CN103107327A - Ti4+, al3+, fe3+, F- doped layer-spinel composite lithium-rich positive electrode material and its preparation method - Google Patents

Ti4+, al3+, fe3+, F- doped layer-spinel composite lithium-rich positive electrode material and its preparation method Download PDF

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CN103107327A
CN103107327A CN2013100222727A CN201310022272A CN103107327A CN 103107327 A CN103107327 A CN 103107327A CN 2013100222727 A CN2013100222727 A CN 2013100222727A CN 201310022272 A CN201310022272 A CN 201310022272A CN 103107327 A CN103107327 A CN 103107327A
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lithium
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CN103107327B (en
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水淼
程亮亮
杨天赐
舒杰
冯琳
任元龙
郑卫东
高珊
徐晓萍
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Ningbo University
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a Ti4+, Al3+, Fe3+, F-co-doped doped layer-spinel composite lithium- enriched anode material Lix+0.5Mn0.75Ni0.25O05x+2 (x is greater or equal to 0 and less than or equal to 0.5). The anode material is characterized of being in the stoichiometric formula as follows: Lix+0.5+0.5m+0.5p-0.5n-y (Mn 0.75 and Ni 0.25) 1-m-n-pAlmTinFepO0.5x+2-yFy, wherein x is greater or equal to 0 and less than or equal to 0.5; m is greater or equal to 0.01 and less than or equal to 0.05; n is greater or equal to 0.01 and less than or equal to 0.05; p is greater or equal to 0.01 and less than or equal to 0.05; and y is greater or equal to 0.01 and less than or equal to 0.06. According to the stoichiometric ratio of the molecular formula, soluble lithium compounds, soluble nickel salts, butyl titanate, Al(NO3)3.9H2O, soluble iron salts and lithium fluoride are dissolved in deionized water; after tartaric acid with the adding mount of 2.5 to 4.0 times as the total amount of all metal ions is added, all the components are fully stirred until being dissolved completely; and then the solution is concentrated, gelled, dried, grinded, decomposed, tabletted and calcined, thereby obtaining the anode material. The prepared anode material has the good circulation capacity retaining ability and the ratio multiplying characteristic.

Description

Ti 4+, Al 3+, Fe 3+, F -doped layer-spinelle composite lithium-rich anode material and preparation method
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 global portable power source market and exceed 30,000,000,000 dollars of/year shares the occupation rate of market that surpasses other batteries far away, the chemical power source [Wu Yuping that there is future develop most, Wan Chunrong, Jiang Changyin, lithium rechargeable battery, Beijing: Chemical Industry Press, 2002.].Yet, since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time between 100-180mAh/g, the low bottleneck that promotes the lithium ion battery specific energy that become of positive electrode specific capacity.If want effectively to improve the energy density of lithium ion battery, must consider from voltage difference and two aspects of exploitation height ratio capacity electrode material of improving between positive and negative pole material.
The current commercial lithium ion battery positive electrode of practicality the most widely is LiCoO 2, 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 larger toxicity arranged.Therefore in recent years, the researcher 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 reaches tens of kinds, but potential commercial applications prospect is really arranged or the positive electrode that appeared on market very few really.As lithium manganate having spinel structure LiMn 2o 4, its cost is lower, and than being easier to preparation, security performance is also relatively good, however capacity is lower, and theoretical capacity is 148mAh/g, and actual capacity is at 100-120mAh/g, and this material capacity circulation hold facility is not good, and under high temperature, capacity attenuation is very fast, Mn 3+john-Teller effect and dissolving in electrolyte perplexing for a long time the researcher.The LiNiO of layer structure 2and LiMnO 2although larger theoretical specific capacity is arranged, be respectively 275mAh/g and 285mAh/g, their preparations are very difficult, poor heat stability, cyclicity is very poor, and capacity attenuation is very fast.And business-like LiFePO4 LiFePO progressively at present 4cost is low, Heat stability is good, environmental friendliness, but its theoretical capacity approximately only has 170mAh/g, and actual capacity is in the 140mAh/g left and right.
