CN101562245A - Method for modifying high-rate lithium-rich anode material - Google Patents

Method for modifying high-rate lithium-rich anode material Download PDF

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CN101562245A
CN101562245A CNA2009100854612A CN200910085461A CN101562245A CN 101562245 A CN101562245 A CN 101562245A CN A2009100854612 A CNA2009100854612 A CN A2009100854612A CN 200910085461 A CN200910085461 A CN 200910085461A CN 101562245 A CN101562245 A CN 101562245A
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lithium
solution
anode material
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mnso
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CN101562245B (en
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赵煜娟
赵春松
孙少瑞
王绥军
夏定国
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Beijing University of Technology
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Beijing University of Technology
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    • Y02E60/10Energy storage using batteries

Abstract

The invention belongs to the fields of lithium ion battery anode materials and electrochemistry. A lithium-rich material with high capacity and stable cycle performance cannot meet the requirement of quick charge and discharge of a high-power lithium ion battery. A surface modified lithium-rich material comprises a coating layer MnO2 and a main phase Li[NixLi1/3-2x/3Mn2/3-x/3]O2(x is more than or equal to 1/5 and less than or equal to 1/3), and the mass ratio of the coating layer and the main phase is 0 to 6 percent. A preparation method comprises that: the obtained lithium-rich anode material Li[Ni0.2Li0.2Mn0.6]O2 is dispersed in 0.194-1.17 g/L MnSO4 solution, subjected to ultrasound for 1 hour, and violently stirred for 2 hours; and 0.122-0.731 g/L Na2CO3 solution is added into the violently stirred MnSO4 solution dropwise by a peristaltic pump, and the mixed solution is filtered after the dropwise addition, dried at 120 DEG C and sintered at a temperature of between 300 and 500 DEG C for 4 to 8 hours to obtain the surface modified Li[NixLi1/3-2x/3Mn2/3-x/3]O2(x is more than or equal to 1/5 and less than or equal to 1/3). The preparation method reduces initial irreversible capacity loss of the lithium-rich material, greatly improves the cycle performance under high rate, and can meet the requirement of the high-power lithium ion battery.

Description

A kind of method of modifying of high-rate lithium-rich anode material
Technical field
The present invention relates to a kind of a kind of surface modifying method of high rate capability lithium-rich anode material, belong to anode material for lithium-ion batteries and electrochemical field.
Background technology
Present business-like positive electrode LiCoO 2Capacity is relatively low, and the 3G electronic product that battery capacity is had higher requirements and the marketization of electric automobile bring certain difficulty, and the lithium-rich anode material that has high voltage and higher capacity in recent years causes extensive concern.
Lithium-rich anode material mainly is stratified material Li 2MnO 3With LiMO 2(M=Ni, Co, Fe, Cr) the solid solution xLi of Xing Chenging 2MnO 3(1-x) LiMO 2, also can write Li[M xLi 1/3-2x/3Mn 2/3-x/3] O 2Li[Li 1/3Mn 2/3] O 2Have and LiCoO 2Similar desirable layer structure, the number of Li and Mn ratio is 1: 2 in the M layer, Li and [Li 1/3Mn 2/3] alternately occupy octahedral site.The anodal material Li[M of solid solution xLi 1/3-2x/3Mn 2/3-x/3] O 2Has α-NaFeO 2The stratiform configuration belongs to hexagonal crystal system, the R-3m space group, and Li occupies 3a, and transition metal Ni and Mn occupy the 3b position.
Lithium ion battery lithium-rich anode material Li[M xLi 1/3-2x/3Mn 2/3-x/3] O 2(1/5≤x≤1/3) and commercial LiCoO 2Compare and have higher reversible capacity (250mAh/g), and show cyclical stability preferably in the charging and discharging process.But relatively poor high rate performance has seriously hindered its large-scale application.Though people such as J.Cho adopt hydrothermal method to synthesize the Li of high rate capability 0.88[Li 0.18Co 0.33Mn 0.49] O 2And Li 0.93[Li 0.21Co 0.28Mn 0.51] O 2Nano wire and nanometer sheet, but very harsh experiment condition makes it be difficult to carry out industrial and large-scale production.
