CN108054371A - A kind of high-tap density, high magnification and long-life lithium-rich manganese-based anode material and preparation method thereof - Google Patents
A kind of high-tap density, high magnification and long-life lithium-rich manganese-based anode material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- 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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- 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
A kind of high-tap density, high magnification and long-life lithium-rich manganese-based anode material and preparation method thereof, belong to field of material synthesis technology.The chemical formula of the positive electrode is Li [Lia(MnxNiyCoz)1−a]O2.Preparation method is：Manganese nickel cobalt carbonate spherical precursor is prepared using coprecipitation；Manganese nickel cobalt carbonate spherical precursor with lithium source is uniformly mixed, is calcined, obtains spherical lithium-rich manganese-based anode material；Spherical lithium-rich manganese-based anode material is subjected to hydro-thermal post processing, obtains high-tap density, high magnification and long-life lithium-rich manganese-based anode material.The collective effect that the present invention passes through crystal nucleation controlling agent and complexing agent, reduce the crystal surface energy of co-precipitation system, improve material tap density, high discharge capacity is provided using the more metal synergistic effects of manganese nickel cobalt, being reacted using hydro-thermal solid liquid interface reduces second particle surface nickel lithium mixing layer thickness and mixing ratio, lithium ion diffusion coefficient, reinforcing material rate capability are improved, and promotes material circulation stability.
Description
Technical field
The invention belongs to field of material synthesis technology, are related to a kind of anode material for lithium-ion batteries and preparation method thereof, especially
It is related to a kind of high-tap density, high magnification and long-life lithium-rich manganese-based anode material and preparation method thereof.
Background technology
Lithium ion battery is widely used in field of portable electronic apparatus, while in electric vehicle and energy-accumulating power station
The fields of grade have also shown huge application prospect.Positive electrode is that lithium ion solely or mainly carries in current lithium ion battery
Donor, it has also become lithium ion battery energy density improves and the bottleneck of price reduction.High-performance lithium ion positive electrode should possess
Following element：Higher discharge voltage and capacity, reliable and stable cycle performance, good thermal stability, higher electrons/ions
Electrical conductivity, be readily synthesized, production cost is low, environmental-friendly.At present, the research of anode material for lithium-ion batteries is concentrated mainly on
Several classes below：Layer structure LiTMO2（TM is transition metal ions, such as Co, Ni, Mn）, spinel structure LiMn2O4And olive
Stone structure LiFePO4Deng.
The actual capacity of above-mentioned a few class materials is between 100 ~ 200 mAh/g, it is difficult to which meeting that positive electrode is in urgent need to be improved can
Inverse specific capacity, the growth requirement for reducing cost.In contrast, rich lithium manganese base solid solution Li [Lia(MnvNixCoy)1−a]O2Anode material
Material is under the charging voltage higher than 4.5 V, it is possible to provide the actual reversible specific capacity of 250 ~ 300 mAh/g, have energy density it is high,
Thermal stability is good, cost of material is low, advantages of environment protection, is development high-energy density（>300 Wh/kg）, inexpensive lithium from
Important candidate's positive electrode of sub- battery.Research shows that micron-size spherical structure is conducive to lithium-rich manganese base material and improves volume energy
Density, but the lithium-rich manganese-based anode material grain size obtained by conventional preparation techniques is bigger than normal, lithium ion diffusion path is longer, causes
Material is large current discharge and high rate capability is poor；Grain structure is not fine and close, and tap density is relatively low, limits material volume energy
Density is promoted；In addition particle surface easily generates metallic element segregation, causes surface nickel lithium mixing degree high, easily induces surface
Heterogeneous phase generation, so as to capacity attenuation of the accelerated material in cyclic process, these shortcomings have become to limit lithium-rich manganese-based anode
The technical bottleneck of material application.