In recent years, the researcher gradually by high lithium than on positive electrode, particularly the high lithium of manganese base manganese-nickel binary and manganese base manganese-nickel-cobalt ternary solid solution system compares positive electrode, these materials have very high Capacity Ratio, high stability and relative cheap cost and are subject to people's concern [Young-Sik Hong, Yong Joon Park, et al., Solid State Ionics, 2005,176:1035～1042].Rich lithium material can be regarded Li as 2mnO 3and LiM ' O 2(M '=Mn, Co, Ni, Mn 0.5ni 0.5deng) continuous solid solution xLi 2mnO 3. (1-x) LiM ' O 2.As M '=Mn 0.5ni 0.5the time, be xLi 2mnO 3. (1-x) LiMn 0.5ni 0.5o 2the rich lithium composite positive pole of layer-layer.Li 2mnO 3have the halite structure, symmetry is C2/m.Can be write as Li[Li 1/3mn 2/3] O 2form is the layer structure of Li layer and manganese layer formation, Li +and Mn 4+common formation manganese layer, each octahedra Li +by six octahedra Mn 4+the formation Li (Mn) that surrounds 6structure, and the lithium ion in the Li layer is tetrahedral structure.Li 2mnO 3electro-chemical activity lower, electronic conductivity and ionic conductivity are also very little.As itself and the LiMn that is all layer structure 0.5ni 0.5o 2after compound, form the rich lithium layered cathode material xLi of layered-layered structure 2mnO 3. (1-x) Li Mn 0.5ni 0.5o 2, make the positive electrode of this structure that the discharge capacity over 200mAh/g be arranged.This material is when charging voltage is less than 4.6V, and Mn keeps+4 valencys constant, Li 2mnO 3structure keeps inertia, and the stability of positive electrode structure is provided, and prevents that material structure caves in charge and discharge process, and Ni, from+become+4 valencys of divalent state, is the active component of generation capacity.When charging voltage surpasses 4.6V, will there will be a platform in the 4.6V position, this is Li 2o is from Li 2mnO 3deviate from fully in lattice and become MnO 2, more than at this moment cell voltage will reach 4.8V; When battery starts to discharge, the Li before deviate from 2o does not return in lattice, along with the Ni that carries out of electric discharge 4+be reduced to gradually Ni 2+, the Mn in material subsequently 4+also be reduced the participation electrochemical process, so Li 2mnO 3activation while surpassing 4.6V is that this material has the reason [Johnson, C.S., N.Li, et al., Electrochemistry communications, 2007,9 (4): 787-795.] over 200mAh/g.
Yet, xLi2MnO in fact 3. (1-x) LiM ' O 2the microstructure of the rich lithium layered cathode material of layered-layered structure is very complicated, as Thackeray M.M.[Thackeray M M, Kang S-H, Johnson C S, et al.Journal of Materials Chemistry, 2007,17:3112-3125.] etc. the people point out like that, the result of study of XRD and x ray absorption near edge structure test all shows xLi 2mnO 3. (1-x) LiMn 0.5ni 0.5o 2the rich lithium layered cathode material of layered-layered structure is not pure solid solution, and excessive lithium ion is distributed in transition metal layer by arest neighbors Mn 4+surround, form the LiMn of local cluster 6structure, and LiMn 6li just 2mnO 3feature structure.So xLi 2mnO 3. (1-x) LiMn 0.5ni 0.5o 2material structure is regarded stratiform Li as 2mnO 3with stratiform LiMn 0.5ni 0.5o 2compound on nanoscale, its lithium ion and the arranging shortrange order of transition metal ions and long-range is unordered more suitable.Like this, due to insulation phase Li 2mnO 3existence, Li 2mnO 3the electronic conductivity of feature structure and ionic conductivity are all very low, on the other hand, and xLi 2mnO 3. (1-x) LiMn 0.5ni 0.5o 2laminate Li 2mnO 3interlamellar spacing and LiMn 0.5ni 0.5o 2it is larger that interlamellar spacing differs, and both does not mate the embedding that causes lithium ion and deviate from more difficultly, causes the overall lithium ion conductivity