CN107204429A - The preparation method and anode material for lithium-ion batteries and lithium ion battery of nickel-cobalt-manganese ternary material - Google Patents
The preparation method and anode material for lithium-ion batteries and lithium ion battery of nickel-cobalt-manganese ternary material Download PDFInfo
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- 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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- H01M4/525—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 belongs to technical field of lithium ion, it is related to the preparation method and anode material for lithium-ion batteries and lithium ion battery of a kind of nickel-cobalt-manganese ternary material.A kind of preparation method for nickel-cobalt-manganese ternary material that the present invention is provided, comprises the following steps：(a) ternary material precursor, lithium compound and solvent are mixed, obtains compound；(b) compound is subjected to ball milling, obtains hybrid particles A；(c) the hybrid particles A is spray-dried, obtains mixed material B；(d) the mixed material B is sintered, obtains nickel-cobalt-manganese ternary material.The nickel-cobalt-manganese ternary material tap density that the present invention is prepared is high, and uniformity is good, and granularity is controllable, and performance is stable, and with excellent physically and electrically chemical property, the nickel-cobalt-manganese ternary material can be used as anode material for lithium-ion batteries.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to the preparation method and lithium of a kind of nickel-cobalt-manganese ternary material
Ion battery positive electrode and lithium ion battery.
Background technology
In existing secondary cell system, no matter from development space, or from the life-span, specific energy, operating voltage and from
From the point of view of the technical indicators such as discharge rate, lithium ion battery is all current most competitive secondary cell.And the pass of lithium ion battery
Key material is positive electrode, accounts for the 30% of lithium ion battery cost.The positive electrode that lithium ion battery is used in the market
Mainly there are cobalt acid lithium, LiFePO4, LiMn2O4 and ternary material etc..Ternary material is a kind of new cell positive material, with
The other materials such as cobalt acid lithium are compared, with specific discharge capacity height, good heat endurance, good cycle, operating temperature be wide, energy is close
The advantages of spending big.Good combination property so that ternary material turns into the main flow of existing market, and most potential one kind electricity
Pond positive electrode, has good application scenarios in fields such as digital electronic goods, electric bicycle, electric tools.
At present, after the preparation method of ternary material is mainly mixed using presoma with lithium source dry or wet, burnt through high temperature
Tie, crush, except iron, sieving packaging, ternary material being made, nickel cobalt manganese hydroxide is a kind of persursor material of good performance,
Now it is widely used.And nickel cobalt manganese hydroxide precursor is to the sintering process of ternary material and the physics and chemistry of ternary material and electrically
Energy index has important influence.
The size distribution of ternary material depends mainly on the size distribution of ternary material precursor, so ternary material is to three
The size distribution requirements of first material precursor have very high requirement.The life of current ternary material precursor (nickel cobalt manganese hydroxide)
Production predominantly control crystalline co-precipitate method, one-pot quantity-produced pattern.However, in ternary material precursor production process, shadow
The technological parameter for ringing granularity is more, for example：Nickel cobalt manganese salinity, reactor bottom liquid caustic soda concentration, reactor bottom liquid temperature degree, nickel cobalt manganese
Salt adds solution ph control, reactor mixing speed etc. when speed, nickel cobalt manganese salt are added can have to presoma size distribution
Influence.Numerous affecting parameters cause ternary material precursor size distribution disqualification rate higher, and grain diameter is difficult to control, no
The waste of ample resources is only caused, increases unnecessary production cost, and directly affect shaking for anode material for lithium-ion batteries
Real density, cycle performance etc. so that the stability of final products is difficult to control to.
In consideration of it, special propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of preparation method of nickel-cobalt-manganese ternary material, and this method is not only reduced
To the size distribution requirements of ternary material precursor, and the homogeneity of ternary material size distribution is improved, uniformity is good, grain
Degree is controllable, it is ensured that ternary material possesses excellent physically and electrically chemical property.
The second object of the present invention is to provide a kind of anode material for lithium-ion batteries, above-mentioned nickel-cobalt-manganese ternary material is made
Used for anode material for lithium-ion batteries, good with uniformity, granularity is controllable, performance is stable, and physically and electrically chemical property is good
Advantage.
The third object of the present invention is to provide a kind of lithium ion battery, and the performance of lithium ion battery is stable, physically and electrically
Chemical property is excellent.
