CN103107326B - A kind of La3+,Co3+,Fe3+,F-Codope composite lithium-rich anode material and preparation method - Google Patents
A kind of La3+,Co3+,Fe3+,F-Codope composite lithium-rich anode material and preparation method Download PDFInfo
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Abstract
A kind of La3+, Co3+, 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-y(Mn0.5Ni0.5)1-m-n-pComLanFepO2-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, La (NO3)3·6H2O、Co(NO3)2·6H2O, soluble ferric iron salt and lithium fluoride join in deionized water, add the tartaric acid that amount of substance is all metal ions total amount 1.2-2.0 times and stir to being completely dissolved；Solution is prepared after concentration, gel, dry, grindings, decompositions, tabletting, calcining step, and the positive electrode prepared has excellent circulation volume holding capacity and multiplying power property.
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 the energy density being effectively improved lithium ion battery, it is necessary to from the viewpoint 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 commonly used practicality of lithium ion battery commercial at present 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.Therefore 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 lithium ion cell positive filtered out is up to tens of kinds, but really has potential commercial applications prospect or the positive electrode that is already present on market very few really.Such as lithium manganate having spinel structure LiMn2O4, it is less costly, is easier preparation, and security performance is also 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 not good, 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 prepare extremely difficult, poor heat stability, and cyclicity is very poor, and capacity attenuation is quickly.And current progressively business-like LiFePO4 LiFePO4Cost is low, 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, particularly the 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 significantly high Capacity Ratio, high stability and relative moderate and are subject to the concern [Young-SikHong of people, YongJoonPark, etal., SolidStateIonics, 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, for the layer structure that Li layer and manganese layer are constituted, 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 also only small.As itself and the LiMn being all layer structure0.5Ni0.5O2After compound, form the lithium-rich positive electrode xLi of layered-layered structure2MnO3.(1-x)LiMn0.5Ni0.5O2So 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, it is prevented that material structure caves in charge and discharge process, and Ni becomes+4 valencys from+divalent state, 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 Li previously deviate from2O does not return in lattice, carries out Ni along with what discharge4+It is gradually reduced to Ni2+, the Mn in material subsequently4+Also participation electrochemical process it is reduced, therefore Li2MnO3Activation during more than 4.6V is the reason [Johnson, C.S., N.Li, etal., Electrochemistrycommunications, 2007,9 (4): 787-795.] that this material has more than 200mAh/g.
But, actually xLi2MnO3.(1-x)LiM′O2The microstructure of the lithium-rich positive electrode of layered-layered structure is extremely complex, as ThackerayM.M. [ThackerayMM, KangS-H, JohnsonCS, etal.JournalofMaterialsChemistry, that 2007,17:3112-3125.] et al. points out is such, and the result of study of XRD and x ray absorption near edge structure test all shows xLi2MnO3.(1-x)LiMn0.5Ni0.5O2O2The lithium-rich positive electrode of layered-layered structure is not pure solid solution, and excessive lithium ion 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 LiMn0.5Ni0.5O2Compound on nanoscale, 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, Li2MnO3The electronic conductivity of feature structure and ionic conductivity are all very low, on the other hand, and xLi2MnO3.(1-x)LiMn0.5Ni0.5O2Laminate Li2MnO3Interlamellar spacing and LiMn0.5Ni0.5O2Interlamellar spacing difference is relatively big, and both does not mate the embedding causing lithium ion and deviate from relatively difficult, causes that the overall lithium ion conductivity of composite is low, and lithium ion diffusion coefficient is 10-12-10-13S/cm2Between.So xLi2MnO3.(1-x)LiMn0.5Ni0.5O2Cyclical stability not good, repeatedly after circulation, capacity attenuation is very fast, and when charging and discharging currents increases, capacity attenuation is quickly
Ion doping is one of the multiplying power property and the relatively effective means of Capacity fading that improve 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 [KangSH, ThackerayMM., ElectrochemicalSociety, 2008,155:A269-A275.] of material circulation.And Co doping often can improve the ionic conductivity of material, thus increasing discharge capacity, promoting multiplying power property.But dopant ion is extremely complex with the interaction of matrix, the chemical property of material is all had considerable influence by the characteristics such as the size of dopant ion, electronic structure, electronegativity, and have interaction between different dopant ions, it is promote or suppress the degree of chemical property and promotion and suppression all can have very big difference along with the ionic species mixed and concentration.Actually, doping not only affects the quantity of dopant ion and 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, the performance of positive electrode is also had very big impact by this.The mechanism of action of material electrochemical performance is also not yet recognized by doped lithium ion completely.Therefore the kind of dopant ion and content are studied 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 La provided for existing background technology3+, Co3+, 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 oxonium ion under high potential and deviates from the quantity of lattice, reduce 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 and deviates from charging and again can not reduce irreversible capacity loss by the lithium ion in embedding time rich lithium material；Co3+Doping improves the lithium ion conductivity of material；La3+Radius is relatively big, replaces (Mn0.5Ni0.5) structure contribute to expand Lithium-ion embeding deintercalation passage；The synergism of these factors makes layer-layer composite lithium-rich anode material xLi2MnO3.(1-x)LiMn0.5Ni0.5O2(0≤x≤0.5) has better circulation volume holding capacity and multiplying power property.