of composite material low, and the lithium ion diffusion coefficient is 10 -12-10 -13s/cm 2between.So xLi 2mnO 3. (1-x) LiMn 0.5ni 0.5o 2cyclical stability not good, repeatedly the circulation after capacity attenuation very fast, when charging and discharging currents increases, capacity attenuation is very fast.Because the lithium manganate having spinel structure platform voltage is high, ionic diffusion coefficient is large, also someone proposes the rich lithium composite material of layer-spinel-type x (Li 2mnO3.LiMn 0.5ni 0.5o 2). (1-x) LiMn 1.5ni 0.5o 4or be written as Li x+0.5mn 0.75ni 0.25o 0.5x+2all there is the high power capacity of layer structure and the high magnification characteristic [S.-H.Park of spinel structure, S.-H.Kang, C.S.Johnson, K.Amine, M.M.Thackeray, Electrochemistry Communications9 (2007) 262-268.], yet in fact because this composites has local features on said structure, the inconsistent Li that caused of layer structure and spinel structure lithium interlamellar spacing 2mnO 3the low ionic conductivity of phase remains the bottleneck of bulk material properties.
Ion doping is to improve one of the multiplying power property of lithium ion anode and the more effective means of Capacity fading, and the F-ion doping makes the oxonium ion of part be replaced by F-, has reduced at high voltage lower surface oxygen activity, has suppressed separating out of oxygen.Contribute to improve the Capacitance reserve ability [Kang S H, Thackeray M M., ElectrochemicalSociety, 2008,155:A269-A275.] of material circulation.And the Co doping often can improve the ionic conductivity of material, thereby increase discharge capacity, lifting multiplying power property.But the interaction of doping ion and matrix is very complicated, the characteristics such as the size of doping ion, electronic structure, electronegativity all have considerable influence to the chemical property of material, and have interaction between different doping ions, be that promotion or the degree that suppresses chemical property and promotion and inhibition all can be along with the ionic species mixed and concentration have very large difference.In fact, doping not only affects in lattice the quantity of adulterate ion and main body ion, therefore because material monolithic need to keep electric neutrality, thereby also can have influence on the whole crystal structure of valence state of other transition metal ionss, this performance on positive electrode also has very large impact.Doped lithium ion also is familiar with not yet fully to the mechanism of action of material electrochemical performance.Therefore further study the contamination of doping ion to developing high performance layer-spinelle composite lithium-rich anode material Li x+0.5mn 0.75ni 0.25o 0.5x+2very important meaning is arranged.
Summary of the invention
Technical problem to be solved by this invention is a kind of Ti provided for existing background technology 4+, Al 3+, Fe 3+, F -codoped layers-spinelle composite lithium-rich anode material Li x+0.5mn 0.75ni 0.25o 0.5x+2(0≤x≤0.5).Adulterate by F-, reduce the quantity that under high potential, oxonium ion is deviate from lattice, reduce oxygen defect concentration in the lattice surface, improve the surface stability under the material high potential; Fe 3+/ Fe 2+lower and the good reversibility of oxidation-reduction potential, receive in charging and deviate from and embedding is returned in rich lithium material again lithium ion reduces irreversible capacity loss; The Al-O structure has higher ionic conductivity; Ti 4+radius ratio Mn 4+and Ni 2+radius is bigger, is conducive to improve the multiplying power property of material and the charge/discharge capacity under equal conditions; The synergy of these factors makes layer-layer composite lithium-rich anode material Li x+0.5mn 0.75ni 0.25o 0.5x+2(0≤x≤0.5) has better circulation volume hold facility and multiplying power property.
