CN102013481A - Method for synthesizing spherical gradient lithium-rich anode material - Google Patents
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Abstract
The invention discloses a method for synthesizing a spherical gradient lithium-rich anode material, which comprises the following steps of: adding deionized water into MnSO4 and [Ni0.4Co0.2Mn0.4](OH)2 in a molar ratio of x:1-x to form suspension, and dripping 0.025 to 0.1mol/L NaCO3 solution into the suspension in a 60 DEG C water bath to form a compact manganese carbonate precipitate layer; filtering, washing, and drying at the temperature of between 80 and 120 DEG C; and uniformly mixing precursor particles and lithium hydroxide in a molar ratio of 1:1.15-1.45, performing heat treatment in air at the temperature of between 400 and 500 DEG C for 3 to 5 hours, raising the temperature for 22 to 32 hours, and sintering at the temperature of between 750 and 900 DEG C for 12 to 15 hours. The material synthesized by the method has certain Mn concentration gradient, improves the tap density of lithium-rich materials, has high cyclical stability and specific capacity, and keeps high rate performance.
Description
Technical field
The present invention relates to a kind of synthetic method of spherical gradient lithium-rich anode material, belong to anode material for lithium-ion batteries and electrochemical field.
Background technology
Traditional positive electrode LiCoO
2Capacity is low, cost is high; LiNiO
2The synthesis condition harshness, invertibity is bad; The spinelle shape positive electrode LiMn that is easy to synthesize
2O
4Exist the problem that capacity is significantly decayed under the high temperature; And cheap olivine shape material LiFePO
4Because its ion and electronic conductivity be low to be hampered it and further develops.Therefore select the lithium-rich anode material of the cheap stable circulation of the high relative price of research capacity to have great importance.These materials can be showed unusual chemical property, such as height ratio capacity, outstanding circulation ability and new charge discharge mechanism.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
2The 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.
The synthetic method of traditional rich lithium material mainly contains coprecipitation, sol-gal process and hydro thermal method etc.Though adopt the synthetic rich lithium material of coprecipitation and sol-gal process to keep higher recycle ratio capacity usually, its size is less, tap density is lower and high rate performance is relatively poor; Synthetic very big concern, the Li that wherein adopts hydro thermal method to synthesize of being subjected to that much had the lithium-rich anode material of nanostructure in recent years
0.88[Li
0.18Co
0.33Mn
0.49] O
2Nano wire and the Li[Ni that adopts the Hydrothermal Template method to synthesize
0.25Li
0.15Mn
0.6] though the O2 nano wire has very superior recycle ratio capacity and higher high rate performance, but its hydrothermal synthesis method is comparatively harsh, material small-sized (＜100nm), be not suitable for commercially producing, and more side reaction takes place in bigger specific area and the electrolyte of nano material under high potential.
Therefore, preparation not only has higher reversible capacity and outstanding cycle performance but also has the lithium-rich anode material that higher power density is fit to large-scale industrial production, has become the trend of present research.
Summary of the invention
The purpose of this invention is to provide the spherical gradient lithium-rich anode material of a kind of lithium ion battery xLi
2MnO
3-(1-x) Li[Ni
0.4Co
0.2Mn
0.4] O
2Synthetic method.Method with simple precipitation coating and subsequent heat treatment makes to have the concentration gradient of certain Mn from the ball surface to core at synthetic spherical lithium-rich anode material, He Cheng rich lithium material has cyclical stability and higher reversible capacity preferably by this method, the tap density height, and this method technology is simple, operation is row easily, nontoxic, with low cost and environmental friendliness is fit to large-scale industrial production.