The content of the invention
The purpose of the present invention is to solve current lithium-rich manganese-based anode material tap density is relatively low, high rate performance is poor and holds
The problem of amount attenuation is fast, provides a kind of high-tap density, high magnification and long-life lithium-rich manganese-based anode material and preparation method thereof,
The positive electrode is prepared by presoma, is prepared with three steps of lithium sintering and hydro-thermal post processing.This method is by constructing
Micron order compact spheroidal particle, provides high-tap density, and providing high electric discharge using multi-element metal synergistic effect in second particle holds
Amount, being reacted using hydro-thermal solid liquid interface reduces second particle surface nickel lithium mixing layer thickness with reducing surface nickel lithium mixing ratio,
So as to improve lithium ion diffusion coefficient, reinforcing material rate capability promotes material circulation performance.Regulated and controled by coprecipitation method brilliant
Grain nucleation and growth is prepared moderate in grain size, the high jolt ramming lithium-rich manganese-based anode material of compact structure, and is adjusted using hydro-thermal post processing
The arrangement of second particle surface atom is controlled, reduce surface nickel lithium mixing layer thickness and reduces surface nickel lithium mixing ratio, improves material
High rate performance and cycle life.
To achieve the above object, the technical solution that the present invention takes is as follows：
A kind of high-tap density, high magnification and long-life lithium-rich manganese-based anode material, the chemical formula of the positive electrode is Li
[Lia(MnxNiyCoz)1−a]O2, wherein, 0<a<0.5, x+y+z=1,0≤y<X, 0≤z<x, x<1,0≤y≤0.5,0≤z≤
0.5。
The preparation method of a kind of above-mentioned high-tap density, high magnification and long-life lithium-rich manganese-based anode material, the side
Method step is as follows：
Step 1：Manganese nickel cobalt carbonate spherical precursor is prepared using coprecipitation, is as follows：
（1）By chemical formula Li [Lia(MnxNiyCoz)1−a]O2Weigh the soluble manganese salt of corresponding mol ratio, nickel salt, cobalt salt and one
Quantitative crystal nucleation controlling agent, above-mentioned raw materials are dissolved in deionized water be configured to manganese nickel cobalt total concentration for 0.5 ~ 5 mol/L,
Crystal nucleation controls the solution M that agent concentration is 0.05 ~ 0.5 mol/L；
（2）Carbonate deposition agent and complexing agent are configured to carbonate deposition agent solubility as 0.5 ~ 5 mol/L, network with deionized water
Mixture concentration is the solution B of 0.1 ~ 0.5 mol/L；
（3）Under strong stirring, solution B is added in solution M, control mixed metal salt, crystal nucleation controlling agent, carbonate sink
The molar ratio of shallow lake agent and complexing agent is 1:0.05~0.2:1:0.1 ~ 0.5, low whipping speed is 500 ~ 1500 revs/min, temperature
To react 3 ~ 10 h under conditions of 10 ~ 25 DEG C, manganese nickel cobalt carbonate spherical precursor is obtained；
Step 2：Manganese nickel cobalt carbonate spherical precursor with lithium source is uniformly mixed, is calcined, it is lithium-rich manganese-based just to obtain spherical shape
Pole material, is as follows：
（1）Manganese nickel cobalt carbonate spherical precursor is uniformly mixed with lithium source；
（2）600 ~ 900 DEG C are risen to from room temperature with 1 ~ 5 DEG C/min heating rates, calcines 6 ~ 15 h, it is lithium-rich manganese-based just to obtain spherical shape
Pole material；
Step 3：Spherical lithium-rich manganese-based anode material is subjected to hydro-thermal post processing, is as follows：
（1）A certain amount of spherical lithium-rich manganese-based anode material is added in deionized water, it is 1 to control solid-liquid mass ratio:1 ~ 5, it will
Mixing solid-liquid is put into the stainless steel water heating kettle that liner is polytetrafluoroethylene (PTFE), at the hydro-thermal for carrying out certain time at a certain temperature
Reason；
（2）Collection is filtered to sample after reaction, and is put into Muffle furnace, 100 ~ 300 oC12 h are dried in air,
Obtain high-tap density, high magnification and long-life lithium-rich manganese-based anode material.