The present invention reaches by the following technical solutions, and this technical scheme provides the layer of a kind of high circulation volume hold facility and multiplying power property-layer lithium-rich anode material, and its stoichiometric equation is Li x+0.5 + 0.5m+0.5p-0.5n-y(Mn 0.75Ni 0.25) 1-m-n-pAl mti nfepO 0.5x+2-yf ywherein: 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, will be according to the stoichiometric proportion of above-mentioned molecular formula by soluble lithium compounds, soluble manganese salt, soluble nickel salt, butyl titanate, Al (NO 3) 39H 2o, soluble ferric iron salt and lithium fluoride join in deionized water, and adding amount of substance is that all metal ions total amount 2.5-4.0 tartaric acid doubly stirs to dissolving fully; The temperature of system is risen to 70-85 ℃ and continue to stir until the water evaporation of 70-85%, at this moment become gradually thickness form gelatin of solution.Gelatin material is ground in the baking oven of 130-200 ℃ in mortar to 10-30 minute after dry 20-48 hour.The powder that obtains is warmed up to 500-600 ℃ and at this temperature lower calcination 3-5 hour with the speed of 2-10 ℃/minute in tube furnace, cooling rear taking-up powder, continue to grind 10-30 minute in mortar, with the pressure of 100-300MPa, powder is pressed into to sheet, then be warmed up to 850-950 ℃ of calcining 5-15 hour with the speed of 2-10 ℃/minute in tube furnace, obtain this lithium-rich anode material after cooling with stove.Wherein: the solubility lithium salts is LiNO 3, CH 3a kind of in COOLi; Soluble manganese salt is Mn (CH 3cOO) 24H 2o, MnSO 4h 2a kind of in O; Soluble nickel salt is Ni (CH 3cOO) 24H 2o, NiSO 46H 2a kind of in O; Soluble ferric iron salt is Fe (NO 3) 39H 2o, FeCl 36H 2a kind of in O.Charging capacity, discharge capacity and the efficiency for charge-discharge figure of front 20 circulations of this richness lithium material of Fig. 1.
Compared with prior art, the invention has the advantages that: pass through F -doping, reduce the quantity that under high potential, oxonium ion is deviate from lattice, reduces oxygen defect concentration in the lattice surface, improves the surface stability under the material high potential; Fe 3+/ Fe 2+lower and the good reversibility of oxidation-reduction potential, receive in charging and deviate from and embedding is returned in rich lithium material again lithium ion reduces irreversible capacity loss; The Al-O structure has higher ionic conductivity; Ti 4+radius ratio Mn 4+and Ni 2+radius is bigger, is conducive to improve the multiplying power property of material and the charge/discharge capacity under equal conditions; The synergy of these factors makes layer-layer composite lithium-rich anode material Li x+0.5mn 0.75ni 0.25o 0.5x+2(0≤x≤0.5) has better circulation volume hold facility and multiplying power property.
The accompanying drawing explanation
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of front 20 circulations of this richness lithium material of Fig. 1.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: by LiNO 3: Mn (CH 3cOO) 24H 2o: Ni (CH 3cOO) 24H 2o: butyl titanate: Fe (NO 3) 39H 2o: Al (NO 3) 39H 2o: LiF is 0.585: 0.7275: 0.2425: 0.01: 0.01: 0.01: the ratio of 0.01 (mol ratio) is evenly mixed, join in deionized water, add the tartaric acid that amount of substance is 2.5 times of all metal ions total amounts to stir to dissolving fully; The temperature of system is risen to 70 ℃ and continue to stir until 71% water evaporation, at this moment become gradually thickness form gelatin of solution.Gelatin material is ground 10 minutes after dry 22 hours in the baking oven of 130 ℃ in mortar.The powder that obtains is warmed up to 500 ℃ and this temperature lower calcination 3 hours with the speed of 2 ℃/minute in tube furnace, cooling rear taking-up powder, in mortar, continue to grind 10 minutes, with the pressure of 100MPa, powder is pressed into to sheet, then be warmed up to 850 ℃ of calcinings 5 hours with the speed of 2 ℃/minute in tube furnace, obtain this lithium-rich anode material after cooling with stove.
