CN103078104A - A kind of La3+, al3+, fe3+, F- codoped composite lithium-rich positive electrode material and its prepn - Google Patents

A kind of La3+, al3+, fe3+, F- codoped composite lithium-rich positive electrode material and its prepn Download PDF

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CN103078104A
CN103078104A CN2013100223537A CN201310022353A CN103078104A CN 103078104 A CN103078104 A CN 103078104A CN 2013100223537 A CN2013100223537 A CN 2013100223537A CN 201310022353 A CN201310022353 A CN 201310022353A CN 103078104 A CN103078104 A CN 103078104A
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lithium
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CN103078104B (en
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徐玲霞
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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Abstract

The invention discloses a La<3+>, Al<3+>, Fe<3+> and F<-> co-doped composite lithium-rich anode material xLi2MnO3.(1-x)LiMn0.5Ni0.5O2 (x is not less than 0 and not more than 0.5). The anode material is characterized in that a chemical stoichiometric equation is xLi2MnO3.(1-x)Li1-y(Mn0.5Ni0.5)1-m-n-pAlmLanFepO2-yFy, wherein x is not less than 0 and not more than 0.5, m is not less than 0.01 and not more than 0.05, n is not less than 0.01 and not more than 0.05, p is not less than 0.01 and not more than 0.05 and y is not less than 0.01 and not more than 0.06. A preparation method for the anode material comprises the steps as follows: dissolving a soluble lithium compound, soluble magnesium salt, soluble nickel salt, La(NO3)3.6H2O, Al(NO3)3.9H2O, soluble iron salt and lithium fluoride in de-ionized water according to the chemical stoichiometric equation of the molecular formula; adding tartaric acid which is 1.2-2.0 times of the total amount of all metal ions; fully and uniformly stirring until tartaric acid is fully dissolved; and concentrating, gelling, drying, grinding, decomposing, tabletting and calcining a solution to obtain the anode material. The prepared anode material is excellent in cyclic capacity retention capability and rate performance.