The present invention is compared with the advantageous effect of the prior art：
（1）The present invention reduces the crystal surface energy of co-precipitation system by the collective effect of crystal nucleation controlling agent and complexing agent,
In the case where pH value and cryogenic conditions need not be adjusted（10~25℃）Realize the quick preparation of dense spherical lithium-rich manganese-based anode material（3~
10 h）, the grain size of material is about 3 ~ 5 μm, and tap density is 2.4 ~ 2.8 g/cm3, active material load capacity is high during coating（>8
mg/cm2）.
（2）High discharge capacity is provided using the more metal synergistic effects of manganese nickel cobalt（Capacity is up to 270 ~ 310 mAh/ under 0.1C
g）, hydro-thermal solid liquid interface reaction reduction second particle surface nickel lithium mixing layer thickness（<3 nm）With reducing surface nickel lithium mixing ratio
Example（<2%）, so as to improve lithium ion diffusion coefficient（>7.0×10-13 cm2/s）, reinforcing material rate capability（Capacity can under 1 C
Up to 220 ~ 260 mAh/g, capacity is up to 150 ~ 190 mAh/g under 5 C, and capacity is up to 110 ~ 150 mAh/g under 10 C）, promoted
The cycle performance of material（Capacity retention ratio is all higher than 85% after lower 200 Xun Huans of 1 C, lower 400 Xun Huans of 3 C）.
（3）Present invention process is simple, performance boost is substantially reliable, is suitble to large-scale production.
Description of the drawings
Fig. 1 is the SEM figures of positive electrode prepared by the present invention.
Fig. 2 is the XRD diagram of positive electrode prepared by the present invention.
Fig. 3 is the STEM figures of secondary particle surface before the hydro-thermal process of positive electrode prepared by the present invention.
Fig. 4 is the STEM enlarged drawings of secondary particle surface before the hydro-thermal process of positive electrode prepared by the present invention.
Fig. 5 is the STEM figures on second particle surface after the hydro-thermal process of positive electrode prepared by the present invention.
Fig. 6 is the STEM enlarged drawings on second particle surface after the hydro-thermal process of positive electrode prepared by the present invention.
Fig. 7 is the high rate performance graph of positive electrode button electricity prepared by the present invention.
Fig. 8 is the capacity curve figure that positive electrode button electricity prepared by the present invention cycles 200 times under 1 C.
Fig. 9 is the capacity curve figure that positive electrode button electricity prepared by the present invention cycles 400 times under 3 C.
Specific embodiment
Technical scheme is further described with reference to the accompanying drawings and examples, but is not limited thereto,
It is every that technical solution of the present invention is modified or replaced equivalently, without departing from the spirit and scope of technical solution of the present invention,
It should all cover in protection scope of the present invention.
Specific embodiment one：What present embodiment was recorded is a kind of high-tap density, high magnification and long-life richness lithium manganese
Base anode material, the chemical formula of the positive electrode is Li [Lia(MnxNiyCoz)1−a]O2, wherein, 0<a<0.5, x+y+z=1,0
≤y<X, 0≤z<x, x<1,0≤y≤0.5,0≤z≤0.5.