Seek a kind of method for preparing lithium-rich anode material, make lithium-rich anode material have reversible capacity and high rate performance preferably, and suitable large-scale industrial production, become the trend of present research.
Summary of the invention
The purpose of this invention is to provide a kind of high-lithium ion battery lithium-rich anode material Li[Ni xLi 1/3-2x/3Mn 2/3-x/3] O 2The method of modifying of (1/5≤x≤1/3).With simple precipitation and heat-treating methods at Li[Ni xLi 1/3-2x/3Mn 2/3-x/3] O 2The surface of (1/5≤x≤1/3) coats MnO 2, the high rate performance of raising lithium ion battery lithium-rich anode material.This method technology is simple, and operation is easily gone, and is nontoxic, and with low cost and environmental friendliness is fit to large-scale industrial production.
The method of modifying of a kind of high-rate lithium-rich anode material of the present invention is characterized in that, may further comprise the steps:
High magnification surface modification lithium ion battery lithium-rich anode material Li[Ni xLi 1/3-2x/3Mn 2/3-x/3] O 2The synthetic method of (1/5≤x≤1/3) is as follows:
1, by molecular formula Li[Ni xLi 1/3-2x/3Mn 2/3-x/3] O 2The ratio of Ni, Mn preparation NiSO in (1/5≤x≤1/3) 4And MnSO 4Mixed solution, cation concn is 1-3mol/L;
2, with peristaltic pump mixed solution and LiOH solution are added drop-wise in the reactor jointly, and control the pH value between 9-12,60 ℃ of water-bath heating.After reaction finishes, filter, wash, behind 120 ℃ vacuum drying chamber inner drying 12h, obtain presoma M (OH) 2(M=Mn, Ni);
3, with presoma and LiOHH 2O is by molecular formula Li[Ni xLi 1/3-2x/3Mn 2/3-x/3] O 2In mixed evenly after, 450 ℃ of insulation 6-10h under air atmosphere at 700-950 ℃ of insulation 10-20h down, with the stove cool to room temperature, obtain anode material for lithium-ion batteries Li[Ni xLi 1/3-2x/3Mn 2/3-x/3] O 2(1/5≤x≤1/3);
4, with the above-mentioned Li[Ni that makes xLi 1/3-2x/3Mn 2/3-x/3] O 2(1/5≤x≤1/3) is dissolved in the MnSO that concentration is 0.194-1.178g/L 4In the solution, ultrasonic dispersion 1h is strong agitation 2h then, to wherein splashing into the Na that concentration is 0.122-0.731g/L 2CO 3Solution and the Mn that is adsorbed on the persursor material 2+Form MnCO 3, filter, 120 ℃ of oven dry down;
5, the Li[Ni after will drying xLi 1/3-2x/3Mn 2/3-x/3] O 2(1/5≤x≤1/3) is burnt 4-8h down at 300-500 ℃ and is promptly got high magnification surface modification anode material for lithium-ion batteries Li[Ni xLi 1/3-2x/3Mn 2/3-x/3] O 2(1/5≤x≤1/3).
Usefulness of the present invention is:
We pass through MnO 2Coat Li[M xLi 1/3-2x/3Mn 2/3-x/3] O 2(1/5≤x≤1/3) (MnO 2With principal phase Li[Ni xLi 1/3-2x/3Mn 2/3-x/3] O 2Both mass ratioes are 0-6%), not only can improve the high rate performance of this composite material greatly, make it can satisfy the needs of high power electronic equipment such as electric motor car, hybrid electric vehicle development, the more important thing is that this method technology is simple, only need precipitate MnCO at presoma 3, Low Temperature Heat Treatment gets final product then, and this operation is row easily, and is nontoxic, and with low cost and environmental friendliness is fit to large-scale industrial production.