The present invention reaches by the following technical solutions, and this technical scheme provides the layer-layer lithium-rich anode material of a kind of high circulation volume holding capacity and multiplying power property, and its stoichiometric equation is xLi2MnO3.(1-x)Li1-y(Mn0.5Ni0.5)1-m-n-pComLanFepO2-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, La (NO3)3·6H2O、Co(NO3)2·6H2O, soluble ferric iron salt and lithium fluoride join in deionized water, add the tartaric acid that amount of substance is all metal ions total amount 1.2-2.0 times and stir to being completely dissolved；The temperature of system rising to the 70-90 DEG C of continuously stirred water until 70-85% evaporate, at this moment solution becomes thickness gradually and is formed gelatin.Gelatin material is ground 10-30 minute after dry 20-50 hour in the baking oven of 150-200 DEG C in mortar.By the powder that obtains in tube furnace with the ramp of 2-10 DEG C/min to 500-600 DEG C calcining 3-6 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 of 2-10 DEG C/min to 850-950 DEG C 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 oxonium ion under high potential and deviates from the quantity of lattice, reduce 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 and deviates from charging and again can not reduce irreversible capacity loss by the lithium ion in embedding time rich lithium material；Co3+Doping improves the lithium ion conductivity of material；La3+Radius is relatively big, replaces (Mn0.5Ni0.5) structure contribute to expand Lithium-ion embeding deintercalation passage；The synergism of these factors makes layer-layer composite lithium-rich anode material xLi2MnO3.(1-x)
LiMn0.5Ni0.5O2(0≤x≤0.5) has better 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∶La(NO3)3·6H2O∶Fe(NO3)3·9H2O∶Co(NO3)2·6H2O: LiF is the ratio uniform mixing of 1.082: 0.5365: 0.4365: 0.009: 0.009: 0.009: 0.009 (mol ratio), join in deionized water, add the tartaric acid that amount of substance is all metal ions total amount 1.2 times and stir to being completely dissolved；The temperature of system rising to 70 DEG C of continuously stirred water until 71% evaporate, at this moment solution becomes thickness gradually and is formed gelatin.Gelatin material is ground 10 minutes after dry 22 hours in the baking oven of 150 DEG C in mortar.By the powder that obtains in tube furnace with the ramp of 2 DEG C/min to 500 DEG C 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 of 2 DEG C/min to 850 DEG C in tube furnace, after furnace cooling, obtain this lithium-rich anode material.
Embodiment 2: by LiNO3∶Mn(CH3COO)2·4H2O∶Ni(CH3COO)2·4H2O∶La(NO3)3·6H2O∶Fe(NO3)3·9H2O∶Co(NO3)2·6H2O: LiF is the ratio uniform mixing of 1.44: 0.7125: 0.2125: 0.025: 0.025: 0.025: 0.03 (mol ratio), join in deionized water, add the tartaric acid that amount of substance is all metal ions total amount 1.8 times and stir to being completely dissolved；The temperature of system rising to 90 DEG C of continuously stirred water until 85% evaporate, at this moment solution becomes thickness gradually and is formed gelatin.Gelatin material is ground 30 minutes after dry 48 hours in the baking oven of 200 DEG C in mortar.By the powder that obtains in tube furnace with the ramp of 10 DEG C/min to 600 DEG C calcining 6 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 of 9 DEG C/min to 950 DEG C in tube furnace, after furnace cooling, obtain this lithium-rich anode material.