Specific embodiment two：High-tap density, high magnification and long-life richness lithium described in a kind of specific embodiment one
The preparation method of manganese-based anode material, the method being combined using co-precipitation, high temperature sintering with hydro-thermal reaction, the method step
It is as follows：
Step 1：Manganese nickel cobalt carbonate spherical precursor is prepared using coprecipitation, is as follows：
（1）By chemical formula Li [Lia(MnxNiyCoz)1−a]O2Weigh the soluble manganese salt of corresponding mol ratio, nickel salt, cobalt salt and one
Quantitative crystal nucleation controlling agent, above-mentioned raw materials are dissolved in deionized water be configured to manganese nickel cobalt total concentration for 0.5 ~ 5 mol/L,
Crystal nucleation controls the solution M that agent concentration is 0.05 ~ 0.5 mol/L；
（2）Carbonate deposition agent and complexing agent are configured to carbonate deposition agent solubility as 0.5 ~ 5 mol/L, network with deionized water
Mixture concentration is the solution B of 0.1 ~ 0.5 mol/L；
（3）Under strong stirring, solution B is added in solution M, control mixed metal salt, crystal nucleation controlling agent, carbonate sink
The molar ratio of shallow lake agent and complexing agent is 1:0.05~0.2:1:0.1 ~ 0.5, low whipping speed is 500 ~ 1500 revs/min, temperature is
3 ~ 10 h are reacted under conditions of 10 ~ 25 DEG C, obtain manganese nickel cobalt carbonate spherical precursor；
Step 2：Manganese nickel cobalt carbonate spherical precursor with lithium source is uniformly mixed, is calcined, it is lithium-rich manganese-based just to obtain spherical shape
Pole material, is as follows：
（1）Manganese nickel cobalt carbonate spherical precursor is uniformly mixed with lithium source；
（2）600 ~ 900 DEG C are risen to from room temperature with 1 ~ 5 DEG C/min heating rates, calcines 6 ~ 15 h, it is lithium-rich manganese-based just to obtain spherical shape
Pole material；
Step 3：Spherical lithium-rich manganese-based anode material is subjected to hydro-thermal post processing, is as follows：
（1）A certain amount of spherical lithium-rich manganese-based anode material is added in deionized water, it is 1 to control solid-liquid mass ratio:1 ~ 5, it will
Mixing solid-liquid is put into the stainless steel water heating kettle that liner is polytetrafluoroethylene (PTFE), at the hydro-thermal for carrying out certain time at a certain temperature
Reason；
（2）Collection is filtered to sample after reaction, and is put into Muffle furnace, 100 ~ 300 oC12 h are dried in air,
Obtain hydro-thermal process lithium-rich manganese-based anode material, i.e. high-tap density, high magnification and long-life lithium-rich manganese-based anode material.
Specific embodiment three：A kind of high-tap density, high magnification and long-life richness lithium described in specific embodiment two
The preparation method of manganese-based anode material, in step 1, the manganese salt is manganese sulfate, formic acid manganese, manganese acetate, manganese oxalate, manganese chloride
Or one or more mixtures in manganese nitrate；The nickel salt for nickel sulfate, nickel formate, nickel acetate, nickel oxalate, nickel chloride or
One or more mixtures in nickel nitrate；The cobalt salt is cobaltous sulfate, cobaltous formate, cobalt acetate, cobalt oxalate, cobalt chloride or nitre
One or more mixtures in sour cobalt；The crystal nucleation controlling agent leads to for Qula, polyvinylpyrrolidone, cetyl
One or more mixtures of trimethylammonium bromide, polyvinyl alcohol；The carbonate deposition agent for sodium carbonate, sodium acid carbonate,
One or more mixtures in ammonium carbonate；The complexing agent is one in ammonium hydrogen carbonate, ammonium hydrogen sulfate, ammonium sulfate, ammonium hydroxide
Kind or a variety of mixtures.
Specific embodiment four：A kind of high-tap density, high magnification and long-life richness lithium described in specific embodiment two
The preparation method of manganese-based anode material, in step 2, the lithium source is lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, formic acid
One or more mixtures in lithium, lithium carbonate, lithium chloride；The manganese nickel cobalt carbonate spherical precursor is mixed with lithium source
When the hybrid mode taken be liquid phase mixing or solid phase mixing, liquid phase mixed solvent is absolute ethyl alcohol, total solid salt and solvent
Mass ratio is 1:1.
Specific embodiment five：A kind of high-tap density, high magnification and long-life richness lithium described in specific embodiment two
The preparation method of manganese-based anode material, in step 3, the hydro-thermal process temperature is 120 ~ 220oC；The hydro-thermal process
Time is 5 ~ 10 h.
