is gradually by high lithium ratio on positive electrode, the particularly high lithium of manganio manganese-nickel binary and manganio manganese-nickel-cobalt ternary solid solution system compares positive electrode, these materials have the cost of the highest Capacity Ratio, high stability and relative moderate and are paid close attention to [Young-Sik Hong by people, Yong Joon Park, et al., Solid State Ionics, 2005,176:1035～1042].Rich lithium material can regard Li as2MnO3With LiM ' O2(M '=Mn, Co, Ni, Mn0.5Ni0.5Deng) continuous solid solution xLi2MnO3.(1-x)LiM′O2.As M '=Mn0.5Ni0.5Time, it is xLi2MnO3.(1-x)LiMn0.5Ni0.5O2Layer-layer richness lithium composite positive pole.Li2MnO3Having halite structure, symmetry is C2/m.Can be write as Li [Li1/3Mn2/3]O2Form, the layer structure constituted for Li layer and manganese layer, Li+And Mn4+Collectively form manganese layer, each octahedra Li+By six octahedra Mn4+Surrounded formation Li (Mn)6Structure, and the lithium ion in Li layer is tetrahedral structure.Li2MnO3Electro-chemical activity relatively low, electronic conductivity and ionic conductivity are the least.As itself and the LiMn being all layer structure0.5Ni0.5O2After Fu He, form the lithium-rich positive electrode xLi of layered-layered structure2MnO3.(1-x)Li Mn0.5Ni0.5O2So that the positive electrode of this structure has more than the discharge capacity of 200mAh/g.This material is when charging voltage is less than 4.6V, and Mn keeps+4 valencys constant, Li2MnO3Structure keeps inertia, it is provided that the stability of cathode material structure, prevents material structure in charge and discharge process from caving in, and Ni becomes+4 valencys from+2 valence, is the active component producing capacity.When charging voltage is more than 4.6V, in 4.6V position it would appear that a platform, this is Li2O is from Li2MnO3In lattice completely out and become MnO2, at this moment cell voltage is up to more than 4.8V；When battery starts to discharge, the previously Li of abjection2O does not returns in lattice, carries out Ni along with discharge4+It is gradually reduced to Ni2+, the Mn in material subsequently4+Also participation electrochemical process, therefore Li it are reduced2MnO3It is the reason [Johnson, C.S., N.Li, et al., Electrochemistry communications, 2007,9 (4): 787-795.] that this material has more than 200mAh/g more than activation during 4.6V.
But, actually xLi2MnO3.(1-x)LiM′O2The microstructure of the lithium-rich positive electrode of layered-layered structure is extremely complex, as Thackeray M.M. [Thackeray M M, Kang S-H, Johnson C S, et al.Journal ofMaterials Chemistry, 2007,17:3112-3125.], as et al. pointing out, the result of study of XRD and x ray absorption near edge structure test all shows xLi2MnO3.(1-x)LiMn0.5Ni0.5O2The solid solution that the lithium-rich positive electrode of layered-layered structure is not pure, the lithium ion of excess is distributed in transition metal layer by arest neighbors Mn4+Surround, form the LiMn of local cluster6Structure, and LiMn6Li just2MnO3Feature structure.Therefore xLi2MnO3.(1-x)LiMn0.5Ni0.5O2Material structure regards as stratiform Li2MnO3With stratiform LiMn0.5Ni0.5O2On nanoscale compound, the arrangement shortrange order of its lithium ion and transition metal ions and longrange disorder is more particularly suitable.So, due to insulation phase Li2MnO3Existence, Li2MnO3Electronic conductivity and the ionic conductivity of feature structure are the lowest, on the other hand, and xLi2MnO3.(1-x)LiMn0.5Ni0.5O2Laminate Li2MnO3Interlamellar spacing and LiMn0.5Ni0.5O2Interlamellar spacing difference is relatively big, and both do not mate causes the embedding of lithium ion and deviate from relatively difficult, and the overall lithium ion conductivity causing composite is low, and lithium ion diffusion coefficient is 10-12-10-13S/cm2Between.So xLi2MnO3.(1-x)LiMn0.5Ni0.5O2Cyclical stability the best, repeatedly after circulation, capacity attenuation is very fast, and when charging and discharging currents increases, capacity attenuation is quickly.