A kind of spherical gradient lithium-rich anode material xLi of the present invention
2MnO
3-(1-x) Li[Ni
0.4Co
0.2Mn
0.4] O
2(0.1≤x≤0.4), it is synthetic mainly to may further comprise the steps:
(1) preparation of spherical presoma: at the spherical presoma [Ni of existing commercialization
0.4Co
0.2Mn
0.4] (OH)
2The coating of manganese element is carried out on the surface, does the manganese source with manganese sulfate, according to MnSO
4: [Ni
0.4Co
0.2Mn
0.4] (OH)
2(mol ratio)=x: (1-x), take by weighing the spherical presoma [Ni of existing commercialization
0.4Co
0.2Mn
0.4] (OH)
2And add deionized water formation suspension-turbid liquid behind the manganese sulfate, in 60 ℃ of water-baths, stir then;
(2) preparation of spherical presoma coating layer: the NaCO of preparation 0.025～0.1mol/L
3Drips of solution is added in the above-mentioned suspension-turbid liquid of continuous stirring, controls certain speed forms one deck densification on the surface of spherical presoma manganese carbonate precipitation of dripping;
(3) subsequent treatment of presoma: leave standstill 12～24h after sodium carbonate liquor is added dropwise to complete, after filtration, after the washing, dry 12～24h in 80～120 ℃ vacuum drying oven obtains having the spherical presoma of coating layer;
(4) heat treatment of coated particle: will have the spherical granular precursor of dry coating layer and lithium hydroxide is that 1: 1.15～1.45 mixed evenly places tube furnace earlier at 400～500 ℃ of following heat treatment 3～5h under air atmosphere in the back according to mol ratio, heat up through the time of 22～32h then, under 750 ℃～900 ℃ temperature, burn till 12～15h then, promptly obtain spherical lithium-rich anode material, wherein in 750 ℃～850 ℃ temperature range, the Gradient distribution that manganese is in spheric granules.
Spherical granular precursor and the normal ratio of lithium hydroxide are 1: 1.1～1.4 in the step (4), but the loss that causes for the volatilization that is reduced in the high temperature sintering process owing to lithium, make wherein Li excessive 5%.
Usefulness of the present invention is:
We are by the synthetic lithium-rich anode material with concentration gradient of certain Mn of the method for this surface deposition Mn, because its spherical morphology can improve the tap density of rich lithium material greatly, and this material also has good cyclical stability and higher specific capacity, simultaneously also kept high rate performance preferably, made it can satisfy the needs of high power electronic equipment such as electric motor car, hybrid electric vehicle development.The more important thing is this sphere material size big (average diameter is greater than 10 μ m), and have higher bulk density (about 2.0g/cm
3), and this method technology is simple, only needs at spherical presoma surface deposition MnCO
3High-temperature process can obtain then, and is nontoxic, and with low cost and environmental friendliness is fit to large-scale industrial production.
Description of drawings
Fig. 1 is the spherical presoma [Ni of existing commercialization
0.4Co
0.2Mn
0.4] (OH)
2Scanning electron microscope sem figure;
Fig. 2 is spherical presoma surface deposition MnCO
3After scanning electron microscope sem figure;
Fig. 3 is the spherical gradient lithium-rich anode material synthetic under the different temperatures and the XRD diffracting spectrum of Comparative Examples
A: implement 1; B: implement 2; C: implement 3; D: implement 4; E: Comparative Examples
Fig. 4 is the scanning electron microscope sem figure of synthesizing spherical gradient lithium-rich anode material and Comparative Examples under the different temperatures;
A: implement 1; B: implement 2; C: implement 3; D: implement 4; E: Comparative Examples
Fig. 5 is the profile scanning Electronic Speculum SEM figure of synthesizing spherical gradient lithium-rich anode material under the different temperatures;
A: implement 1; B: implement 2; C: implement 3
Fig. 6 is synthesizing spherical gradient lithium-rich anode material section EDS energy spectrum analysis figure under the different temperatures;