Specific embodiment six：A kind of high-tap density, high magnification and long-life richness lithium described in specific embodiment two
The preparation method of manganese-based anode material, Step 2: in three, the lithium-rich manganese-based anode material has fine and close spherical structure,
Grain size is 3 ~ 5 μm, and tap density is 2.4 ~ 2.8 g/cm3。
Embodiment 1：
Mn in molar ratio:Ni:Co = 0.54:0.13:0.13 weighs manganese sulfate, nickel sulfate, cobaltous sulfate, and weighs a certain amount of
Crystal nucleation controlling agent（Polyvinylpyrrolidone）, above-mentioned raw materials are dissolved in deionized water and is configured to manganese nickel cobalt total concentration and is
0.5 mol/L, crystal nucleation control the solution M that agent concentration is 0.05 mol/L, using the method for co-precipitation by 0.5 mol/L carbon
The solution of sour sodium precipitating reagent, 0.2 mol/L complexing agents（Ammonium hydrogen carbonate）It adds in above-mentioned solution M, control mixed metal salt, crystal
The molar ratio for being nucleated controlling agent, carbonate deposition agent and complexing agent is 1:0.1:1:0.2, mixing speed is 1200 revs/min, temperature
5 h of conditioned response for 20 DEG C is spent, filters, washs repeatedly after reaction, impurity is removed, manganese nickel cobalt carbonate is obtained after dry
Spherical precursor.In molar ratio 1.2:0.8 weighs lithium carbonate mixes with manganese nickel cobalt carbonate spherical precursor and homogeneous solid, will
It is put into Muffle furnace air atmosphere, is risen to 800 DEG C of 10 h of calcining from room temperature with 5 DEG C/min heating rates, is obtained spherical richness
Lithium manganese-based anode material.A certain amount of spherical lithium-rich manganese-based anode material is added in deionized water, it is 1 to control solid-liquid mass ratio:
2, solid-liquid will be mixed and be put into the stainless steel water heating kettle that liner is polytetrafluoroethylene (PTFE), 180oThe hydro-thermal process of 6 h is carried out under C,
Collection is filtered to sample after reaction, and in Muffle furnace 200 oC12 h are dried in air, obtain hydro-thermal process richness lithium manganese
Sill, i.e. high-tap density, high magnification and long-life lithium-rich manganese-based anode material.Chemical formula is
Li1.2Mn0.54Ni0.13Co0.13O2.As shown in Figure 1, spherical shape lithium-rich manganese-based anode material manufactured in the present embodiment has homogeneous ball
Shape pattern, it is about 3 μm to be embodied in the spherical grain size of material, about 2.6 g/cm of tap density3.As shown in Figure 2, this implementation
There is superlattices characteristic peak in the XRD curves that example prepares material, and it is lithium-rich manganese base material to illustrate synthetic material.As shown in Figure 3,4, it is former
Sub- scale high resolution scanning transmission electron microscope shows the nickel lithium mixing of about 3 nm of material secondary particle surface presence before hydro-thermal process
Layer, nickel lithium mixing ratio are 3.5 %.As shown in Figure 5,6, hydro-thermal process rear surface nickel lithium mixing layer<0.5 nm, nickel lithium mixing ratio
Example is 1.3 %.The lithium ion diffusion system of high-tap density, high magnification and long-life lithium-rich manganese-based anode material obtained by hydro-thermal process
Number is 7.9 × 10-13 cm2/s.Under 0.1 C, resulting materials 2 ~ 4.8 V specific discharge capacity up to 301 mAh/g；Such as Fig. 7
Shown in high rate performance curve, the present embodiment prepare material specific discharge capacity under 1,3,5,10 C respectively may be about 248,201,163,
133 mAh/g；As shown in figure 8, it is 91.5% that capacity retention ratio after 200 Xun Huans is carried out under 1C；As shown in figure 9, under 3C into
Capacity retention ratio is 89.0% after 400 Xun Huans of row.