Description of drawings
Fig. 1 is the XRD figure of lithium-rich anode material before and after coating
Fig. 2 is the chemical property figures of different covering amounts at 0.5C (1C=200mA/g)
Fig. 3 is the chemical property figure when 1C before and after coating
Fig. 4 is the chemical property figure when 2C before and after coating
Embodiment
Further specify the present invention below by embodiment and Comparative Examples.
Embodiment 1
1, at first by molecular formula Li[Ni 0.2Li 0.2Mn 0.6] O 2Middle Ni, the ratio preparation NiSO of Mn 4And MnSO 4Mixed solution, cation concn are 2mol/L;
2, with peristaltic pump mixed solution and LiOH solution are added drop-wise in the reactor jointly, and control the pH value about 11,60 ℃ of water-bath heating.After reaction finishes, filter, wash, behind 120 ℃ vacuum drying chamber inner drying 12h, obtain presoma M (OH) 2(M=Mn, Ni):
3, presoma and LiOHH 2O is by molecular formula Li[Ni 0.2Li 0.2Mn 0.6] O 2Mixed evenly after, 450 ℃ of insulation 6h under air atmosphere continue to be warmed up to 950 ℃ of insulation 10h, with the stove cool to room temperature, obtain anode material for lithium-ion batteries Li[Ni 0.2Li 0.2Mn 0.6] O 2
4, the above-mentioned lithium-rich anode material that obtains is dispersed in the MnSO of 0.194g/L 4Ultrasonic 1h in the solution, and strong agitation 2h are then with the Na of 0.122g/L 2CO 3Solution splashes into intensively stirred MnSO by peristaltic pump 4In the solution, after dripping off solution is filtered, 120 ℃ of oven dry;
5 and then at 400 ℃ of sintering 6h, promptly get the Li[Ni of surface modification 0.2Li 0.2Mn 0.6] O 2
X-ray diffraction (XRD) the analysis showed that the product principal phase is Li[Ni 0.2Li 0.2Mn 0.6] O 2(see figure 1) coats its structure of back and is not destroyed.
Electro-chemical test shows that when 1C and 2C discharge capacity is 245mAh/g (see figure 3) and 240mAh/g (see figure 4) first, still keep higher capacity after 50 circulations, illustrate that the material after the surface modification can increase substantially the high rate performance of material, this is because the coating layer of the nanoaperture structure that generates has strengthened the contact area with electrolyte, more helps the carrying out of electrochemical reaction.And coating layer can prevent the HF of electrolyte generation and the generation of active material negative reaction effectively.
Embodiment 2
The 1-3 step is with embodiment 1;
4, the lithium-rich anode material that obtains is dispersed in the MnSO of 0.777g/L 4Ultrasonic 1h in the solution, and strong agitation 2h are then with the Na of 0.487g/L 2CO 3Solution splashes into intensively stirred MnSO by peristaltic pump 4In the solution, after dripping off solution is filtered, 120 ℃ of oven dry;
5 and then at 300 ℃ of sintering 6h, promptly get the Li[Ni of surface modification 0.2Li 0.2Mn 0.6] O 2
X-ray diffraction (XRD) the analysis showed that the product principal phase is Li[Ni 0.2Li 0.2Mn 0.6] O 2(see figure 1) coats its structure of back and is not destroyed.
Electro-chemical test shows that when 0.5C discharge capacity is the 192mAh/g (see figure 2) first, still the capacity that keeps 190mAh/g after 50 circulations, capability retention is up to 98.9%, illustrate that material its stable circulation performance in little electric current charge and discharge process after the surface modification is better, capacity is unattenuated basically behind 50 fantasies.
