CN105591098A - Li-rich positive electrode material with La doping and lithium amount change at same time and preparing method thereof - Google Patents
Li-rich positive electrode material with La doping and lithium amount change at same time and preparing method thereof Download PDFInfo
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- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a Li-rich positive electrode material with La doping and lithium amount change at the same time. The composition expression formula is La doped Li1.2(1-x)yNi0.3Mn0.6O2, wherein x represents the La doping molar fraction, 0.01<=x<=0.04, y represents the lithium amount adjusting coefficient, and 85%<=y<=95%. The material is uniform in morphology, high in crystallinity and even in distribution, has high specific discharge capacity when used as the positive electrode material of a lithium ion battery and can obviously reduce the first-time irreversible capacity loss. The involved preparing method is simple, short in preparation period and wide in application prospect.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries field, be specifically related to a kind of La doping lithium-rich anode material of lithium quantitative change simultaneouslyMaterial and preparation method thereof.
Background technology
The exploitation of the development of electronic product, particularly new-energy automobile and application, requirement has the lithium ion battery of high-energy-density,And at present traditional positive electrode is difficult to meet electric automobile to battery high energy metric density and demand, therefore development of new cheaplyThe power lithium-ion battery positive electrode that specific energy is higher, price is cheaper, the life-span is longer has become ev industry developmentKey factor. Lithium ion battery negative material is mainly taking graphite-like material with carbon element as main, and reversible specific capacity can reach 300mAh/gEven more, the specific capacity of positive electrode only has about half of negative material by contrast, and production cost but far beyondNegative material. Therefore, the research emphasis in anode material for lithium-ion batteries field is exactly effectively to improve the performance of positive electrode at presentAnd reduce production costs.
The lithium-rich manganese-based anode material xLi of layer structure2MnO3·(1-x)LiMO2(M＝Ni，Mn，Ni1/2Mn1/2), with itHigh actual active volume, good heat endurance, wider charging/discharging voltage scope and cheap, the spies such as environmental friendlinessVery potential energy-storage battery, the power battery anode material that becomes following main flow of point, compared with current business-like positive electrode,There is certain superiority. xLi2MnO3·(1-x)LiMO2Cause in recent years scholar's extensive concern, it is Li2MnO3WithLiNi1/2Mn1/2O2The solid solution forming, has higher electro-chemical activity, and its reversible specific discharge capacity is up to 250mAh/g,There is significant capacity advantage. It has not only retained LiNi1/2Mn1/2O2The characteristic of high power capacity, but also retained Li2MnO3Good structural stability.
Also there are several larger problems in this type of material at present, restricting its business-like development. This is irreversible capacity first whereinLoss is more greatly a larger problem.
About the larger problem of irreversible capacity loss first, relevant scientific paper both domestic and external is improved one's methods and is reported it.The method adopting mainly contains following several: one is material to be carried out to surface be coated, and clad can play and stop partial oxygen roomFrom structure cell, deviate from, reduce the effect of irreversible capacity loss first thereby play. As Zheng[ZhengJM, LiJ, ZhangZR，etal.TheeffectsofTiO2coatingontheelectrochemicalperformanceofLi[Li0.2Mn0.54Ni0.13Co0.13]O2cathodematerialforlithium-ionbattery[J].SolidStateIonics，2008，179 (27 – 32): 1794-1799.] etc. people with TiO2The rich lithium material of this class is carried out after surface is coated to irreversible capacity loss firstDrop to 54mAh/g by 75.5mAh/g. As Wu[WuY, ManthiramA.Effectofsurfacemodificationsonthelayeredsolidsolutioncathodes(1-z)Li[Li1/3Mn2/3]O2-(z)Li[Mn0.5-yNi0.5-yCo2y]O2[J].SolidStateIonics, 2009,180 (1): 50-56.] etc. people adopts four kinds of different clad materials to probe into clad material to material electrochemical performanceImpact, wherein Al2O3It is best that clad reduces the effect of irreversible capacity loss first. Another kind be by rich lithium material with can embeddingThe lithium ion carrier of lithium is compound, and after both are compound, lithium ion carrier that can embedding lithium has just become the host of lithium ion, irreversible de-The lithium ion going out just can be embedded in host's carrier, thereby has reduced irreversible capacity loss. As Gao[GaoJ, KimJ,ManthiramA.HighcapacityLi[Li0.2Mn0.54Ni0.13Co0.13]O2-V2O5compositecathodeswithlowirreversiblecapacitylossforlithiumionbatteries[J].ElectrochemistryCommunications，2009，11 (1): 84 – 86.] etc. people by rich lithium material and V2O5Not only irreversible capacity first of the composite being mixed to get by a certain percentageLoss reduces, and discharge capacity is also improved. And for example Wu[WuF, WangZ, SuY, etal.Li[Li0.2Mn0.54Ni0.13Co0.13]O2–MoO3compositecathodeswithlowirreversiblecapacitylossforLithiumionbatteries[J] .JournalofPowerSources, 2014,247 (3): 20-25.] etc. people by rich lithium material and MoO3Compoundly irreversible capacity loss first can be reduced equally.