Embodiment 2：
Mn in molar ratio:Ni:Co = 0.5:0.15:0.1 weighs manganese sulfate, nickel nitrate, cobalt acetate, and weighs a certain amount of crystalline substance
Body is nucleated controlling agent（Cetyl trimethylammonium bromide：Polyvinyl alcohol=1:1 mol/mol）, above-mentioned raw materials are dissolved in deionization
It is configured to that manganese nickel cobalt total concentration is 1 mol/L, crystal nucleation controls the solution M that agent concentration is 0.2 mol/L in water, use is coprecipitated
The method in shallow lake is by 2 mol/L precipitating reagents（Sodium acid carbonate：Ammonium carbonate=1:1 mol/mol）, 1 mol/L complexing agents solution（Carbonic acid
Hydrogen ammonium：Ammonium hydroxide=1:2 mol/mol）It adds in above-mentioned solution M, control mixed metal salt, crystal nucleation controlling agent, carbonate sink
The molar ratio of shallow lake agent and complexing agent is 1:0.05:1:0.4, the condition that mixing speed is 1000 revs/min, temperature is 10 DEG C is anti-
8 h are answered, are filtered after reaction, are washed repeatedly, impurity is removed, manganese nickel cobalt carbonate spherical precursor is obtained after dry.Massage
That ratio 1.25:0.75 weighs lithium carbonate and manganese nickel cobalt carbonate spherical precursor and uniformly mixes, and hybrid mode is liquid phase mixing,
Liquid phase mixed solvent is absolute ethyl alcohol, and the mass ratio of total solid salt and solvent is 1:1, it puts it into Muffle furnace air atmosphere,
900 DEG C of 12 h of calcining are risen to from room temperature with 3 DEG C/min heating rates, obtain spherical lithium-rich manganese-based anode material.It will be a certain amount of
Spherical lithium-rich manganese-based anode material add in deionized water, control solid-liquid mass ratio as 1:5, mixing solid-liquid is put into liner is
In the stainless steel water heating kettle of polytetrafluoroethylene (PTFE), 160oThe hydro-thermal process of 5 h is carried out under C, sample was carried out after reaction
Filter is collected, and in Muffle furnace 250 oC12 h are dried in air, obtain hydro-thermal process lithium-rich manganese base material, i.e. high-tap density, height
Multiplying power and long-life lithium-rich manganese-based anode material.Chemical formula is Li1.25Mn0.5Ni0.15Co0.1O2.It is manufactured in the present embodiment spherical rich
Lithium manganese-based anode material has homogeneous spherical morphology, and it is about 4 μm to be embodied in the spherical grain size of material, tap density about 2.5
g/cm3.There is superlattices characteristic peak in the XRD curves that the present embodiment prepares material, and it is lithium-rich manganese base material to illustrate synthetic material.It is former
Before sub- scale high resolution scanning transmission electron microscope shows hydro-thermal process there are about 5 nm nickel lithium mixing layers in material secondary particle surface,
Nickel lithium mixing ratio be 5.5 %, hydro-thermal process rear surface nickel lithium mixing layer<2 nm, nickel lithium mixing ratio are 1.8 %.At hydro-thermal
The lithium ion diffusion coefficient of reason gained high-tap density, high magnification and long-life lithium-rich manganese-based anode material is 7.3 × 10-13
cm2/s.Under 0.1 C, resulting materials 2 ~ 4.8 V specific discharge capacity up to 285 mAh/g；The present embodiment prepares material and exists
1st, specific discharge capacity respectively may be about 236,191,153,115 mAh/g under 3,5,10 C；Carry out capacity after cycling under 1C 200 times
Conservation rate is 89.5%；Capacity retention ratio is 87.4% after 400 Xun Huans are carried out under 3C.