Embodiment 2: by LiNO 3: Mn (CH 3cOO) 24H 2o: Ni (CH 3cOO) 224H 2o: butyl titanate: Fe (NO 3) 39H 2o: Al (NO 3) 39H 2o: LiF is 0.905: 0.6375: 0.2125: 0.05: 0.05: 0.05: the ratio of 0.06 (mol ratio) is evenly mixed, join in deionized water, add the tartaric acid that amount of substance is 4.0 times of all metal ions total amounts to stir to dissolving fully; The temperature of system is risen to 85 ℃ and continue to stir until 85% water evaporation, at this moment become gradually thickness form gelatin of solution.Gelatin material is ground 30 minutes after dry 48 hours in the baking oven of 200 ℃ in mortar.The powder that obtains is warmed up to 600 ℃ and this temperature lower calcination 5 hours with the speed of 10 ℃/minute in tube furnace, cooling rear taking-up powder, in mortar, continue to grind 30 minutes, with the pressure of 300MPa, powder is pressed into to sheet, then be warmed up to 950 ℃ of calcinings 15 hours with the speed of 9 ℃/minute in tube furnace, obtain this lithium-rich anode material after cooling with stove.
Embodiment 3: by LiNO 3: Mn (CH 3cOO) 24H 2o: Ni (CH 3cOO) 24H 2o: butyl titanate: Fe (NO 3) 39H 2o: Al (NO 3) 39H 2o: LiF is 0.65: 0.705: 0.235: 0.02: 0.02: 0.02: the ratio of 0.03 (mol ratio) is evenly mixed, join in deionized water, add the tartaric acid that amount of substance is 3.2 times of all metal ions total amounts to stir to dissolving fully; The temperature of system is risen to 78 ℃ and continue to stir until 78% water evaporation, at this moment become gradually thickness form gelatin of solution.Gelatin material is ground 20 minutes after dry 35 hours in the baking oven of 170 ℃ in mortar.The powder that obtains is warmed up to 550 ℃ and this temperature lower calcination 4 hours with the speed of 7 ℃/minute in tube furnace, cooling rear taking-up powder, in mortar, continue to grind 20 minutes, with the pressure of 200MPa, powder is pressed into to sheet, then be warmed up to 900 ℃ of calcinings 10 hours with the speed of 6 ℃/minute in tube furnace, obtain this lithium-rich anode material after cooling with stove.
Embodiment 4: by CH 3cOOLi: MnSO 4h 2o: Ni (CH 3cOO) 24H 2o: butyl titanate: Fe (NO 3) 39H 2o: Al (NO 3) 39H 2o: LiF is 0.9: 0.705: 0.235: 0.03: 0.02: 0.01: the ratio of 0.05 (mol ratio) is evenly mixed, join in deionized water, add the tartaric acid that amount of substance is 3.0 times of all metal ions total amounts to stir to dissolving fully; The temperature of system is risen to 80 ℃ and continue to stir until 82% water evaporation, at this moment become gradually thickness form gelatin of solution.Gelatin material is ground 10 minutes after dry 45 hours in the baking oven of 190 ℃ in mortar.The powder that obtains is warmed up to 550 ℃ and this temperature lower calcination 4 hours with the speed of 5 ℃/minute in tube furnace, cooling rear taking-up powder, in mortar, continue to grind 10 minutes, with the pressure of 200MPa, powder is pressed into to sheet, then be warmed up to 900 ℃ of calcinings 10 hours with the speed of 6 ℃/minute in tube furnace, obtain this lithium-rich anode material after cooling with stove.