Although have pertinent literature report to reduce the irreversible capacity loss first of rich lithium material, what exist in preparation process asksTopic is: surface is coated needs target positive electrode and coated or composite to carry out secondary high speed ball milling and two degree heat with complex methodProcess, not only step is many, and experimental period is long, preparation process complexity, and increased production cost, be unfavorable for large-scale production.
Summary of the invention
For not enough in above-mentioned preparation process with to the wanting of high-performance lithium-rich anode material, the present invention proposes La doping lithium simultaneouslyThe lithium-rich anode material of quantitative change, this material pattern homogeneous, degree of crystallinity be high, be evenly distributed, and has good chemical property,First irreversible capacity loss be improved significantly; And the preparation method who relates to is simple, and manufacturing cycle is short, be applicable to applying.
For achieving the above object, the technical solution used in the present invention is:
A La doping lithium-rich anode material for lithium quantitative change simultaneously, its composition expression formula is: La Li doped1.2(1-x) yNi0.3Mn0.6O2, wherein x is the molar fraction of La doping, 0.01≤x≤0.04, and y is lithium amount adjustment factor, 85%≤y≤95％。
Above-mentioned a kind of La doping preparation method of the lithium-rich anode material of lithium quantitative change simultaneously, comprises the steps:
1) taking nickel salt, manganese salt, lithium salts and containing lanthanum compound as raw material, by La Li doped1.2(1-x)yNi0.3Mn0.6O2Chemistry meterAmount is than taking each raw material, and wherein x is the molar fraction of La doping, 0.01≤x≤0.04, and y is lithium amount adjustment factor, 85%≤y≤ 95%; By soluble in water to nickel salt and manganese salt, prepare to obtain uniform mixed liquor I; Soluble carbonate salt is soluble in water, prepareThe carbonate solution mixing, in the carbonate mole that wherein soluble carbonate salt is introduced and mixed liquor I, nickel salt and manganese salt are introducedThe integral molar quantity of metal ion is identical; Under stirring condition, carbonate solution is dropwise splashed in mixed liquor I, then in sealingUnder condition, carry out water-bath, carry out while hot suction filtration, washing and dry, grinding, and mix with lithium salts with containing lanthanum compound, enterRow ball milling, dry gained grinding product obtains presoma;
2) by gained presoma successively through pre-burning, high-temperature calcination, cooling described modification lithium-rich anode material.
In such scheme, described nickel salt is one or more in nickel acetate, nickel nitrate, nickelous sulfate, nickel chloride; Manganese salt is secondOne or more in acid manganese, manganese nitrate, manganese sulfate, manganese chloride.
In such scheme, described soluble carbonate salt is one or more in sodium carbonate, potash, carbonic acid ammonia.
In such scheme, described lithium salts is one or more in lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide, lithium chloride.
In such scheme, described is one or more in lanthana, lanthanum sulfate, lanthanum nitrate containing lanthanum compound.
In such scheme, described water-bath temperature is 70～90 DEG C, and the time is 10～14h.
Preferably, described bath temperature is 78～82 DEG C; Temperature retention time is 11.5～12.5 hours.
In such scheme, described ball milling speed is 800～1000 revs/min, and the time is 6～8h.
Preferably, described rotational speed of ball-mill is 930～970 revs/min.
Preferably, described Ball-milling Time is 6～6.5 hours.
In such scheme, described pre-sinter process is: be heated to 500～600 DEG C of insulations 4～6 hours.
Preferably, described calcined temperature is 580～600 DEG C, and the pre-burning time is 5.5～6 hours.
In such scheme, described high-temperature calcination technique is: be heated to 850～950 DEG C of insulations 10～14 hours.