Embodiment 3：
Mn in molar ratio:Ni:Co = 0.7:0.15:0.05 weighs manganese chloride, nickel nitrate, cobaltous sulfate, and weighs a certain amount of crystalline substance
Body is nucleated controlling agent（Qula is led to：Polyvinylpyrrolidone：Polyvinyl alcohol=1:1:1mol/mol）, by above-mentioned raw materials be dissolved in from
It is configured to that manganese nickel cobalt total concentration is 1.5 mol/L, crystal nucleation controls the solution M that agent concentration is 0.05 mol/L in sub- water, adopts
With the method for co-precipitation by 2 mol/L precipitating reagents（Sodium carbonate：Sodium acid carbonate：Ammonium carbonate=1:1:1 mol/mol）、0.5 mol/L
The solution of ammonium hydrogen carbonate complexing agent is added in above-mentioned solution M, control mixed metal salt, crystal nucleation controlling agent, carbonate deposition
The molar ratio of agent and complexing agent is 1:0.2:1:0.3, the conditioned response 5 that mixing speed is 1000 revs/min, temperature is 15 DEG C
H is filtered after reaction, is washed repeatedly, removes impurity, manganese nickel cobalt carbonate spherical precursor is obtained after dry.In molar ratio
1.1:0.9 weighs lithium carbonate mixes with manganese nickel cobalt carbonate spherical precursor and homogeneous solid, puts it into Muffle stove air gas
In atmosphere, 850 DEG C of 10 h of calcining are risen to from room temperature with 4 DEG C/min heating rates, obtain spherical lithium-rich manganese-based anode material.By one
Quantitative spherical lithium-rich manganese-based anode material is added in deionized water, and it is 1 to control solid-liquid mass ratio:3, mixing solid-liquid is put into interior
It serves as a contrast in the stainless steel water heating kettle for polytetrafluoroethylene (PTFE), 220oThe hydro-thermal process of 5 h is carried out under C, after reaction to sample into
Row is collected by filtration, and in Muffle furnace 300 oC12 h are dried in air, obtain hydro-thermal process lithium-rich manganese base material, i.e., high vibration density
Degree, high magnification and long-life lithium-rich manganese-based anode material.Chemical formula is Li1.1Mn0.7Ni0.15Co0.05O2.It is manufactured in the present embodiment
Spherical lithium-rich manganese-based anode material has homogeneous spherical morphology, and it is about 5 μm to be embodied in the spherical grain size of material, vibration density
Spend about 2.8 g/cm3.There is superlattices characteristic peak in the XRD curves that the present embodiment prepares material, and it is rich lithium manganese to illustrate synthetic material
Sill.Before atomic scale high resolution scanning transmission electron microscope shows hydro-thermal process there are about 4 nm nickel in material secondary particle surface
Lithium mixing layer, nickel lithium mixing ratio be 4.5 %, hydro-thermal process rear surface nickel lithium mixing layer<1 nm, nickel lithium mixing ratio are 1.5
%.The lithium ion diffusion coefficient of high-tap density, high magnification and long-life lithium-rich manganese-based anode material obtained by hydro-thermal process is 7.6
×10-13 cm2/s.Under 0.1 C, resulting materials 2 ~ 4.8 V specific discharge capacity up to 295 mAh/g；It is prepared by the present embodiment
Material specific discharge capacity under 1,3,5,10 C respectively may be about 239,198,154,112 mAh/g；200 Xun Huans are carried out under 1C
Capacity retention ratio is 88.7% afterwards；Capacity retention ratio is 86.9% after 400 Xun Huans are carried out under 3C.
Claims (6)
1. a kind of high-tap density, high magnification and long-life lithium-rich manganese-based anode material, it is characterised in that：The positive electrode
Chemical formula is Li [Lia(MnxNiyCoz)1−a]O2, wherein, 0<a<0.5, x+y+z=1,0≤y<X, 0≤z<x, x<1,0≤y≤
0.5,0≤z≤0.5.