A: implement 1; B: implement 2; C: implement 3;
Fig. 7 is the chemical property figure of synthesizing spherical gradient lithium-rich anode material and Comparative Examples under the different temperatures;
A: implement 1; B: implement 2; C: implement 3; D: implement 4; E: Comparative Examples
Fig. 8 is 800 ℃ of synthetic down spherical functionally gradient material (FGM)s and the chemical property figure under the Comparative Examples different multiplying;
A: implement 1; B: implement 2; C: implement 3; D: implement 4; E: Comparative Examples.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment
Embodiment 1
1, in order (OH) to carry out the coating of manganese element in 2 surfaces, do the manganese source with manganese sulfate at the spherical presoma of existing commercialization [Ni0.4Co0.2Mn0.4], according to MnSO4: [Ni0.4Co0.2Mn0.4] (OH)
2(mol ratio)=0.2: 0.8, take by weighing the spherical presoma [Ni of existing commercialization
0.4Co
0.2Mn
0.4] (OH)
2And add deionized water formation suspension-turbid liquid behind the manganese sulfate, in 60 ℃ of water-baths, stir then;
Take by weighing the spherical presoma [Ni of existing commercialization
0.4Co
0.2Mn
0.4] (OH)
2And add deionized water dissolving behind the manganese sulfate, and cationic solution concentration is 0.05mol/L, ultrasonic dispersion 1～2h is placed in 60 ℃ of water-baths and stirs 1～2h.
2, the NaCO of preparation 0.05mol/L
3Solution, with peristaltic pump with this Na
2CO
3Drips of solution is added to the MnSO in 1
4In the solution, control certain speed of dripping, make Na
2CO
3Solution be adsorbed on the lip-deep Mn of persursor material
2+Form the MnCO of one deck densification
3Precipitation.
3, work as Na
2CO
3Be added dropwise to complete the back and continue stir about 0.5～1h, the product with gained leaves standstill 12h then, filters, washing, and dry 24h in 80 ℃ vacuum drying oven obtains having the spherical presoma of dry coating layer;
4, spherical presoma with dry coating layer and the lithium hydroxide that oven dry in 3 is obtained is 1: 1.25 mixed according to mol ratio and grinds 1h in agate mortar, both are mixed the back places tube furnace earlier at 450 ℃ of following heat treatment 3h under air atmosphere, under 750 ℃, carry out the heat treatment of 12h through the slow intensification of 22h then, promptly obtain material requested.
From pattern is that diameter is about the spheric granules about 10 μ m at 750 ℃ of gained samples as can be seen, and its profile this granule interior as can be seen is a solid construction.Can draw the CONCENTRATION DISTRIBUTION of Mn element particle from the EDS power spectrum, the highest at the sample Mn of 750 ℃ of processing concentration of element in particle surface concentration, along diameter by outside inward concentration reduce gradually, presented certain gradient.
The analysis showed that from X-ray diffraction (XRD) product is α-NaFeO2 stratiform configuration, space group is R-3m, it can also be seen that from figure that still each diffraction maximum broad and intensity are low, degree of crystallinity is poor, layer structure is not obvious, does not also exist the superlattice peak, and this is low relevant with the temperature of burning till.
Electro-chemical test shows that when 0.2C discharge capacity is the 174mAh/g (see figure 7) first, still maintain the capacity of 160mAh/g after 50 circulations, but still keeping comparatively stable cycle performance though illustrate that this material degree of crystallinity is relatively poor, the gradient of its Mn concentration of element is kept cyclical stability to it and is also played a part certain from outside to inside.
The 1-3 step is with embodiment 1;
4, spherical presoma with dry coating layer and the lithium hydroxide that oven dry in 3 is obtained is 1: 1.25 mixed according to mol ratio and grinds 1h in agate mortar, both are mixed the back places tube furnace earlier at 450 ℃ of following heat treatment 3h under air atmosphere, under 800 ℃, carry out the heat treatment of 12h through the slow intensification of 25h then, promptly obtain material requested.