Preferably, described high-temperature calcination temperature is 880～920 DEG C, and sintering time is 11.5～12.5 hours.
Principle of the present invention is: the present invention passes through Li2MnO3And LiNi0.5Mn0.5O2Two kinds of compound solid solution of stratified material enterRow La3+Adulterate and contain lithium quantitative change to Li1.2Ni0.3Mn0.6O2Material carries out modification; Wherein a part of La of doping3+EnterLi1.2Ni0.3Mn0.6O2Lattice, some La3+Form LaMnO3，LaMnO3Be a kind of fast-ionic conductor, be coated onPositive electrode particle surface, has improved the electric conductivity of material, thereby has improved the chemical property of material; In addition, LaMnO3The reduction of oxygen is had to high electro-chemical activity, oxygen ion hole is retained, irreversible capacity loss is fallen firstLow; On the other hand, the present invention is by regulating and controlling containing lithium amount, makes to have occurred in material structure Spinel, SpinelHave to be beneficial to and improve the irreversible capacity loss first of material; Spinel in discharge process, when in negative pole from structureWhen the Li deviating from embeds back spinel structure, the extra Li just having in negative pole lithium sheet embeds the octahedra 16c of spinelle room,Thereby make first coulomb efficiency very high, even > 100%, irreversible capacity loss is also very little first accordingly, is even negative value;When to Li1.2Ni0.3Mn0.6O2When material carries out La doping and the regulation and control of lithium amount simultaneously, in material system, there is impurity LaMnO simultaneously3And Spinel, the two synergy is obviously reduced irreversible capacity loss first.
Beneficial effect of the present invention is:
1) products therefrom pattern homogeneous of the present invention, degree of crystallinity high, be evenly distributed, particle size distribution is at nanoscale, specific areaLarger.
2) chemical property of modification lithium-rich anode material of the present invention is superior, capacity is high, good cycle, discharge voltage are high,High rate performance improves, and irreversible capacity loss reduces obviously especially first, and coulomb efficiency is obviously promoted first.
3) modification lithium-rich anode material of the present invention is rich lithium layer structure, and its preparation method is simple, not containing environment is hadPollute expensive cobalt element, raw material reserves are abundant, and environmental friendliness is cheap, is the lithium ion battery that has very much application prospectPositive electrode, is easy to realize industrialization, has practicable meaning.
Brief description of the drawings
Fig. 1 is the synthetic La doping of the embodiment of the present invention 6 XRD figure of the lithium-rich anode material of lithium quantitative change simultaneously.
Fig. 2 is the synthetic La doping of the embodiment of the present invention 6 SEM figure of the lithium-rich anode material of lithium quantitative change simultaneously.
Fig. 3 is the synthetic La doping circulation discharge curve of the lithium-rich anode material of lithium quantitative change simultaneously of the embodiment of the present invention 6.
Fig. 4 is the synthetic La doping lithium-rich anode material first charge-discharge curve map of lithium quantitative change simultaneously of the embodiment of the present invention 6.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, to thisBright being further elaborated. Should be appreciated that specific embodiment described herein is only in order to explain the present invention, and need notIn limiting the present invention. In addition, in each embodiment of described the present invention involved technical characterictic if each other itBetween do not form conflict just can mutually combine.
Comparative example 1
A kind of lithium-rich anode material, its preparation method comprises the following steps:
1) 0.2mol nickelous sulfate and 0.4mol manganese sulfate are dissolved in deionized water, then dropwise add uniform solution of potassium carbonate,Carbonate mole and the nickel ion wherein introduced are suitable from total mole number (0.6mol) with manganese ion metal, after being added dropwise to complete,Gained solution system is placed in to 90 DEG C of thermostat water baths and constantly stirs 10 hours, by gained nickel manganese sediment carry out while hot suction filtration,Wash, be dried, grind, pack for subsequent use; By 0.02mol nickel manganese sediment (NiCO3·2MnCO3) put with 0.04mol lithium carbonateIn ball grinder, carry out high speed ball milling, rotational speed of ball-mill is 800 revs/min, and Ball-milling Time is 8 hours, dry gained grinding productObtain presoma;
2), under air atmosphere, gained presoma is placed in to Muffle furnace and is heated to 500 DEG C of constant temperature pre-burnings 6 hours, then be heated toCalcine 12 hours for 950 DEG C, obtain described lithium-rich anode material, its structural formula is Li1.2Ni0.3Mn0.6O2(x＝0，y＝100％)。
By the present embodiment gained Li1.2Ni0.3Mn0.6O2(x=0, y=100%) for positive electrode forms half Denso pond, record 2～Within the scope of 4.8V, when under room temperature, current density is 20mA/g, its first discharge specific capacity is 244.6mAh/g, first coulomb efficiencyBe 77.65%, irreversible capacity loss is 70.4mAh/g first.