Embodiment 3
The 1-3 step is with embodiment 1;
4, the lithium-rich anode material that obtains is dispersed in the MnSO of 0.777g/L 4Ultrasonic 1h in the solution, and strong agitation 2h are then with the Na of 0.487g/L 2CO 3Solution splashes into intensively stirred MnSO by peristaltic pump 4In the solution, after dripping off solution is filtered, 120 ℃ of oven dry;
5 and then at 500 ℃ of sintering 6h, promptly get the Li[Ni of surface modification 0.2Li 0.2Mn 0.6] O 2
X-ray diffraction (XRD) the analysis showed that the product principal phase is Li[Ni 0.2Li 0.2Mn 0.6] O 2(see figure 1) coats its structure of back and is not destroyed.But, MnCO 3Separating the product that obtains 500 ℃ of time-divisions is not MnO 2, but Mn 5O 8
Embodiment 4
The 1-3 step is with embodiment 1;
4, the lithium-rich anode material that obtains is dispersed in the MnSO of 0.194g/L 4Ultrasonic 1h in the solution, and strong agitation 2h are then with the Na of 0.122g/L 2CO 3Solution splashes into intensively stirred MnSO by peristaltic pump 4In the solution, after dripping off solution is filtered, 120 ℃ of oven dry;
5 and then at 450 ℃ of sintering 6h, promptly get the Li[Ni of surface modification 0.2Li 0.2Mn 0.6] O 2
X-ray diffraction (XRD) the analysis showed that the product principal phase is Li[Ni 0.2Li 0.2Mn 0.6] O 2(see figure 1) coats its structure of back and is not destroyed.
Electro-chemical test shows that when 1C and 2C discharge capacity is 234mAh/g (see figure 3) and 200mAh/g (see figure 4) first, still keeps higher capacity after 50 circulations, illustrates that the material after the surface modification can increase substantially the high rate performance of material.This is because the coating layer of the nanoaperture structure that generates has strengthened the contact area with electrolyte, more helps the carrying out of electrochemical reaction.And coating layer can prevent the HF of electrolyte generation and the generation of active material negative reaction effectively.
Embodiment 5
The 1-3 step is with embodiment 1;
4, the lithium-rich anode material that obtains is dispersed in the MnSO of 0.777g/L 4Ultrasonic 1h in the solution, and strong agitation 2h are then with the Na of 0.487g/L 2CO 3Solution splashes into intensively stirred MnSO by peristaltic pump 4In the solution, after dripping off solution is filtered, 120 ℃ of oven dry;
5 and then at 450 ℃ of sintering 6h, promptly get the Li[Ni of surface modification 0.2Li 0.2Mn 0.6] O 2
X-ray diffraction (XRD) the analysis showed that the product principal phase is Li[Ni 0.2Li 0.2Mn 0.6] O 2(see figure 1) coats its structure of back and is not destroyed.
Electro-chemical test shows that when 1C and 2C discharge capacity is 236mAh/g (see figure 3) and 245mAh/g (see figure 4) first, still keeps higher capacity after 50 circulations, illustrates that the material after the surface modification can increase substantially the high rate performance of material.This is because the coating layer of the nanoaperture structure that generates has strengthened the contact area with electrolyte, more helps the carrying out of electrochemical reaction.And coating layer can prevent the HF of electrolyte generation and the generation of active material negative reaction effectively.
Embodiment 6
The 1-3 step is with embodiment 1;
4, the lithium-rich anode material that obtains is dispersed in the MnSO of 1.178g/L 4Ultrasonic 1h in the solution, and strong agitation 2h are then with the Na of 0.731g/L 2CO 3Solution splashes into intensively stirred MnSO by peristaltic pump 4In the solution, after dripping off solution is filtered, 120 ℃ of oven dry;
5 and then at 450 ℃ of sintering 6h, promptly get the Li[Ni of surface modification 0.2Li 0.2Mn 0.6] O 2
X-ray diffraction (XRD) the analysis showed that the product principal phase is Li[Ni 0.2Li 0.2Mn 0.6] O 2(see figure 1) coats its structure of back and is not destroyed.