From pattern is that diameter is the solid spheric granules about 10 μ m at 800 ℃ of gained samples as can be seen, can draw the CONCENTRATION DISTRIBUTION of Mn element particle from the EDS power spectrum, the sample Mn of 800 ℃ of processing concentration of element along particle diameter by outside inward concentration reduce gradually, presented certain gradient, but surperficial Mn ion concentration and inner concentration margin are a little less than 750 ℃ sample.
The analysis showed that from X-ray diffraction (XRD) product is α-NaFeO2 stratiform configuration, space group is R-3m, and each diffraction maximum is sharp-pointed, and intensity is big, and degree of crystallinity is higher, has occurred faint superlattice peak near 21 °.
Electro-chemical test shows that when 0.2C discharge capacity is 242mAh/g first, still maintains the high power capacity of 221mAh/g after 50 circulations, and stable cycle performance also has high rate performance (see figure 8) preferably simultaneously.Under 1C, 2C multiplying power (current density is respectively 200mAh/g, 400mAh/g), its first cyclic discharge capacity be respectively 171mAh/g, 162mAh/g, still maintain the high power capacity of 180mAh/g, 160mAh/g after 50 circulations respectively, do not compare not decay with discharge capacity first, cycle performance is highly stable.The sample that this explanation is burnt till under 800 ℃ can form stable Li
2MnO
3-LiMO
2Shape stratiform solid solution, and the Mn element from particle surface to inner infiltration in gradient, both helped the stable of material structure, kept higher recycle ratio capacity again.
Embodiment 3
The 1-3 step is with embodiment 1;
4, spherical presoma with dry coating layer and the lithium hydroxide that oven dry in 3 is obtained is 1: 1.25 mixed according to mol ratio and grinds 1h in agate mortar, both are mixed the back places tube furnace earlier at 450 ℃ of following heat treatment 3h under air atmosphere, under 850 ℃, carry out the heat treatment of 15h through the slow intensification of 28h then, promptly obtain material requested.
From pattern is that diameter is the solid spheric granules about 10 μ m at 850 ℃ of gained samples as can be seen, can draw the CONCENTRATION DISTRIBUTION of Mn element particle from the EDS power spectrum, the sample Mn of 850 ℃ of processing concentration of element along particle diameter by outside the gradient that presents inward and not obvious, surperficial Mn ion concentration and inner concentration almost maintain an equal level.The rising of this explanation firing temperature makes that the distribution of Mn element in particle is more even, the gradient reduction.
The analysis showed that from X-ray diffraction (XRD) product is α-NaFeO2 stratiform configuration, space group is R-3m, and each diffraction maximum is sharp-pointed, and intensity is big, and tangible superlattice peak appears in the degree of crystallinity height near 21 °.
Electro-chemical test shows that when 0.2C discharge capacity is the 220mAh/g (see figure 7) first, 50 times circulation back capacity is 205mAh/g, illustrate that this material is still keeping higher specific capacity, descend but compare with 800 ℃ of samples to some extent, the concentration distribution gradient in particle that has also confirmed the Mn element more helps this material and has higher recycle ratio capacity.
The 1-3 step is with embodiment 1;
4, spherical presoma with dry coating layer and the lithium hydroxide that oven dry in 3 is obtained is 1: 1.25 mixed according to mol ratio and grinds 1h in agate mortar, both are mixed the back places tube furnace earlier at 450 ℃ of following heat treatment 3h under air atmosphere, under 900 ℃, carry out the heat treatment of 15h through the slow intensification of 32h then, promptly obtain material requested.
From pattern is that diameter is the solid spheric granules about 10 μ m at 850 ℃ of gained samples as can be seen, can draw the CONCENTRATION DISTRIBUTION of Mn element particle from the EDS power spectrum, the sample Mn of 900 ℃ of processing concentration of element along particle diameter by outside do not present certain gradient inward, the firing temperature that this explanation is 900 ℃ makes the Mn element distribute uniformly in particle, and gradient disappears.