Ion doping is one of multiplying power property and the relatively effective means of Capacity fading of improving lithium ion anode, F-Ion doping makes the oxonium ion of part by F-Replace, reduce Surface Oxygen activity under high voltages, it is suppressed that the precipitation of oxygen.It is favorably improved the capacity holding capacity [Kang S H, Thackeray M M., ElectrochemicalSociety, 2008,155:A269-A275.] of material circulation.And Co doping often can improve the ionic conductivity of material, thus increase discharge capacity, promote multiplying power property.But dopant ion is extremely complex with the interaction of matrix, the characteristics such as the size of dopant ion, electronic structure, electronegativity all chemical properties to material have considerable influence, and have interaction between different dopant ions, it is that the degree promoting or suppressing chemical property and promotion and suppression all can have the biggest difference along with the ionic species mixed and concentration.Actually, doping not only affects dopant ion and the quantity of host ions in lattice, because material entirety needs to keep electric neutrality, therefore also affecting the valence state of other transition metal ionss thus whole crystal structure, this also has the biggest impact to the performance of positive electrode.The mechanism of action of material electrochemical performance is recognized by doped lithium ion the most completely.Study the kind of dopant ion and content the most further to developing high performance composite lithium-rich anode material xLi layer by layer2MnO3.(1-x)LiMn0.5Ni0.5O2There is critically important meaning.
Summary of the invention
The technical problem to be solved is a kind of Ti provided for existing background technology4+, Al3+, Fe3+, F-Codoped layers-layer composite lithium-rich anode material xLi2MnO3.(1-x)LiMn0.5Ni0.5O2(0≤x≤0.5).Pass through F-Doping, reduces the quantity of oxonium ion abjection lattice under high potential, reduces oxygen defect concentration in crystalline surface, improve the surface stability under material high potential；Fe3+/Fe2+Oxidation-reduction potential is relatively low and good reversibility, receives abjection in charging and can not reduce irreversible capacity loss by the lithium ion in the most embedding time rich lithium material；Al-O structure has higher ionic conductivity；Ti4+Radius ratio Mn4+And Ni2+Radius is bigger, is conducive to improving the charge/discharge capacity under the multiplying power property of material and equal conditions；The synergism of these factors makes layer-layer composite lithium-rich anode material xLi2MnO3.(1-x)LiMn0.5Ni0.5O2(0≤x≤0.5) has more preferable circulation volume holding capacity and multiplying power property.
The present invention reaches by the following technical solutions, and this technical scheme provides a kind of high circulation volume holding capacity and the layer-layer lithium-rich anode material of multiplying power property, and its stoichiometric equation is xLi2MnO3.(1-x)Li1-n-y(Mn0.5Ni0.5)1-m-n-pAlm TinFepO2-yFyWherein: 0≤x≤0.5；0.01≤m≤0.05；0.01≤n≤0.05；0.01≤p≤0.05；0.01≤y≤0.06.
In this technical scheme, by the stoichiometric proportion according to above-mentioned molecular formula by soluble lithium compounds, soluble manganese salt, soluble nickel salt, butyl titanate, Al (NO3)3·9H2O, soluble ferric iron salt and lithium fluoride join in deionized water, and the tartaric acid that amount is all metal ions total amount 2.5-4.0 times adding material stirs to being completely dissolved；The temperature of system rises to the 70-85 DEG C of continuously stirred water evaporation until 70-85%, and at this moment solution gradually becomes thickness and is formed gelatin.Grind 10-30 minute in mortar after gelatin material is dried 20-48 hour in the baking oven of 130-200 DEG C.By the powder that obtains in tube furnace with the ramp to 500-600 DEG C of 2-10 DEG C/min calcining 3-5 hour at this temperature, powder is taken out after cooling, mortar continues grind 10-30 minute, with the pressure of 100-300MPa, powder is pressed into sheet, then calcine 5-15 hour with the ramp to 850-950 DEG C of 2-10 DEG C/min in tube furnace, after furnace cooling, obtain this lithium-rich anode material.Wherein: soluble lithium salt is LiNO3、CH3One in COOLi；Soluble manganese salt is Mn (CH3COO)2·4H2O、MnSO4·H2One in O；Soluble nickel salt is Ni (CH3COO)2·4H2O、NiSO4·6H2One in O；Soluble ferric iron salt is Fe (NO3)3·9H2O、FeCl3·6H2One in O.