Description

A kind of La 3+, Al 3+, Fe 3+, F -Codope 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 make the 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 the occupation rate of market that exceedes 30,000,000,000 dollars of/year shares and far surpass other batteries in global portable power source market, the chemical power source [Wu Yuping that has 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 paced up and down 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 the positive and negative pole material.
The present commercial lithium ion battery the most widely positive electrode of practicality 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, and is 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 that filters out reaches tens of kinds, but potential commercial applications prospect is really arranged or the positive electrode that appeared on the market very few really.Such 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 capacity attenuation is very fast under the high temperature, 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 present business-like LiFePO4 LiFePO progressively 4Cost is low, Heat stability is good, environmental friendliness, but its theoretical capacity approximately only has 170mAh/g, and actual capacity is about 140mAh/g.
In recent years, the researcher gradually with high lithium than on the 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 2As 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, so that the positive electrode of this structure has the discharge capacity above 200mAh/g.During less than 4.6V, Mn keeps+4 valencys constant to this material, Li in charging voltage 2MnO 3Structure keeps inertia, and the stability of positive electrode structure is provided, and prevents that material structure caves in charge and discharge process, Ni from+the divalent attitude becomes+4 valencys, is the active component of generation capacity.When charging voltage surpasses 4.6V, one platform will appear in the 4.6V position, and this is Li 2O is from Li 2MnO 3Deviate from fully in the lattice and become MnO 2, at this moment cell voltage will reach more than the 4.8V; When battery begins to discharge, the Li that had before deviate from 2O does not return in the lattice, along with the Ni that carries out of discharge 4+Be reduced to gradually Ni 2+, the Mn in the material subsequently 4+Also be reduced the participation electrochemical process, so Li 2MnO 3Activation when surpassing 4.6V is that this material has the reason [Johnson, C.S., N.Li, et al., Electrochemistry communications, 2007,9 (4): 787-795.] above 200mAh/g.
Yet, xLi in fact 2MnO 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 ofMaterials 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 2O 2The rich lithium layered cathode material of layered-layered structure is not pure solid solution, and excessive lithium ion is distributed in the 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 0.5Ni0 .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, because 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 relatively difficulty, 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 increased, capacity attenuation was very fast.
Ion doping is to improve one of the multiplying power property of lithium ion anode and the more effective means of Capacity fading, F -Ion doping so that the part oxonium ion by F -Replace, reduced at high voltage lower surface oxygen activity, suppressed separating out of oxygen.Help 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 increases 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 the 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 that mixes and concentration have very large difference.In fact, doping not only affects the quantity of doping ion and main body ion in the lattice, 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 by layer composite lithium-rich anode material xLi 2MnO 3. (1-X) LiMn 0.5Ni 0.5O 2Very important meaning is arranged.
Summary of the invention
Technical problem to be solved by this invention is a kind of La that provides for existing background technology 3+, Al 3+, Fe 3+, F -Codoped layers-layer composite lithium-rich anode material xLi 2MnO 3. (1-x) LiMn 0.5Ni 0.5O 2(0≤x≤0.5).Mix by F-, reduce the quantity that oxonium ion is deviate from lattice under the high potential, 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 deviate from the charging and again the lithium ion that returns in the rich lithium material of embedding reduce irreversible capacity loss; The Al-O structure has higher ionic conductivity; La 3+Radius is larger, replaces (Mn 0.5Ni 0.5) structure helps to enlarge lithium ion and embed and to take off the embedding passage; The synergy of these factors is so that layer-layer composite lithium-rich anode material xLi 2MnO 3. (1-x) LiMn 0.5Ni 0.5O 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 xLi 2MnO 3. (1-x) Li 1-y(Mn 0.5Ni 0.5) 1-m-n-pAl mLa nFe pO 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 with soluble lithium compounds, soluble manganese salt, soluble nickel salt, La (NO 3) 36H 2O, Al (NO 3) 39H 2O, soluble ferric iron salt and lithium fluoride join in the deionized water, and adding amount of substance is that all metal ions total amount 1.2-2.0 tartaric acid doubly stirs to fully dissolving; The temperature of system is risen to 70-85 ℃ continue to stir until the water evaporation of 70-85%, at this moment become gradually thickness and form gelatin of solution.Gelatin material was ground 10-30 minute in mortar after dry 20-48 hour in 130-200 ℃ baking oven.The powder that obtains is warmed up to 500-600 ℃ and this temperature lower calcination 3-5 hour with 2-10 ℃/minute speed in tube furnace, take out powder after the cooling, in mortar, continue to grind 10-30 minute, pressure with 100-300MPa is pressed into sheet with powder, then the speed with 2-10 ℃/minute is warmed up to 850-950 ℃ of calcining 5-15 hour in tube furnace, with obtaining this lithium-rich anode material after the stove cooling.Wherein: the solubility lithium salts is LiNO 3, CH 3A kind of among the COOLi; Soluble manganese salt is Mn (CH 3COO) 24H 2O, MnSO 4H 2A kind of among the O; Soluble nickel salt is Ni (CH 3COO) 24H 2O, NiSO 46H 2A kind of among the O; Soluble ferric iron salt is Fe (NO 3) 39H 2O, FeCl 36H 2A kind of among the O.