Comparative example 2
A kind of lithium-rich anode material, its preparation method comprises the following steps:
1) 0.2mol nickel nitrate and 0.4mol manganese nitrate are dissolved in deionized water, then dropwise add uniform carbonic acid ammonia solution,Carbonate mole and the nickel ion wherein introduced are suitable from total mole number (0.6mol) with manganese ion metal, after being added dropwise to complete,Gained solution system is placed in to 70 DEG C of thermostat water baths and constantly stirs 14 hours, by gained nickel manganese sediment suction filtration while hot, washWash, dry, grind, pack for subsequent use; By 0.02mol nickel manganese sediment (NiCO3·2MnCO3) with 0.0784mol lithium nitrate and0.0016mol lanthanum nitrate is placed in ball grinder and carries out high speed ball milling, and rotational speed of ball-mill is 900 revs/min, and Ball-milling Time is 8 hours,Dry gained grinding product obtains presoma;
2), under air atmosphere, gained presoma is placed in to Muffle furnace and is heated to 600 DEG C of constant temperature pre-burnings 5 hours, then be heated to900 DEG C of sintering 12 hours, obtain described modification lithium-rich anode material, 2%La Li doped1.176Ni0.3Mn0.6O2(x＝0.02，y＝100％)。
This comparative example gained lithium-rich anode material is assembled into half-cell, records within the scope of 2～4.8V, current density under room temperatureDuring for 20mA/g, first discharge specific capacity is 277.5mAh/g, and coulomb efficiency has reached 80.67%, irreversible capacity first firstLoss is reduced to 66.5mAh/g.
Comparative example 3
A kind of modification lithium-rich anode material, its preparation method comprises the following steps:
1) 0.2mol nickel acetate and 0.4mol manganese acetate are dissolved in deionized water, then dropwise add uniform solution of potassium carbonate,Carbonate mole and the nickel ion wherein introduced are suitable from total mole number (0.6mol) with manganese ion metal, after being added dropwise to complete,Gained solution system is placed in to 80 DEG C of thermostat water baths and constantly stirs 12 hours, gained nickel manganese sediment is filtered while hot, washWash, dry, grind, pack for subsequent use; By 0.02mol nickel manganese sediment (NiCO3·2MnCO3) and 0.0768mol lithium hydroxideBe placed in ball grinder with 0.0032mol lanthanum nitrate and carry out high speed ball milling, rotational speed of ball-mill is 900 revs/min, and Ball-milling Time is 14Hour, dry gained grinding product obtains presoma;
2), under air atmosphere, gained presoma is placed in to Muffle furnace and is heated to 600 DEG C of constant temperature pre-burnings 4 hours, then be heated to900 DEG C of sintering 14 hours, obtain described modification lithium-rich anode material 4%La Li doped1.152Ni0.3Mn0.6O2(x＝0.04，y＝100％)。
The present embodiment gained modification lithium-rich anode material is assembled into half-cell, records within the scope of 2～4.8V electric current under room temperatureWhen density is 20mA/g, first discharge specific capacity is 219.2mAh/g, and coulomb efficiency has reached 79.18% first, irreversible firstCapacitance loss is reduced to 57.2mAh/g.
Embodiment 1
A La doping lithium-rich anode material for lithium quantitative change simultaneously, its preparation method comprises the following steps:
1) prepare nickel manganese method for producing precipitate and catalyst identical with comparative example 2; By 0.02mol nickel manganese sediment (NiCO3·2MnCO3)Be placed in ball grinder with 0.07448mol lithium hydroxide and 0.0008mol lanthana and carry out high speed ball milling, rotational speed of ball-mill is 1000Rev/min, Ball-milling Time is 7 hours, dry gained grinding product obtains presoma;
2), under air atmosphere, gained presoma is placed in to Muffle furnace and is heated to 600 DEG C of constant temperature pre-burnings 6 hours, then be heated to900 DEG C of sintering 12 hours, obtain described La doping lithium-rich anode material (the modification lithium-rich anode material 2%La of lithium quantitative change simultaneouslyLi doped1.1172Ni0.3Mn0.6O2，x＝0.02，y＝95％)。
The lithium-rich anode material of the present embodiment gained La doping while lithium quantitative change is assembled into half-cell, records the model at 2～4.8VIn enclosing, when under room temperature, current density is 20mA/g, first discharge specific capacity is 249.7mAh/g, and coulomb efficiency has reached first82.14%, irreversible capacity loss is reduced to 54.3mAh/g first.