2. the preparation method of a kind of high-tap density described in claim 1, high magnification and long-life lithium-rich manganese-based anode material,
It is characterized in that：The method step is as follows：
Step 1：Manganese nickel cobalt carbonate spherical precursor is prepared using coprecipitation, is as follows：
（1）By chemical formula Li [Lia(MnxNiyCoz)1−a]O2Weigh the soluble manganese salt of corresponding mol ratio, nickel salt, cobalt salt with it is certain
Above-mentioned raw materials are dissolved in deionized water and are configured to manganese nickel cobalt total concentration as 0.5 ~ 5 mol/L, crystalline substance by the crystal nucleation controlling agent of amount
Body nucleation controls the solution M that agent concentration is 0.05 ~ 0.5 mol/L；
（2）Carbonate deposition agent and complexing agent are configured to carbonate deposition agent solubility as 0.5 ~ 5 mol/L, network with deionized water
Mixture concentration is the solution B of 0.1 ~ 0.5 mol/L；
（3）Under strong stirring, solution B is added in solution M, control mixed metal salt, crystal nucleation controlling agent, carbonate sink
The molar ratio of shallow lake agent and complexing agent is 1:0.05~0.2:1:0.1 ~ 0.5, low whipping speed is 500 ~ 1500 revs/min, temperature
To react 3 ~ 10 h under conditions of 10 ~ 25 DEG C, manganese nickel cobalt carbonate spherical precursor is obtained；
Step 2：Manganese nickel cobalt carbonate spherical precursor with lithium source is uniformly mixed, is calcined, it is lithium-rich manganese-based just to obtain spherical shape
Pole material, is as follows：
（1）Manganese nickel cobalt carbonate spherical precursor is uniformly mixed with lithium source；
（2）600 ~ 900 DEG C are risen to from room temperature with 1 ~ 5 DEG C/min heating rates, calcines 6 ~ 15 h, it is lithium-rich manganese-based just to obtain spherical shape
Pole material；
Step 3：Spherical lithium-rich manganese-based anode material is subjected to hydro-thermal post processing, is as follows：
（1）A certain amount of spherical lithium-rich manganese-based anode material is added in deionized water, it is 1 to control solid-liquid mass ratio:1 ~ 5, it will
Mixing solid-liquid is put into the stainless steel water heating kettle that liner is polytetrafluoroethylene (PTFE), at the hydro-thermal for carrying out certain time at a certain temperature
Reason；
（2）Collection is filtered to sample after reaction, and is put into Muffle furnace, 100 ~ 300 oC12 h are dried in air,
Obtain high-tap density, high magnification and long-life lithium-rich manganese-based anode material.
3. the preparation of a kind of high-tap density according to claim 2, high magnification and long-life lithium-rich manganese-based anode material
Method, it is characterised in that：In step 1, the manganese salt is manganese sulfate, formic acid manganese, manganese acetate, manganese oxalate, manganese chloride or manganese nitrate
In one or more mixtures；The nickel salt is in nickel sulfate, nickel formate, nickel acetate, nickel oxalate, nickel chloride or nickel nitrate
One or more mixtures；The cobalt salt is in cobaltous sulfate, cobaltous formate, cobalt acetate, cobalt oxalate, cobalt chloride or cobalt nitrate
One or more mixtures；The crystal nucleation controlling agent leads to for Qula, polyvinylpyrrolidone, cetyl trimethyl bromine
Change one or more mixtures of ammonium, polyvinyl alcohol；The carbonate deposition agent is sodium carbonate, in sodium acid carbonate, ammonium carbonate
One or more mixtures；The complexing agent is ammonium hydrogen carbonate, the one or more in ammonium hydrogen sulfate, ammonium sulfate, ammonium hydroxide
Mixture.
4. the preparation of a kind of high-tap density according to claim 2, high magnification and long-life lithium-rich manganese-based anode material
Method, it is characterised in that：In step 2, the lithium source is lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, lithium formate, carbonic acid
One or more mixtures in lithium, lithium chloride；The manganese nickel cobalt carbonate spherical precursor is taken when being mixed with lithium source
Hybrid mode mixed for liquid phase or solid phase mixing, liquid phase mixed solvent is absolute ethyl alcohol, the mass ratio of total solid salt and solvent
For 1:1.
5. the preparation of a kind of high-tap density according to claim 2, high magnification and long-life lithium-rich manganese-based anode material
Method, it is characterised in that：In step 3, the hydro-thermal process temperature is 120 ~ 220oC；The hydrothermal conditions are 5
~10 h。
6. the preparation of a kind of high-tap density according to claim 2, high magnification and long-life lithium-rich manganese-based anode material
Method, it is characterised in that：Step 2: in three, the lithium-rich manganese-based anode material grain size is 3 ~ 5 μm, tap density for 2.4 ~
2.8 g/cm3。
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| CN108832118A (en) * | 2018-06-25 | 2018-11-16 | 西南交通大学 | MnO2The preparation method of intermediate and preparation method thereof and lithium-rich manganese-based anode material |
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