Compared with prior art, the invention has the advantages that: pass through F -Mix, reduce the quantity that oxonium ion is deviate from lattice under the high potential, 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 deviate from the charging and again the lithium ion that returns in the rich lithium material of embedding reduce irreversible capacity loss; The Al-O structure has higher ionic conductivity; La 3+Radius is larger, replaces (Mn 0.5Ni 0.5) structure helps to enlarge lithium ion and embed and to take off the embedding passage; The synergy of these factors is so that layer-layer composite lithium-rich anode material xLi 2MnO 3. (1-x) LiMn 0.5Ni 0.5O 2(0≤x≤0.5) has better circulation volume hold facility and multiplying power property.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1: with LiNO 3: Mn (CH 3COO) 24H 2O: Ni (CH 3COO) 24H 2O: La (NO 3) 36H 2O: Fe (NO 3) 39H 2O: Al (NO 3) 39H 2O: LiF is 1.082: 0.5365: 0.4365: 0.009: 0.009: 0.009: the ratio of 0.009 (mol ratio) is evenly mixed, join in the deionized water, the adding amount of substance is that the tartaric acid of 1.2 times of all metal ions total amounts stirs to fully dissolving; The temperature of system is risen to 70 ℃ continue to stir until 71% water evaporation, at this moment become gradually thickness and form gelatin of solution.Gelatin material was ground 10 minutes in mortar after dry 22 hours in 130 ℃ baking oven.The powder that obtains is warmed up to 500 ℃ and this temperature lower calcination 3 hours with 2 ℃/minute speed in tube furnace,
Take out powder after the cooling, continue to grind 10 minutes in mortar, with the pressure of 100MPa powder is pressed into sheet, then the speed with 2 ℃/minute is warmed up to 850 ℃ of calcinings 5 hours in tube furnace, obtains this lithium-rich anode material after cooling off with stove.
Embodiment 2: with LiNO 3: Mn (CH 3COO) 24H 2O: Ni (CH 3COO) 24H 2O: La (NO 3) 36H 2O: Fe (NO 3) 39H 2O: Al (NO 3) 39H 2O: LiF is 1.44: 0.7125: 0.2125: 0.025: 0.025: 0.025: the ratio of 0.03 (mol ratio) is evenly mixed, join in the deionized water, the adding amount of substance is that the tartaric acid of 1.8 times of all metal ions total amounts stirs to fully dissolving; The temperature of system is risen to 85 ℃ continue to stir until 85% water evaporation, at this moment become gradually thickness and form gelatin of solution.Gelatin material was ground 30 minutes in mortar after dry 48 hours in 200 ℃ baking oven.The powder that obtains is warmed up to 600 ℃ and this temperature lower calcination 5 hours with 10 ℃/minute speed in tube furnace, take out powder after the cooling, in mortar, continue to grind 30 minutes, pressure with 300MPa is pressed into sheet with powder, then the speed with 9 ℃/minute is warmed up to 950 ℃ of calcinings 15 hours in tube furnace, with obtaining this lithium-rich anode material after the stove cooling.
Embodiment 3: with LiNO 3: Mn (CH 3COO) 24H 2O: Ni (CH 3COO) 24H 2O: La (NO 3) 36H 2O: Fe (NO 3) 39H 2O: Al (NO 3) 39H 2O: LiF is 1.152: 0.576: 0.376: 0.016: 0.016: 0.016: the ratio of 0.024 (mol ratio) is evenly mixed, join in the deionized water, the adding amount of substance is that the tartaric acid of 1.6 times of all metal ions total amounts stirs to fully dissolving; The temperature of system is risen to 78 ℃ continue to stir until 78% water evaporation, at this moment become gradually thickness and form gelatin of solution.Gelatin material was ground 20 minutes in mortar after dry 35 hours in 170 ℃ baking oven.The powder that obtains is warmed up to 550 ℃ and this temperature lower calcination 4 hours with 7 ℃/minute speed in tube furnace, take out powder after the cooling, in mortar, continue to grind 20 minutes, pressure with 200MPa is pressed into sheet with powder, then the speed with 6 ℃/minute is warmed up to 900 ℃ of calcinings 10 hours in tube furnace, with obtaining this lithium-rich anode material after the stove cooling.
Embodiment 4: with CH3COOLi: MnSO 4H 2O: Ni (CH 3COO) 24H 2O: La (NO 3) 36H 2O: Fe (NO 3) 39H 2O: Al (NO 3) 39H 2O: LiF is 1.45: 0.735: 0.235: 0.015: 0.01: 0.005: the ratio of 0.025 (mol ratio) is evenly mixed, join in the deionized water, the adding amount of substance is that the tartaric acid of 1.8 times of all metal ions total amounts stirs to fully dissolving; The temperature of system is risen to 80 ℃ continue to stir until 82% water evaporation, at this moment become gradually thickness and form gelatin of solution.Gelatin material was ground 10 minutes in mortar after dry 45 hours in 190 ℃ baking oven.The powder that obtains is warmed up to 550 ℃ and this temperature lower calcination 4 hours with 5 ℃/minute speed in tube furnace, take out powder after the cooling, in mortar, continue to grind 10 minutes, pressure with 200MPa is pressed into sheet with powder, then the speed with 6 ℃/minute is warmed up to 900 ℃ of calcinings 10 hours in tube furnace, with obtaining this lithium-rich anode material after the stove cooling.
Embodiment 5: with LiNO 3: Mn (CH 3COO) 24H 2O: NiSO 46H 2O: La (NO 3) 36H 2O: FeCl 36H 2O: Al (NO 3) 39H 2O: LiF is 1.272: 0.6115: 0.3115: 0.021: 0.021: 0.035: the ratio of 0.014 (mol ratio) is evenly mixed, join in the deionized water, the adding amount of substance is that the tartaric acid of 1.3 times of all metal ions total amounts stirs to fully dissolving; The temperature of system is risen to 73 ℃ continue to stir until 75% water evaporation, at this moment become gradually thickness and form gelatin of solution.Gelatin material was ground 30 minutes in mortar after dry 25 hours in 150 ℃ baking oven.The powder that obtains is warmed up to 550 ℃ and this temperature lower calcination 4 hours with 10 ℃/minute speed in tube furnace, take out powder after the cooling, in mortar, continue to grind 30 minutes, pressure with 300MPa is pressed into sheet with powder, then the speed with 6 ℃/minute is warmed up to 950 ℃ of calcinings 15 hours in tube furnace, with obtaining this lithium-rich anode material after the stove cooling.