To achieve the above object, the technical solution adopted by the present invention is：
According to an aspect of the present invention, the present invention provides a kind of preparation method of nickel-cobalt-manganese ternary material, including following
Step：
(a) ternary material precursor, lithium compound and solvent are mixed, obtains compound；
(b) compound is subjected to ball milling, obtains hybrid particles A；
(c) the hybrid particles A is spray-dried, obtains mixed material B；
(d) the mixed material B is sintered, obtains nickel-cobalt-manganese ternary material.
As further preferred technical scheme, in the step (a), the chemical formula of the ternary material precursor is
NixCoyMnz(OH)2, wherein 0.3≤x≤1,0≤y≤0.3,0≤z≤0.3, and x+y+z=1.
As further preferred technical scheme, in the step (a), the ternary material precursor and Li in lithium compound
Mol ratio be 1：1~1：1.07；
The solid content of the compound is controlled between 10%~70%.
As further preferred technical scheme, in the step (b), the mode of ball milling is pre- first to be carried out using Ball-stirring mill
Mill, then fine grinding is carried out using sand mill.
As further preferred technical scheme, the time of Ball-stirring mill progress pre-grinding is used for 0.5h~10h, using sand mill
The time for carrying out fine grinding is 0.5h~20h；
Or, with voltameter, pre-grinding 0.1kwh/kg~20kwh/kg is carried out using Ball-stirring mill, carried out using sand mill thin
Grind 0.5kwh/kg~20kwh/kg.
As further preferred technical scheme, in the step (c), it is spray-dried using drying machine with centrifugal spray,
The rotating speed of atomizer is 5000rpm~30000rpm；Or, it is spray-dried using Pressuresprayingdrier, atomizing pressure
For 0.05Mpa~0.75MPa；
Preferably, the EAT of the spray drying is 100 DEG C~350 DEG C, and leaving air temp is 60 DEG C~160 DEG C.
As further preferred technical scheme, in the step (d), described sintering temperature is 750 DEG C~1200 DEG C, is burnt
The knot time is 2h~20h；
Preferably, in described sintering process, 750 DEG C~1200 are risen to 2 DEG C/min~20 DEG C/min heating rate
DEG C, and constant temperature 2h~15h, then room temperature is cooled to 5 DEG C/min~100 DEG C/min rate of temperature fall；
Preferably, in described sintering process, gas dew point Td is controlled between -100 DEG C~-5 DEG C, and gas flow is
0.1L/min/kg~2L/min/kg；
Preferably, described sintering atmosphere is the one or more in oxygen, air or compressed air.
As further preferred technical scheme, the lithium compound includes oxide, halide, hydroxide, the carbon of lithium
One or more in hydrochlorate, nitrate, acetate and oxalates；
Preferably, the solvent is deionized water or ethanol water.
According to another aspect of the present invention, the present invention also provides a kind of anode material for lithium-ion batteries, by above-mentioned technology
The nickel-cobalt-manganese ternary material that preparation method described in scheme is obtained is as anode material for lithium-ion batteries.
As further preferred technical scheme, the chemical formula of described nickel-cobalt-manganese ternary material is LiαNixCoyMnzO2, its
In 1≤α≤1.07,0.3≤x≤1,0≤y≤0.3,0≤z≤0.3, and x+y+z=1；In ball-type and/or class ball-type.
According to another aspect of the present invention, the present invention also provides a kind of lithium ion battery, including housing, is placed in housing
Positive pole, negative pole, barrier film and electrolyte, the barrier film be located between the positive pole and negative pole, the positive pole include it is described above
Anode material for lithium-ion batteries.
Compared with prior art, the beneficial effects of the present invention are：
1st, the preparation method of nickel-cobalt-manganese ternary material that the present invention is provided, by ternary material precursor, lithium compound and
Ball milling is carried out after solvent mixing, the problem of doping of dry method batch mixing is uneven is not only solved, and ideal has been reached by ball milling
The mixing of state and cause material particle size it is uniform；Then ternary material precursor and lithium compound are carried out by being spray-dried
Granulate again, the size distribution of ternary material can be adjusted in the process, prepare the ternary material of stoichiometric proportion, and energy
Ensure that lithium ion is uniformly embedded into presoma during follow-up sintering；Material after spray-dried is sintered again, is further improved
The processing characteristics of material, it is ensured that the uniformity of pole piece in cell manufacturing process.The material that this method is prepared, uniformity is good, grain
Degree is controllable, and second particle good dispersion, size is homogeneous, improves the tap density and energy density per unit volume of material, improves material
High rate performance, so as to improve the chemical property of material so that material has good combination property.