Embodiment 3: by LiNO3∶Mn(CH3COO)2·4H2O∶Ni(CH3COO)2·4H2O∶La(NO3)3·6H2O∶Fe(NO3)3·9H2O∶Co(NO3)2·6H2O: LiF is the ratio uniform mixing of 1.152: 0.576: 0.376: 0.016: 0.016: 0.016: 0.024 (mol ratio), join in deionized water, add the tartaric acid that amount of substance is all metal ions total amount 1.6 times and stir to being completely dissolved；The temperature of system rising to 80 DEG C of continuously stirred water until 78% evaporate, at this moment solution becomes thickness gradually and is formed gelatin.Gelatin material is ground 20 minutes after dry 35 hours in the baking oven of 170 DEG C in mortar.By the powder that obtains in tube furnace with the ramp of 7 DEG C/min to 550 DEG C 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 of 6 DEG C/min to 900 DEG C in tube furnace, after furnace cooling, obtain this lithium-rich anode material.
Embodiment 4: by CH3COOLi∶MnSO4·H2O∶Ni(CH3COO)2·4H2O∶La(NO3)3·6H2O∶Fe(NO3)3·9H2O∶Co(NO3)2·6H2O: LiF is the ratio uniform mixing of 1.258: 0.622: 0.322: 0.021: 0.014: 0.021: 0.021 (mol ratio), join in deionized water, add the tartaric acid that amount of substance is all metal ions total amount 1.8 times and stir to being completely dissolved；The temperature of system rising to 80 DEG C of continuously stirred water until 82% evaporate, at this moment solution becomes thickness gradually and is formed gelatin.Gelatin material is ground 10 minutes after dry 45 hours in the baking oven of 190 DEG C in mortar.By the powder that obtains in tube furnace with the ramp of 5 DEG C/min to 550 DEG C 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 of 6 DEG C/min to 900 DEG C in tube furnace, after furnace cooling, obtain this lithium-rich anode material.
Embodiment 5: by LiNO3∶Mn(CH3COO)2·4H2O∶NiSO4·6H2O∶La(NO3)3·6H2O∶FeCl3·6H2O∶Co(NO3)2·6H2O: LiF is the ratio uniform mixing of 1.34: 0.67: 0.27: 0.018: 0.018: 0.024: 0.03 (mol ratio), join in deionized water, add the tartaric acid that amount of substance is all metal ions total amount 1.3 times and stir to being completely dissolved；The temperature of system rising to 73 DEG C of continuously stirred water until 75% evaporate, at this moment solution becomes thickness gradually and is formed gelatin.Gelatin material is ground 30 minutes after dry 25 hours in the baking oven of 160 DEG C in mortar.By the powder that obtains in tube furnace with the ramp of 10 DEG C/min to 550 DEG C 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 of 6 DEG C/min to 950 DEG C in tube furnace, after furnace cooling, obtain this lithium-rich anode material.
Claims (1)
1. a La3+, Co3+, 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-y(Mn0.5Ni0.5)1-m-n-pComLanFepO2-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: according to the stoichiometric proportion of above-mentioned stoichiometric equation by soluble lithium compounds, soluble manganese salt, soluble nickel salt, La (NO3)3·6H2O、Co(NO3)2·6H2O, soluble ferric iron salt and lithium fluoride join in deionized water, add the tartaric acid that amount of substance is all metal ions total amount 1.2-2.0 times and stir to being completely dissolved；The temperature of system rising to the 70-90 DEG C of continuously stirred water until 70-85% evaporate, at this moment solution becomes thickness gradually and is formed gelatin；Gelatin material is ground 10-30 minute after dry 20-50 hour in the baking oven of 150-200 DEG C in mortar；By the powder that obtains in tube furnace with the ramp of 2-10 DEG C/min to 500-600 DEG C calcining 3-6 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 of 2-10 DEG C/min to 850-950 DEG C in tube furnace, after furnace cooling, obtain this 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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