The analysis showed that from X-ray diffraction (XRD) product is α-NaFeO2 stratiform configuration, space group is R-3m, compares with other temperature gained samples, each diffraction maximum of the sample that burns till under 900 ℃ is the most sharp-pointed, the intensity maximum, degree of crystallinity is the highest, and near the superlattice that occur 21 ° are also obvious.
Electro-chemical test shows that when 0.2C discharge capacity is the 201mAh/g (see figure 7) first, 50 times circulation back capacity is 191mAh/g, illustrate that this material is still keeping higher specific capacity, with 800 ℃ of samples that burn till mutually specific capacity reduced about 30mAh/g, also can keep this richness lithium material to have higher capacity and cyclical stability though also confirmed the even distribution in particle of Mn element more, the concentration gradient of Mn element has important function to the capacity that improves this richness lithium material.
Comparative Examples
1, adopts the synthetic rich lithium material Li[Ni of common coprecipitation
0.2Li
0.2Mn
0.6] O
2At 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 200mL, cation concn are 0.4mol/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 900 ℃ of insulation 15h, with the stove cool to room temperature, obtain anode material for lithium-ion batteries Li[Ni
0.2Li
0.2Mn
0.6] O
2
From pattern, He Cheng rich lithium material particle is to have the granule reunion about 100-200nm to form by this method.
The analysis showed that from X-ray diffraction (XRD) product is α-NaFeO2 stratiform configuration, space group is R-3m, and each diffraction maximum of sample is sharp-pointed, and intensity is big, and tangible superlattice appear in the degree of crystallinity height near 21 °.
Electro-chemical test shows that when 0.2C discharge capacity is 231mAh/g first, and 50 times circulation back capacity is 179mAh/g, and capacity attenuation is more serious.The also relatively poor (see figure 8) of its high rate performance, under 1C, 2C multiplying power (current density is respectively 200mAh/g, 400mAh/g), its discharge capacity is respectively than hanging down 20mAh/g, 50mAh/g with the following 800 ℃ of synthetic spherical functionally gradient material (FGM)s of multiplying power, this shows that the Mn element is from particle surface to inner distribution gradient, both help the stable of material structure, kept higher recycle ratio capacity again.
Claims (1)
1. spherical gradient lithium-rich anode material xLi
2MnO
3-(1-x) Li[Ni
0.4Co
0.2Mn
0.4] O
2The synthetic method of (0.1≤x≤0.4) is characterized in that, mainly may further comprise the steps:
(1) preparation of spherical presoma
According to MnSO
4: [Ni
0.4Co
0.2Mn
0.4] (OH)
2(mol ratio)=x: (1-x), take by weighing the spherical presoma [Ni of existing commercialization
0.4Co
0.2Mn
0.4] (OH)
2And add deionized water formation suspension-turbid liquid behind the manganese sulfate, in 60 ℃ of water-baths, stir then;
(2) preparation of spherical presoma coating layer
The NaCO of preparation 0.025～0.1mol/L
3Drips of solution is added in the above-mentioned suspension-turbid liquid of continuous stirring, forms the manganese carbonate precipitation of one deck densification on the surface of spherical presoma;
(3) subsequent treatment of presoma
Leave standstill 12～24h after sodium carbonate liquor is added dropwise to complete, after filtration, after the washing, dry 12～24h in 80～120 ℃ vacuum drying oven obtains having the spherical presoma of coating layer;
(4) heat treatment of coated particle
To have the spherical granular precursor of dry coating layer and lithium hydroxide is that 1: 1.15～1.45 mixed evenly places tube furnace earlier at 400～500 ℃ of following heat treatment 3～5h under air atmosphere in the back according to mol ratio, heat up through the time of 22～32h then, under 750 ℃～900 ℃ temperature, burn till 12～15h then, promptly obtain spherical lithium-rich anode material, wherein in 750 ℃～850 ℃ temperature range, the Gradient distribution that manganese is in spheric granules.
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