Compared with the ternary material of different grain size distribution is produced by adjusting presoma size distribution, the granularity point of this method
Cloth adjustment is easier to realization, the size distribution requirements to presoma is reduced to the full extent, and can produce with high-performance
Nickel-cobalt-manganese ternary material.
2nd, the inventive method not only has the advantages that cleaning, efficient, low cost, and grain diameter is easily controlled, produced
Final products stability is good, is easy to steady production；And it is environment-friendly, simple to operate, production efficiency is high, without using complexity
Device systems, easily realize industrialization large-scale production, industrially applicable.
3rd, the nickel-cobalt-manganese ternary material tap density that the present invention is prepared is high, and uniformity is good, and granularity is controllable, and performance is steady
Fixed, with excellent physically and electrically chemical property, the nickel-cobalt-manganese ternary material can be used as anode material for lithium-ion batteries.This
The lithium ion battery that invention is provided includes the anode material for lithium-ion batteries, and energy density is high, with excellent physically and electrically change
Learn performance.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The accompanying drawing used required in embodiment or description of the prior art is briefly described, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 schemes (Scanning Electron for the SEM of nickel-cobalt-manganese ternary material provided in an embodiment of the present invention
Microscope scanning electron microscope (SEM) photographs)；
Fig. 2 is the charging and discharging curve figure (potential region of nickel-cobalt-manganese ternary material provided in an embodiment of the present invention：3.0-
4.25V, 0.1C multiplying power), abscissa is charging and discharging capacity (mAh/g), and ordinate is charging/discharging voltage scope (V)；
SEM figures (the Scanning Electron for the nickel-cobalt-manganese ternary material that Fig. 3 provides for comparative example of the present invention
Microscope scanning electron microscope (SEM) photographs).
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment and embodiment, but this area skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and are not construed as the model of the limitation present invention
Enclose.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.Actual conditions person is indicated, is advised according to normal condition or manufacturer
Condition carry out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional products that can be obtained by commercially available purchase.
In a first aspect, present embodiment provides a kind of preparation method of nickel-cobalt-manganese ternary material, comprise the following steps：
(a) ternary material precursor, lithium compound and solvent are mixed, obtains compound；
(b) compound is subjected to ball milling, obtains hybrid particles A；
(c) the hybrid particles A is spray-dried, obtains mixed material B；
(d) the mixed material B is sintered, obtains nickel-cobalt-manganese ternary material.
Pass through the mixing speed during control preparation ternary material precursor, reaction temperature, alkali mostly in the prior art
The mode of the technological parameters such as liquid concentration, to control the particle diameter distribution of presoma, so that affect the size distribution of ternary material
Homogeneity, tap density etc.；And which needs the parameter controlled more, higher size distribution disqualification rate is easily caused,
Grain diameter is not easily controlled so that the chemical property of final products cannot be ensured, stability is difficult to control to.In view of
This, the present invention provides a kind of preparation method of nickel-cobalt-manganese ternary material, and lithium, ball milling, spray drying and sintering are mixed by wet method
Mode, reduces the size distribution requirements to presoma, with producing what different grain size was distributed by adjusting presoma size distribution
Ternary material is compared, and method size distribution adjustment of the invention is easier to realize, it is achieved thereby that granularity controllability is good, is easy to steady
Fixed production, the performance of product is stable, the good technique effect of chemical property.
Concretely, preparation method of the invention, first passes through ternary material precursor, lithium compound and solvent wet-mixing
Mode, solve dry method batch mixing easily adulterate uneven and grain diameter it is whard to control the problem of；Ball milling is then carried out, is led to
Ball milling is crossed further to have reached the mixing of perfect condition and make it that material particle size is uniform；Again will by spray drying after ball milling
Ternary material precursor is granulated again with lithium compound, and the size distribution of ternary material can be adjusted in the process, system
For the ternary material for going out stoichiometric proportion, and lithium ion is uniformly embedded into presoma when can guarantee that follow-up sintering；It is spray-dried
Material afterwards is sintered again, further improves the processing characteristics of material, it is ensured that the uniformity of pole piece in cell manufacturing process.