Compared with prior art, it is an advantage of the current invention that: pass through F-Doping, reduces the quantity of oxonium ion abjection lattice under high potential, reduces oxygen defect concentration in crystalline surface, improve the surface stability under material high potential；Fe3+/Fe2+Oxidation-reduction potential is relatively low and good reversibility, receives abjection in charging and can not reduce irreversible capacity loss by the lithium ion in the most embedding time rich lithium material；Al-O structure has higher ionic conductivity；Ti4+Radius ratio Mn4+And Ni2+Radius is bigger, is conducive to improving the charge/discharge capacity under the multiplying power property of material and equal conditions；The synergism of these factors makes layer-layer composite lithium-rich anode material xLi2MnO3.(1-x)LiMn0.5Ni0.5O2(0≤x≤0.5) has more preferable circulation volume holding capacity and multiplying power property.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: by LiNO3∶Mn(CH3COO)2·4H2O∶Ni(CH3COO)2·4H2O: butyl titanate: Fe (NO3)3·9H2O∶Al(NO3)3·9H2O: LiF is the ratio uniform mixing of 1.073: 0.5365: 0.4365: 0.009: 0.009: 0.009: 0.009 (mol ratio), joining in deionized water, the tartaric acid that amount is all metal ions total amount 2.5 times adding material stirs to being completely dissolved；The temperature of system rising to 70 DEG C of continuously stirred water until 71% evaporate, at this moment solution gradually becomes thickness and is formed gelatin.Grind 10 minutes in mortar after gelatin material is dried 22 hours in the baking oven of 130 DEG C.By the powder that obtains in tube furnace with the ramp to 500 DEG C of 2 DEG C/min calcining 3 hours at this temperature, powder is taken out after cooling, mortar continues grind 10 minutes, with the pressure of 100MPa, powder is pressed into sheet, then calcine 5 hours with the ramp to 850 DEG C of 2 DEG C/min in tube furnace, after furnace cooling, obtain this lithium-rich anode material.
Embodiment 2: by LiNO3∶Mn(CH3COO)2·4H2O∶Ni(CH3COO)2·4H2O: butyl titanate: Fe (NO3)3·9H2O∶Al(NO3)3·9H2O: LiF is the ratio uniform mixing of 1.415: 0.7125: 0.2125: 0.025: 0.025: 0.025: 0.03 (mol ratio), joining in deionized water, the tartaric acid that amount is all metal ions total amount 4.0 times adding material stirs to being completely dissolved；The temperature of system rising to 85 DEG C of continuously stirred water until 85% evaporate, at this moment solution gradually becomes thickness and is formed gelatin.Grind 30 minutes in mortar after gelatin material is dried 48 hours in the baking oven of 200 DEG C.By the powder that obtains in tube furnace with the ramp to 600 DEG C of 10 DEG C/min calcining 5 hours at this temperature, powder is taken out after cooling, mortar continues grind 30 minutes, with the pressure of 300MPa, powder is pressed into sheet, then calcine 15 hours with the ramp to 950 DEG C of 9 DEG C/min in tube furnace, after furnace cooling, obtain this lithium-rich anode material.
Embodiment 3: by LiNO3∶Mn(CH3COO)2·4H2O∶Ni(CH3COO)2·4H2O: butyl titanate: Fe (NO3)3·9H2O∶Al(NO3)3·9H2O: LiF is the ratio uniform mixing of 1.136: 0.576: 0.376: 0.016: 0.016: 0.016: 0.024 (mol ratio), joining in deionized water, the tartaric acid that amount is all metal ions total amount 3.2 times adding material stirs to being completely dissolved；The temperature of system rising to 78 DEG C of continuously stirred water until 78% evaporate, at this moment solution gradually becomes thickness and is formed gelatin.Grind 20 minutes in mortar after gelatin material is dried 35 hours in the baking oven of 170 DEG C.By the powder that obtains in tube furnace with the ramp to 550 DEG C of 7 DEG C/min calcining 4 hours at this temperature, powder is taken out after cooling, mortar continues grind 20 minutes, with the pressure of 200MPa, powder is pressed into sheet, then calcine 10 hours with the ramp to 900 DEG C of 6 DEG C/min in tube furnace, after furnace cooling, obtain this lithium-rich anode material.