Embodiment 2
A kind of modification lithium-rich anode material, its preparation method comprises the following steps:
1) prepare nickel manganese method for producing precipitate and catalyst identical with comparative example 2; By 0.02mol nickel manganese sediment (NiCO3·2MnCO3)Be placed in ball grinder with 0.07056mol lithium hydroxide and 0.0008mol lanthana and carry out high speed ball milling, rotational speed of ball-mill is 1000Rev/min, Ball-milling Time is 6 hours, dry gained grinding product obtains presoma;
2), under air atmosphere, gained presoma is placed in to Muffle furnace and is heated to 600 DEG C of constant temperature pre-burnings 6 hours, then be heated to900 DEG C of sintering 12 hours, obtain described La doping lithium-rich anode material (the modification lithium-rich anode material 2%La of lithium quantitative change simultaneouslyLi doped1.0584Ni0.3Mn0.6O2(x＝0.02，y＝90％))。
The lithium-rich anode material of the present embodiment gained La doping while lithium quantitative change is assembled into half-cell, records the model at 2～4.8VIn enclosing, when under room temperature, current density is 20mA/g, first discharge specific capacity is 243.8mAh/g, and coulomb efficiency has reached first88.74%, irreversible capacity loss is reduced to 30.9mAh/g first.
Embodiment 3
A La doping lithium-rich anode material for lithium quantitative change simultaneously, its preparation method comprises the following steps:
1) prepare nickel manganese method for producing precipitate and catalyst identical with comparative example 2; By 0.02mol nickel manganese sediment (NiCO3·2MnCO3)Be placed in ball grinder with 0.06664mol lithium hydroxide and 0.0008mol lanthana and carry out high speed ball milling, rotational speed of ball-mill is 1000Rev/min, Ball-milling Time is 6 hours, dry gained grinding product obtains presoma;
2), under air atmosphere, gained presoma is placed in to Muffle furnace and is heated to 600 DEG C of constant temperature pre-burnings 6 hours, then be heated to900 DEG C of sintering 12 hours, obtain described La doping lithium-rich anode material (the described modification lithium-rich anode material of lithium quantitative change simultaneously2%La Li doped0.9996Ni0.3Mn0.6O2(x＝0.02，y＝85％))。
The lithium-rich anode material of the present embodiment gained La doping while lithium quantitative change is assembled into half-cell, records the model at 2～4.8VIn enclosing, first discharge specific capacity 229.2mAh/g when current density is 20mA/g under room temperature, coulomb efficiency has reached first88.45%, irreversible capacity loss is reduced to 29.9mAh/g first.
Embodiment 4
A La doping lithium-rich anode material for lithium quantitative change simultaneously, its preparation method comprises the following steps:
1) prepare nickel manganese method for producing precipitate and catalyst identical with comparative example 2; By 0.02mol nickel manganese sediment (NiCO3·2MnCO3)Be placed in ball grinder with 0.07128mol lithium hydroxide and 0.0004mol lanthana and carry out high speed ball milling, rotational speed of ball-mill is 1000Rev/min, Ball-milling Time is 7 hours, dry gained grinding product obtains presoma;
2), under air atmosphere, gained presoma is placed in to Muffle furnace and is heated to 500 DEG C of constant temperature pre-burnings 6 hours, then be heated to950 DEG C of sintering 10 hours, obtain described La doping lithium-rich anode material (the modification lithium-rich anode material of lithium quantitative change simultaneously1%La Li doped1.0692Ni0.3Mn0.6O2，x＝0.01，y＝90％)。
By La doping described in the present embodiment gained simultaneously the lithium-rich anode material of lithium quantitative change be assembled into half-cell, record 2～Within the scope of 4.8V, first discharge specific capacity 248.4mAh/g when current density is 20mA/g under room temperature, coulomb efficiency reaches first85.1%, irreversible capacity loss is reduced to 43.6mAh/g first.