The present invention controls the pattern and particle diameter of material using the means of physics, improves the stability of material, wherein ball
The special process that the means such as mill and spray drying are provided to the optimal pattern of guarantee material acquisition and size distribution and set.This
Invention mixes lithium, ball milling by wet method, is spray-dried and sinters the mutual cooperation of several steps so that the ternary material one prepared
Cause property is good, and granularity is controllable, second particle good dispersion, and size is homogeneous, improves the chemical property of material so that material has
Good combination property.
In a kind of optional embodiment, in the step (a), the chemical formula of the ternary material precursor is
NixCoyMnz(OH)2, wherein 0.3≤x≤1,0≤y≤0.3,0≤z≤0.3, and x+y+z=1.
In three kinds of components of ternary material, influence of the various elements to material is different, in general, nickel (Ni) element
Content is related to the capacity of material, and Ni constituent contents are higher, and the gram volume of whole multi-element composite material system is higher, but Ni contains
Measuring the cycle performance and heat endurance of too high whole material will decline.The layer structure development of cobalt (Co) constituent content and material
Related to electrical conductivity, Co constituent contents are higher, and whole positive electrode system electrical conductivity is higher, and the layer structure of material is better, but
It is that Co too high levels will increase the preparation cost of polynary positive pole material, while the heat endurance of material can also decline.Manganese (Mn)
The content of element is related to the heat endurance of material, and Mn contents are higher, and the cycle performance of material is better, and heat endurance is higher, but
Mn elements are too high, and material capacity will be caused to reduce, and are eventually converted into instable Mn3+, influence the cycle performance of material.
Consider case above, present embodiment limits 0.3≤x≤1,0≤y≤0.3,0≤z≤0.3, and x+y+z=1, can
So that material has good combination property and stability.
In a detailed embodiment, optionally, the chemical formula of the ternary material precursor is Ni0.6Co0.2Mn0.2
(OH)2。
In a detailed embodiment, optionally, the chemical formula of the ternary material precursor is Ni0.5Co0.3Mn0.2
(OH)2。
In a detailed embodiment, optionally, the chemical formula of the ternary material precursor is Ni0.8Co0.1Mn0.1
(OH)2。
In a detailed embodiment, optionally, the chemical formula of the ternary material precursor is Ni0.3Co0.3Mn0.3
(OH)2.It should be noted that according to the conventional literary style of this area, x, y, z is written as 0.3 herein, and actually x, y, z is
0.333rd, 0.333,0.333, the summation of x, y, z is still 1.
In a kind of optional embodiment, in the step (a), the ternary material precursor and Li in lithium compound
Mol ratio be 1：1~1：1.07；
The solid content of the compound is controlled between 10%~70%.
In operating process, ternary material precursor, lithium compound and solvent are weighed according to a certain percentage, before ternary material
The lithium compound for driving body and respective amount is together added in stirring container, while adding solvent, is expanded through a period of time stirring or liquid phase
After dissipating uniformly, compound is obtained, then ball milling is carried out to compound.
In a detailed embodiment, optionally, the ternary material precursor and the mol ratio of Li in lithium compound
For 1：1、1：1.01、1：1.02、1：1.03、1：1.04、1：1.05、1：1.06 or 1：1.07.
In a detailed embodiment, optionally, the solid content control of the compound 10%, 20%, 30%,
40%th, 50%, 60% or 70%.
In a kind of optional embodiment, in the step (b), the mode of ball milling is pre- first to be carried out using Ball-stirring mill
Mill, then fine grinding is carried out using sand mill.
In a kind of optional embodiment, the time of Ball-stirring mill progress pre-grinding is used for 0.5h~10h, using sand mill
The time for carrying out fine grinding is 0.5h~20h；
Or, with voltameter, pre-grinding 0.1kwh/kg~20kwh/kg is carried out using Ball-stirring mill, carried out using sand mill thin
Grind 0.5kwh/kg~20kwh/kg.