Embodiment 5: by LiNO 3: Mn (CH 3cOO) 24H 2o: NiSO 46H 2o: butyl titanate: FeCl 36H 2o: Al (NO 3) 39H 2o: LiF is 0.785: 0.6675: 0.2225: 0.03: 0.03: 0.05: the ratio of 0.02 (mol ratio) is evenly mixed, join in deionized water, add the tartaric acid that amount of substance is 2.7 times of all metal ions total amounts to stir to dissolving fully; The temperature of system is risen to 73 ℃ and continue to stir until 75% water evaporation, at this moment become gradually thickness form gelatin of solution.Gelatin material is ground 30 minutes after dry 25 hours in the baking oven of 150 ℃ in mortar.The powder that obtains is warmed up to 550 ℃ and this temperature lower calcination 4 hours with the speed of 10 ℃/minute in tube furnace, cooling rear taking-up powder, in mortar, continue to grind 30 minutes, with the pressure of 300MPa, powder is pressed into to sheet, then be warmed up to 950 ℃ of calcinings 15 hours with the speed of 6 ℃/minute in tube furnace, obtain this lithium-rich anode material after cooling with stove.

Claims (3)

1. a Ti 4+, Al 3+, Fe 3+, F -codoped layers-spinelle composite lithium-rich anode material Li x+0.5mn 0.75ni 0.25o 0.5x+2(0≤x≤0.5), is characterized in that stoichiometric equation is Li x+0.5+05m+05p-0.5n-y(Mn 0.75ni 025) 1-m-n-pal mti nfe po 0.5x+2-yf ywherein: 0≤x≤0.5; 0.01≤m≤0.05; 0.01≤2≤0.05; 0.01≤p≤0.05; 0.01≤y≤0.06.
2. layer-spinelle composite lithium-rich anode material according to claim 1, is characterized in that stoichiometric proportion according to above-mentioned molecular formula is by soluble lithium compounds, soluble manganese salt, soluble nickel salt, butyl titanate, Al (NO 3) 39H 2o, soluble ferric iron salt and lithium fluoride join in deionized water, and adding amount of substance is that all metal ions total amount 2.5-4.0 tartaric acid doubly stirs to dissolving fully, the temperature of system is risen to 70-85 ℃ to be continued to stir until the water evaporation of 70-85%, at this moment become gradually thickness form gelatin of solution, gelatin material is ground in the baking oven of 130-200 ℃ in mortar to 10-30 minute after dry 20-48 hour, the powder that obtains is warmed up to 500-600 ℃ and at this temperature lower calcination 3-5 hour with the speed of 2-10 ℃/minute in tube furnace, cooling rear taking-up powder, continue to grind 10-30 minute in mortar, with the pressure of 100-300MPa, powder is pressed into to sheet, then in tube furnace, the speed with 2-10 ℃/minute is warmed up to 850-950 ℃ of calcining 5-15 hour, obtain this lithium-rich anode material after cooling with stove.
3. process according to claim 2, is characterized in that the solubility lithium salts is a kind of in LiNO3, CH3COOLi; Soluble manganese salt is Mn (CH3COO) 24H 2o, MnSO 4h 2a kind of in O; Soluble nickel salt is Ni (CH 3cOO) 24H 2o, NiSO 46H 2a kind of in O; Soluble ferric iron salt is Fe (NO 3) 39H 2o, FeCl 36H 2a kind of in O.
CN201310022272.7A 2013-01-05 2013-01-05 Ti4+,Al3+,Fe3+,F-Doped layer-spinelle composite lithium-rich anode material and preparation method Expired - Fee Related CN103107327B (en)

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CN106663783B (en) * 2014-07-22 2019-11-01 丰田自动车株式会社 The positive electrode active materials of lithium secondary battery, the anode of lithium secondary battery and lithium secondary battery
JP2017033817A (en) * 2015-08-04 2017-02-09 日立化成株式会社 Positive electrode active material for lithium ion secondary battery, positive electrode material for lithium ion secondary battery, and lithium ion secondary battery

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