Embodiment 5
A described La doping lithium-rich anode material for lithium quantitative change simultaneously, its preparation method comprises the following steps:
1) prepare nickel manganese method for producing precipitate and catalyst identical with comparative example 2; By 0.06mol nickel manganese sediment(0.3NiCO3·0.6MnCO3) be placed in ball grinder with 0.06984mol lithium hydroxide and 0.0024mol lanthanum nitrate and carry out clipping the ballMill, rotational speed of ball-mill is 1000 revs/min, and Ball-milling Time is 7 hours, and dry gained grinding product obtains presoma;
2), under air atmosphere, gained presoma is placed in to Muffle furnace and is heated to 600 DEG C of constant temperature pre-burnings 4 hours, then be heated to850 DEG C of sintering 14 hours, obtain (the modification lithium-rich anode material 3%La doping of described modification lithium-rich anode materialLi1.0476Ni0.3Mn0.6O2，x＝0.03，y＝90％)。
By La doping described in the present embodiment gained simultaneously the lithium-rich anode material of lithium quantitative change be assembled into half-cell, record 2～Within the scope of 4.8V, first discharge specific capacity 246.6mAh/g when current density is 20mA/g under room temperature, coulomb efficiency reaches first86.73%, irreversible capacity loss is reduced to 37.7mAh/g first.
Embodiment 6
A described La doping lithium-rich anode material for lithium quantitative change simultaneously, its preparation method comprises the following steps:
1) prepare nickel manganese method for producing precipitate and catalyst identical with comparative example 2; By 0.02mol nickel manganese sediment (NiCO3·2MnCO3)Be placed in ball grinder with 0.068992mol lithium hydroxide and 0.0016mol lanthanum nitrate and carry out high speed ball milling, rotational speed of ball-mill is 1000Rev/min, Ball-milling Time is 7 hours, dry gained grinding product obtains presoma;
2), under air atmosphere, gained presoma is placed in to Muffle furnace and is heated to 600 DEG C of constant temperature pre-burnings 4 hours, then be heated to850 DEG C of sintering 14 hours, obtain the described La doping lithium-rich anode material of lithium quantitative change (the rich lithium layered cathode material of modification simultaneously2%La Li doped1.03488Ni0.3Mn0.6O2，x＝0.02，y＝88％)。
The lithium-rich anode material of the present embodiment gained La doping while lithium quantitative change is carried out to X-ray diffraction analysis (seeing Fig. 1),Result shows that products therefrom has typical α-NaFeO2Layer structure, belongs to R-3m space group, and peak type is sharp-pointed, layer structureFeature splitting peak splitting is obvious, in addition, has also occurred LaMnO3Impurity peaks, this explanation only has small part La3+EnterLattice, some La3+Form LaMnO3，LaMnO3Be a kind of fast-ionic conductor, be coated on positive electrode particle tableFace, has improved the electric conductivity of material, thereby has improved the chemical property of material; On the other hand, LaMnO3To going back of oxygenFormer have a high electro-chemical activity, and oxygen ion hole is retained, and irreversible capacity loss is minimized first.
The scanning electron microscope (SEM) photograph of the present embodiment products therefrom is shown in Fig. 2, and in figure, material granule is evenly distributed, and degree of crystallinity is high, existing without reunitingResemble, particle size, at nanoscale, shows that the specific area of material is larger, is conducive to the deintercalation of lithium ion, thereby chemical propertyPromoted.
The present embodiment products therefrom is assembled into half-cell as positive electrode, records within the scope of 2～4.8V, electric current under room temperatureFirst charge-discharge curve when density is 20mA/g is as shown in Figure 3: initial charge specific capacity is 262.3mAh/g, first electric dischargeSpecific capacity is 236.3mAh/g, and coulomb efficiency has reached 90.1% first, and irreversible capacity loss has been reduced to 26mAh/g first.The reduction of irreversible capacity loss first can attribution be the LaMnO that La doping occurs3The Spinel two that regulation and control occur with lithium amountPerson's synergy, LaMnO3Be a kind of fast-ionic conductor, can improve the electric conductivity of material, thereby improved the electricity of materialChemical property; On the other hand, LaMnO3Be attached to particle surface, the reduction of oxygen is had to high electro-chemical activity, makeOxygen ion hole is retained, and is conducive to the reduction of irreversible capacity loss first. And the irreversible capacity first of Spinel damagesLose the low crystal structure special with it relevant, Spinel is in discharge process, when the Li deviating from from structure in negative pole embedsWhile returning spinel structure, the extra Li in negative pole lithium sheet will embed the octahedra 16c of spinelle room, thereby makes coulomb firstEfficiency is very high, even > 100%, and irreversible capacity loss is also very little first accordingly, is even negative value. When rightLi1.2Ni0.3Mn0.6O2When material carries out La doping and the regulation and control of lithium amount simultaneously, in material system, there is impurity LaMnO simultaneously3And pointSpar phase, the two synergy is obviously reduced irreversible capacity loss first.