First by the way of Ball-stirring mill progress pre-grinding carries out fine grinding using sand mill again, not only production efficiency is high, and cost is low,
Continuity is strong, and controllability is strong, and product fineness is high, granular size more uniform, good mixing effect, be easy to obtain it is homogeneous and
The product of excellent quality.Wherein, kwh/kg is electric quantity unit, represent kilowatt hour/kilogram.
In a detailed embodiment, optionally, use Ball-stirring mill carry out pre-grinding time for 0.5h, 1h, 2h, 3h,
4h, 5h, 6h, 7h, 8h, 9h or 10h；Use sand mill carry out fine grinding time for 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h,
8h, 9h, 10h, 11h, 12h, 14h, 15h, 16h, 17h, 18h, 19h or 20h.
In a detailed embodiment, optionally, using Ball-stirring mill carry out pre-grinding 0.1kwh/kg, 0.5kwh/kg,
1kwh/kg、2kwh/kg、3kwh/kg、4kwh/kg、5kwh/kg、6kwh/kg、7kwh/kg、8kwh/kg、9kwh/kg、
10kwh/kg, 12kwh/kg, 14kwh/kg, 15kwh/kg, 16kwh/kg, 18kwh/kg or 20kwh/kg；Entered using sand mill
Row fine grinding 0.5kwh/kg, 1kwh/kg, 2kwh/kg, 3kwh/kg, 4kwh/kg, 5kwh/kg, 6kwh/kg, 7kwh/kg, 8kwh/
Kg, 9kwh/kg, 10kwh/kg, 12kwh/kg, 14kwh/kg, 15kwh/kg, 16kwh/kg, 18kwh/kg or 20kwh/kg.
In a kind of optional embodiment, in the step (c), it is spray-dried using drying machine with centrifugal spray,
The rotating speed of atomizer is 5000rpm~30000rpm；Or, it is spray-dried using Pressuresprayingdrier, atomizing pressure
For 0.05Mpa~0.75MPa；
Preferably, the EAT of the spray drying is 100 DEG C~350 DEG C, and leaving air temp is 60 DEG C~160 DEG C.
Secondary granulation is carried out by being spray-dried, size distribution is adjusted so that material secondary particle dispersion is good,
Size is homogeneous, with the good uniformity；The diffusion rate of lithium ion can be improved simultaneously, improve the high rate performance of material, from
And improve the chemical property of material.Its mode being spray-dried can select centrifugal spray drying or pressure spray dryer, and enter
Material speed, EAT, leaving air temp etc. granularity difference can be adjusted according to needed for product.
In a detailed embodiment, optionally, the rotating speed of atomizer be 5000rpm, 10000rpm, 15000rpm,
20000rpm, 25000rpm or 30000rpm；Atomizing pressure be 0.05Mpa, 0.10Mpa, 0.15Mpa, 0.20Mpa,
0.25Mpa、0.30Mpa、0.35Mpa、0.40Mpa、0.45Mpa、0.50Mpa、0.55Mpa、0.60Mpa、0.65Mpa、
0.70Mpa or 0.75MPa.
In a detailed embodiment, optionally, EAT be 100 DEG C, 150 DEG C, 200 DEG C, 250 DEG C, 300 DEG C or
350℃；Leaving air temp is 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C or 160 DEG C.
In a kind of optional embodiment, in the step (d), described sintering temperature is 750 DEG C~1200 DEG C, is burnt
The knot time is 2h~20h；
Preferably, in described sintering process, 750 DEG C~1200 are risen to 2 DEG C/min~20 DEG C/min heating rate
DEG C, and constant temperature 2h~15h, then room temperature is cooled to 5 DEG C/min~100 DEG C/min rate of temperature fall；
Preferably, in described sintering process, gas dew point Td is controlled between -100 DEG C~-5 DEG C, and gas flow is
0.1L/min/kg~2L/min/kg；
Preferably, described sintering atmosphere is the one or more in oxygen, air or compressed air.
In sintering process, the fine particle content of material can be controlled, the homogeneity of material particle size distribution is improved, it is ensured that material
Material possesses excellent physically and electrically chemical property.
In a detailed embodiment, optionally, sintering temperature be 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C,
1000 DEG C, 1050 DEG C, 1100 DEG C, 1150 DEG C or 1200 DEG C；Sintering time is 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h
Or 20h.