Claims (3)

1. La 3+, Al 3+, Fe 3+, F -Codoped layers-layer composite lithium-rich anode material xLi 2MnO 3. (1-x) LiMn 0.5Ni 0.5O 2(0≤x≤0.5) is characterized in that stoichiometric equation is xLi 2MnO 3. (1-x) Li 1-y(Mn 0.XNi 0.5) 1-m-n-pAl mLa nFe pO 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.
2. layer according to claim 1-layer composite lithium-rich anode material is characterized in that stoichiometric proportion according to above-mentioned molecular formula is with soluble lithium compounds, soluble manganese salt, soluble nickel salt, La (NO 3) 36H 2O, Al (NO 3) 39H 2O, soluble ferric iron salt and lithium fluoride join in the deionized water, and adding amount of substance is that all metal ions total amount 1.2-2.0 tartaric acid doubly stirs to fully dissolving; The temperature of system is risen to 70-85 ℃ continue to stir until the water evaporation of 70-85%, at this moment become gradually thickness and form gelatin of solution; Gelatin material was ground 10-30 minute in mortar after dry 20-48 hour in 130-200 ℃ baking oven; The powder that obtains is warmed up to 500-600 ℃ and this temperature lower calcination 3-5 hour with 2-10 ℃/minute speed in tube furnace, take out powder after the cooling, in mortar, continue to grind 10-30 minute, pressure with 100-300MPa is pressed into sheet with powder, then the speed with 2-10 ℃/minute is warmed up to 850-950 ℃ of calcining 5-15 hour in tube furnace, with obtaining this lithium-rich anode material after the stove cooling.
3. process according to claim 2 is characterized in that the solubility lithium salts is LiNO 3, CH 3A kind of among the COOLi; Soluble manganese salt is Mn (CH 3COO) 24H 2O, MnSO 4H 2A kind of among the O; Soluble nickel salt is Ni (CH 3COO) 24H 2O, NiSO 46H 2A kind of among the O; Soluble ferric iron salt is Fe (NO 3) 39H 2O, FeCl 36H 2A kind of among the O.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105591098A (en) * 2016-03-18 2016-05-18 武汉理工大学 Li-rich positive electrode material with La doping and lithium amount change at same time and preparing method thereof
CN107994226A (en) * 2017-12-14 2018-05-04 桑顿新能源科技有限公司 A kind of lithium-rich anode material of Mn adulterated lithium manganate and preparation method thereof
CN109461920A (en) * 2018-11-08 2019-03-12 成都理工大学 The nickelic layered oxide material and its preparation method and application of lanthanum aluminium doping

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030134200A1 (en) * 2000-12-28 2003-07-17 Takehiko Tanaka Positive electrode active material and nonaqueous electrolyte secondary cell
CN101006012A (en) * 2004-09-24 2007-07-25 株式会社Lg化学 Powdered lithium transition metal oxide having doped interface layer and outer layer and method for preparation of the same
CN101017914A (en) * 2006-02-08 2007-08-15 三洋电机株式会社 Non-aqueous electrolyte secondary battery
CN101764204A (en) * 2009-10-14 2010-06-30 孙琦 Preparation method of rear earth lanthanum doping type lithium manganate
CN102195042A (en) * 2010-03-09 2011-09-21 中国科学院过程工程研究所 High performance lithium ion battery anode material lithium manganate and preparation method thereof
CN102800840A (en) * 2011-05-23 2012-11-28 中国科学院宁波材料技术与工程研究所 Cathode material of lithium ion battery, and preparation method thereof and lithium ion battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030134200A1 (en) * 2000-12-28 2003-07-17 Takehiko Tanaka Positive electrode active material and nonaqueous electrolyte secondary cell
CN101006012A (en) * 2004-09-24 2007-07-25 株式会社Lg化学 Powdered lithium transition metal oxide having doped interface layer and outer layer and method for preparation of the same
CN101017914A (en) * 2006-02-08 2007-08-15 三洋电机株式会社 Non-aqueous electrolyte secondary battery
CN101764204A (en) * 2009-10-14 2010-06-30 孙琦 Preparation method of rear earth lanthanum doping type lithium manganate
CN102195042A (en) * 2010-03-09 2011-09-21 中国科学院过程工程研究所 High performance lithium ion battery anode material lithium manganate and preparation method thereof
CN102800840A (en) * 2011-05-23 2012-11-28 中国科学院宁波材料技术与工程研究所 Cathode material of lithium ion battery, and preparation method thereof and lithium ion battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杜柯等: "高容量正极材料Li[Li0.2Ni0.2Mn0.6]O2的合成及电化学性能", 《中国有色金属学报》, vol. 22, no. 4, 15 April 2012 (2012-04-15), pages 1201 - 1208 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105591098A (en) * 2016-03-18 2016-05-18 武汉理工大学 Li-rich positive electrode material with La doping and lithium amount change at same time and preparing method thereof
CN107994226A (en) * 2017-12-14 2018-05-04 桑顿新能源科技有限公司 A kind of lithium-rich anode material of Mn adulterated lithium manganate and preparation method thereof
CN109461920A (en) * 2018-11-08 2019-03-12 成都理工大学 The nickelic layered oxide material and its preparation method and application of lanthanum aluminium doping
CN109461920B (en) * 2018-11-08 2022-01-11 成都理工大学 Lanthanum-aluminum-doped high-nickel layered oxide material and preparation method and application thereof

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