The present embodiment products therefrom is assembled into half-cell as positive electrode, the electric discharge specific volume under room temperature in the time of different current densityAs shown in Figure 4, under 20mA/g, after 20 circulations, specific discharge capacity is 190.7mAh/g to amount cyclic curve, and capacity is protectedHoldup is 80.70%, and under 50mA/g, first discharge specific capacity is 211.2mAh/g, after 20 circulations, and electric discharge specific volumeAmount is 184.7mAh/g, and capability retention is 87.45%, and it is because the LaMnO in system that high rate performance is improved3Improve the electric conductivity of material.
The cited each raw material proportioning of the present invention all can realize the present invention, and the bound value of each raw material, interval value all can be realExisting the present invention, the present invention all can be realized in the bound value of technological parameter of the present invention and interval, differs one for example at this.
Those skilled in the art will readily understand, the foregoing is only preferred embodiment of the present invention, in order to restriction not originallyInvention, all any amendments of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included in thisWithin bright protection domain.
Claims (10)
1. a La doping lithium-rich anode material for lithium quantitative change simultaneously, its composition expression formula is: La Li doped1.2(1-x) yNi0.3Mn0.6O2, wherein x is the molar fraction of La doping, 0.01≤x≤0.04; Y is lithium amount adjustment factor, 85%≤y≤95％。
2. the La doping preparation method of the lithium-rich anode material of lithium quantitative change simultaneously described in claim 1, is characterized in that, comprisesFollowing steps:
1) taking nickel salt, manganese salt, lithium salts and containing lanthanum compound as raw material, by La Li doped1.2(1-x)yNi0.3Mn0.6O2Chemistry meterAmount is than taking each raw material, and wherein x is the molar fraction of La doping, 0.01≤x≤0.04, and y is lithium amount adjustment factor, 85%≤y≤ 95%; By soluble in water to nickel salt and manganese salt, prepare to obtain uniform mixed liquor I; Soluble carbonate salt is soluble in water, prepareThe carbonate solution mixing, in the carbonate mole that wherein soluble carbonate salt is introduced and mixed liquor I, nickel salt and manganese salt are introducedThe integral molar quantity of metal ion is identical; Under stirring condition, carbonate solution is dropwise splashed in mixed liquor I, then in sealingUnder condition, carry out water-bath, carry out while hot suction filtration, washing and dry, grinding, and mix with lithium salts with containing lanthanum compound, enterRow ball milling, dry gained grinding product obtains presoma;
2) by gained presoma successively through pre-burning, high-temperature calcination, cooling described modification lithium-rich anode material.
3. preparation method according to claim 2, is characterized in that, described nickel salt be nickel acetate, nickel nitrate, nickelous sulfate,One or more in nickel chloride; Manganese salt is one or more in manganese acetate, manganese nitrate, manganese sulfate, manganese chloride.
4. preparation method according to claim 2, is characterized in that, described soluble carbonate salt be sodium carbonate, potash,One or more in carbonic acid ammonia.
5. preparation method according to claim 2, is characterized in that, described lithium salts be lithium carbonate, lithium nitrate, lithium acetate,One or more in lithium hydroxide, lithium chloride.
6. preparation method according to claim 2, is characterized in that, described containing lanthanum compound be lanthana, lanthanum sulfate,One or more in lanthanum nitrate.
7. preparation method according to claim 2, is characterized in that, described water-bath temperature is 70～90 DEG C, and the time is10～14h。
8. preparation method according to claim 2, is characterized in that, described ball milling speed is 800～1000 revs/min, timeBetween be 6～8h.
9. preparation method according to claim 2, is characterized in that, described pre-sinter process is: be heated to 500～600 DEG CBe incubated 4～6 hours.
10. preparation method according to claim 2, is characterized in that, described high-temperature calcination technique is: be heated to 850～950 DEG C are incubated 10～14 hours.
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