In a detailed embodiment, optionally, heating rate be 2 DEG C/min, 4 DEG C/min, 6 DEG C/min, 8 DEG C/
Min, 10 DEG C/min, 12 DEG C/min, 14 DEG C/min, 16 DEG C/min, 18 DEG C/min or 20 DEG C/min；Rate of temperature fall be 5 DEG C/min,
10℃/min、20℃/min、30℃/min、40℃/min、50℃/min、60℃/min、70℃/min、80℃/min、90℃/
Min or 100 DEG C/min.
In a detailed embodiment, optionally, gas dew point Td control -100 DEG C, -90 DEG C, -80 DEG C, -
70 DEG C, -60 DEG C, -50 DEG C, -40 DEG C, -30 DEG C, -20 DEG C, -10 DEG C or -5 DEG C；Gas flow be 0.1L/min/kg,
0.2L/min/kg、0.4L/min/kg、0.6L/min/kg、0.8L/min/kg、1L/min/kg、1.2L/min/kg、1.4L/
Min/kg, 1.6L/min/kg, 1.8L/min/kg or 2L/min/kg.
In a kind of optional embodiment, the lithium compound includes oxide, halide, hydroxide, the carbon of lithium
One or more in hydrochlorate, nitrate, acetate and oxalates；
Preferably, the solvent is deionized water or ethanol water.
In a detailed embodiment, optionally, the lithium compound is lithium carbonate, lithium nitrate, lithium hydroxide, oxidation
In one or more in lithium, lithium oxalate, lithium acetate, lithium fluoride or lithium chloride, preferably lithium carbonate, lithium hydroxide and lithium acetate
One kind.The present invention originates without special limitation to lithium compound, using mentioned kind well known to those skilled in the art
Lithium compound；It can such as be bought and obtained by market.
In a detailed embodiment, optionally, the solvent be deionized water or ethanol water, preferably go from
Sub- water.The volume content of ethanol is 10%~90%, preferably 30%~60% in the ethanol water.
It should be noted that the preparation method of the ternary material precursor in the present invention does not have special limitation, using this
Technical scheme known to art personnel, such as prepares ternary material precursor using coprecipitation, successive reaction kettle.
Second aspect, present embodiment also provides a kind of anode material for lithium-ion batteries, by described in above-mentioned technical proposal
The nickel-cobalt-manganese ternary material that preparation method is obtained is as anode material for lithium-ion batteries.The nickel prepared by above-mentioned technical proposal
Cobalt-manganese ternary material is used as anode material for lithium-ion batteries, and this lithium ion anode material has preferable electrochemistry
Energy.
In a kind of optional embodiment, the chemical formula of described nickel-cobalt-manganese ternary material is LiαNixCoyMnzO2, its
In 1≤α≤1.07,0.3≤x≤1,0≤y≤0.3,0≤z≤0.3, and x+y+z=1；In ball-type and/or class ball-type, jolt ramming
Density >=1.80g/cm3。
The present invention is scanned electronic microscope photos test to the nickel-cobalt-manganese ternary material prepared, and test result shows, should
It is mostly spherical morphology that the pattern of ternary material, which is, or is ball-type and/or class ball-type, and uniformity is preferable.Lithium ion battery is just
Pole material can be divided into the positive electrode of stratiform pattern and the positive electrode of spherical morphology, the lithium ion cell positive of spherical morphology
Not only tap density is high for material, and with excellent mobility, dispersiveness and processing characteristics, the lithium-ion electric prepared
Pond has higher volume energy density.
The third aspect, present embodiment also provides a kind of lithium ion battery, including housing, the positive pole, negative that is placed in housing
Pole, barrier film and electrolyte, the barrier film are located between the positive pole and negative pole, and the above-described lithium ion battery of positive pole is just
Pole material.
In present embodiment second aspect and the third aspect, anode material for lithium-ion batteries, which is removed, uses above-mentioned nickel-cobalt-manganese ternary
Beyond material is as active material, remaining composition and structure refer to prior art；Positive pole, negative pole and lithium ion battery structure its
Preparation method refers to routine techniques, with differing only in anode material for lithium-ion batteries added with passing through for routine techniques
The nickel-cobalt-manganese ternary material that the preparation method of nickel-cobalt-manganese ternary material described in first aspect is obtained.