Electro-chemical test shows that when 1C and 2C discharge capacity is 215mAh/g (see figure 3) and 205mAh/g (see figure 4) first, still keeps higher capacity after 50 circulations, illustrates that the material after the surface modification can increase substantially the high rate performance of material.This is because the coating layer of the nanoaperture structure that generates has strengthened the contact area with electrolyte, more helps the carrying out of electrochemical reaction.And coating layer can prevent the HF of electrolyte generation and the generation of active material negative reaction effectively.
Comparative Examples
1, at first by molecular formula Li[Ni 0.2Li 0.2Mn 0.6] O 2Middle Ni, the ratio preparation NiSO of Mn 4And MnSO 4Mixed solution, cation concn are 2mol/L;
2, with peristaltic pump mixed solution and LiOH solution are added drop-wise in the reactor jointly, and control the pH value about 11,60 ℃ of water-bath heating.After reaction finishes, filter, wash, behind 120 ℃ vacuum drying chamber inner drying 12h, obtain presoma M (OH) 2(M=Mn, Ni);
3, presoma and LiOHH 2After O mixed, 450 ℃ of insulation 6h under air atmosphere continued to be warmed up to 950 ℃ of insulation 10h, with the stove cool to room temperature, obtain anode material for lithium-ion batteries Li[Ni 0.2Li 0.2Mn 0.6] O 2
X-ray diffraction (XRD) the analysis showed that the product principal phase is Li[Ni 0.2Li 0.2Mn 0.6] O 2(see figure 1).

Claims (1)

1, a kind of method of modifying of high-rate lithium-rich anode material comprises the steps:
1) by molecular formula Li[Ni xLi 1/3-2x/3Mn 2/3-x/3] O 2The ratio of Ni, Mn preparation NiSO in (1/5≤x≤1/3) 4And MnSO 4Mixed solution, cation concn is 1-3mol/L;
2) with peristaltic pump mixed solution and LiOH solution are added drop-wise in the reactor jointly, and control the pH value between 9-12,60 ℃ of water-bath heating.After reaction finishes, filter, wash, behind 120 ℃ vacuum drying chamber inner drying 12h, obtain presoma M (OH) 2(M=Mn, Ni);
3) with presoma and LiOHH 2O is by molecular formula Li[Ni xLi 1/3-2x/3Mn 2/3-x/3] O 2In mixed evenly after, 450 ℃ of insulation 6-10h under air atmosphere at 700-950 ℃ of insulation 10-20h down, with the stove cool to room temperature, obtain anode material for lithium-ion batteries Li[Ni xLi 1/3-2x/3Mn 2/3-x/3] O 2(1/5≤x≤1/3);
It is characterized in that:
4) with the Li[Ni that makes in the step 3) xLi 1/3-2x/3Mn 2/3-x/3] O 2(1/5≤x≤1/3) is dissolved in the MnSO that concentration is 0.194-1.178g/L 4In the solution, ultrasonic dispersion 1h is strong agitation 2h then, to wherein splashing into the Na that concentration is 0.122-0.731g/L 2CO 3Solution filters, 120 ℃ of oven dry down;
5) Li[Ni after will drying xLi 1/3-2x/3Mn 2/3-x/3] O 2(1/5≤x≤1/3) is burnt 4-8h down at 300-500 ℃ and is promptly got high magnification surface modification anode material for lithium-ion batteries Li[Ni xLi 1/3-2x/3Mn 2/3-x/3] O 2(1/5≤x≤1/3).
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CN104466157A (en) * 2013-09-12 2015-03-25 中国科学院宁波材料技术与工程研究所 Lithium-rich manganese based anode material and preparation method thereof
CN104466157B (en) * 2013-09-12 2017-04-12 中国科学院宁波材料技术与工程研究所 Lithium-rich manganese based anode material and preparation method thereof
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