Embodiment 4: by CH3COOLi∶MnSO4·H2O∶Ni(CH3COO)2·4H2O: butyl titanate: Fe (NO3)3·9H2O∶Al(NO3)3·9H2O: LiF is the ratio uniform mixing of 1.435: 0.735: 0.235: 0.015: 0.01: 0.005: 0.025 (mol ratio), joining in deionized water, the tartaric acid that amount is all metal ions total amount 3.0 times adding material stirs to being completely dissolved；The temperature of system rising to 80 DEG C of continuously stirred water until 82% evaporate, at this moment solution gradually becomes thickness and is formed gelatin.Grind 10 minutes in mortar after gelatin material is dried 45 hours in the baking oven of 190 DEG C.By the powder that obtains in tube furnace with the ramp to 550 DEG C of 5 DEG C/min calcining 4 hours at this temperature, powder is taken out after cooling, mortar continues grind 10 minutes, with the pressure of 200MPa, powder is pressed into sheet, then calcine 10 hours with the ramp to 900 DEG C of 6 DEG C/min in tube furnace, after furnace cooling, obtain this lithium-rich anode material.
Embodiment 5: by LiNO3∶Mn(CH3COO)2·4H2O∶NiSO4·6H2O: butyl titanate: FeCl3·6H2O∶Al(NO3)3·9H2O: LiF is the ratio uniform mixing of 1.251: 0.6115: 0.3115: 0.021: 0.021: 0.035: 0.014 (mol ratio), joining in deionized water, the tartaric acid that amount is all metal ions total amount 2.7 times adding material stirs to being completely dissolved；The temperature of system rising to 73 DEG C of continuously stirred water until 75% evaporate, at this moment solution gradually becomes thickness and is formed gelatin.Grind 30 minutes in mortar after gelatin material is dried 25 hours in the baking oven of 150 DEG C.By the powder that obtains in tube furnace with the ramp to 550 DEG C of 10 DEG C/min calcining 4 hours at this temperature, powder is taken out after cooling, mortar continues grind 30 minutes, with the pressure of 300MPa, powder is pressed into sheet, then calcine 15 hours with the ramp to 950 DEG C of 6 DEG C/min in tube furnace, after furnace cooling, obtain this lithium-rich anode material.
Claims (1)
1. a Ti4+, Al3+, Fe3+, F-Codoped layers-layer composite lithium-rich anode material xLi2MnO3·
(1-x)LiMn0.5Ni0.5O2, 0 ＜ x≤0.5, it is characterised in that stoichiometric equation is xLi2MnO3·
(1-x)Li1-n-y(Mn0.5Ni0.5)1-m-n-pAlmTinFepO2-yFy, wherein: 0 ＜ x≤0.5；0.01≤m≤0.05；0.01≤n≤0.05；0.01≤p≤0.05；0.01≤y≤0.06；Its preparation process is that the stoichiometric proportion according to above-mentioned stoichiometric equation is by soluble lithium compounds, soluble manganese salt, soluble nickel salt, butyl titanate, Al (NO3)3·9H2O, soluble ferric iron salt and lithium fluoride join in deionized water, and the tartaric acid that amount is all metal ions total amount 2.5-4.0 times adding material stirs to being completely dissolved；The temperature of system rises to the 70-85 DEG C of continuously stirred water evaporation until 70-85%, and at this moment solution gradually becomes thickness and is formed gelatin；Grind 10-30 minute in mortar after gelatin material is dried 20-48 hour in the baking oven of 130-200 DEG C；By the powder that obtains in tube furnace with the ramp to 500-600 DEG C of 2-10 DEG C/min calcining 3-5 hour at this temperature, powder is taken out after cooling, mortar continues grind 10-30 minute, with the pressure of 100-300MPa, powder is pressed into sheet, then calcine 5-15 hour with the ramp to 850-950 DEG C of 2-10 DEG C/min in tube furnace, after furnace cooling, obtain this layer-layer composite lithium-rich anode material；Above-mentioned soluble lithium compounds is LiNO3、CH3One in COOLi；Soluble manganese salt is Mn (CH3COO)2·4H2O、MnSO4·H2One in O；Soluble nickel salt is Ni (CH3COO)2·4H2O、NiSO4·6H2One in O；Soluble ferric iron salt is Fe (NO3)3·9H2O、FeCl3·6H2One in O.
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