The present invention tests the tap density of the nickel-cobalt-manganese ternary material prepared, test using tap density tester
As a result it is, the tap density >=1.8g/cm for the nickel-cobalt-manganese ternary material that the present invention is obtained3, generally 1.8g/cm3~2.8g/
cm3, tap density is higher.Meanwhile, the nickel-cobalt-manganese ternary material that the present invention is obtained is used as anode material for lithium-ion batteries, test
The chemical property of anode material for lithium-ion batteries, test result is that lithium ion battery carries out discharge and recharge with 20mA/g speed,
Its capacity discharged can reach 150mAh/g~220mAh/g, and discharge and recharge, 50 times~200 times cyclical stabilities of discharge and recharge are good
Good, the anode material for lithium-ion batteries that the present invention is provided has preferable chemical property.
With reference to specific embodiment, comparative example and accompanying drawing, the invention will be further described.
Embodiment 1
A kind of preparation method of nickel-cobalt-manganese ternary material, comprises the following steps：
(a) ternary material precursor Ni is weighed respectively0.5Co0.3Mn0.2(OH)2, lithium compound lithium carbonate and deionized water,
By Ni0.5Co0.3Mn0.2(OH)2With lithium carbonate according to Ni0.5Co0.3Mn0.2(OH)2Mol ratio with Li is 1：1 together adds to stirring
Mix in container, mixed while adding deionized water, obtain compound, the solid content of its compound is controlled 20%；
(b) above-mentioned compound is first subjected to pre-grinding using Ball-stirring mill and carries out ball milling 1h, then fine grinding 2h is carried out using sand mill,
Obtain hybrid particles A；
(c) above-mentioned hybrid particles A is spray-dried using drying machine with centrifugal spray, the rotating speed of atomizer is
20000rpm, EAT is 100 DEG C, and leaving air temp is 60 DEG C, obtains mixed material B；
(d) said mixture material B is sintered under the conditions of oxygen atmosphere, gas dew point Td is controlled in -5 DEG C, gas
Flow is 0.1L/min/kg；750 DEG C, and constant temperature 2h are first risen to 2 DEG C/min heating rate, then with 5 DEG C/min cooling speed
Rate is cooled to room temperature, you can obtain nickel-cobalt-manganese ternary material.
The nickel-cobalt-manganese ternary material obtained to the embodiment of the present invention 1 carries out elementary analysis test, and test result is the nickel cobalt
The molecular formula of manganese ternary material is, LiNi0.5Co0.3Mn0.2O2.The nickel-cobalt-manganese ternary material that the embodiment of the present invention 1 is obtained is carried out
Sem test, test result are as shown in figure 1, the ternary material is spherical morphology, and no fine powder and other small chips are deposited
.The tap density for the nickel-cobalt-manganese ternary material that the embodiment of the present invention 1 is obtained, test result are tested using tap density tester
For the tap density for the nickel-cobalt-manganese ternary material that the present invention is obtained is 2.55g/cm3, tap density is higher.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 1 is obtained tests its electricity as anode material for lithium-ion batteries
Chemical property, its Electrochemical results are as shown in Figure 2.Test result is that charging/discharging voltage scope is 3.0~4.25V, charge and discharge
Electric multiplying power is under conditions of 0.1C, material initial discharge capacity reaches 165.8mAh/g, and capability retention is after 50 circulations
98.9%, capability retention is 98.1% after 100 circulations, and capability retention is 97.2% after 200 circulations.
Embodiment 2
A kind of preparation method of nickel-cobalt-manganese ternary material, comprises the following steps：
(a) ternary material precursor Ni is weighed respectively0.5Co0.3Mn0.2(OH)2, lithium compound lithium carbonate and deionized water,
By Ni0.5Co0.3Mn0.2(OH)2With lithium carbonate according to Ni0.5Co0.3Mn0.2(OH)2Mol ratio with Li is 1：1 together adds to stirring
Mix in container, mixed while adding deionized water, obtain compound, the solid content of its compound is controlled 10%；
(b) above-mentioned compound is first subjected to pre-grinding using Ball-stirring mill and carries out ball milling 10h, then fine grinding is carried out using sand mill
20h, obtains hybrid particles A；
(c) above-mentioned hybrid particles A is spray-dried using drying machine with centrifugal spray, the rotating speed of atomizer is
10000rpm, EAT is 350 DEG C, and leaving air temp is 160 DEG C, obtains mixed material B；
(d) said mixture material B is sintered under the conditions of oxygen atmosphere, gas dew point Td is controlled in -100 DEG C, gas
Body flow is 2L/min/kg；1200 DEG C, and constant temperature 10h are first risen to 20 DEG C/min heating rate, then with 100 DEG C/min's
Rate of temperature fall is cooled to room temperature, you can obtain nickel-cobalt-manganese ternary material.
The nickel-cobalt-manganese ternary material obtained to the embodiment of the present invention 2 carries out elementary analysis test, and test result is the nickel cobalt
The molecular formula of manganese ternary material is, LiNi0.5Co0.3Mn0.2O2.The nickel-cobalt-manganese ternary material that the embodiment of the present invention 2 is obtained is carried out
Sem test, it is spherical morphology as a result to show the ternary material, is existed without fine powder and other small chips.Using jolt ramming
The tap density for the nickel-cobalt-manganese ternary material that the density tester test embodiment of the present invention 1 is obtained, test result is, of the invention to obtain
The tap density of the nickel-cobalt-manganese ternary material arrived is 2.52g/cm3, tap density is higher.
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 2 is obtained tests its electricity as anode material for lithium-ion batteries
Chemical property.Test result is, charging/discharging voltage scope is 3.0~4.25V, under conditions of charge-discharge magnification is 0.1C, material
Initial discharge capacity reaches 170.4mAh/g, and capability retention is 98.1% after 50 circulations, capability retention after 100 circulations
For 97.4%, capability retention is 96.3% after 200 circulations.
Embodiment 3
A kind of preparation method of nickel-cobalt-manganese ternary material, comprises the following steps：
(a) ternary material precursor Ni is weighed respectively0.3Co0.3Mn0.3(OH)2, lithium compound lithium carbonate and deionized water,
By Ni0.3Co0.3Mn0.3(OH)2With lithium carbonate according to Ni0.3Co0.3Mn0.3(OH)2Mol ratio with Li is 1：1.07 together add to
In stirring container, mixed while adding deionized water, obtain compound, the solid content of its compound is controlled 50%；
(b) above-mentioned compound is first subjected to pre-grinding using Ball-stirring mill and carries out ball milling 5h, then fine grinding is carried out using sand mill
15h, obtains hybrid particles A；
(c) above-mentioned hybrid particles A is spray-dried using Pressuresprayingdrier, atomizing pressure is 0.05Mpa,
EAT is 100 DEG C, and leaving air temp is 60 DEG C, obtains mixed material B；
(d) said mixture material B is sintered under the conditions of air atmosphere, gas dew point Td is controlled in -10 DEG C, gas
Body flow is 1L/min/kg；1000 DEG C, and constant temperature 15h are first risen to 10 DEG C/min heating rate, then with 20 DEG C/min drop
Warm speed is cooled to room temperature, you can obtain nickel-cobalt-manganese ternary material.
The nickel-cobalt-manganese ternary material obtained to the embodiment of the present invention 3 carries out elementary analysis test, and test result is the nickel cobalt
The molecular formula of manganese ternary material is, Li1.07Ni0.3Co0.3Mn0.3O2.The nickel-cobalt-manganese ternary material that the embodiment of the present invention 3 is obtained enters
Row sem test, it is spherical morphology as a result to show the ternary material, is existed without fine powder and other small chips.Using shaking
The tap density for the nickel-cobalt-manganese ternary material that the real density tester test embodiment of the present invention 3 is obtained, test result is, of the invention
The tap density of obtained nickel-cobalt-manganese ternary material is 2.28g/cm3。
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 3 is obtained tests its electricity as anode material for lithium-ion batteries
Chemical property.Test result is, charge voltage range is 3.0~4.25V, under conditions of charge-discharge magnification is 0.1C, at the beginning of material
Beginning discharge capacity reaches 157.2mAh/g, and capability retention is 97.2% after 50 circulations, and capability retention is after 100 circulations
96.3%, capability retention is 94.8% after 200 circulations.
Embodiment 4
A kind of preparation method of nickel-cobalt-manganese ternary material, comprises the following steps：
(a) ternary material precursor Ni is weighed respectively0.6Co0.2Mn0.2(OH)2, lithium compound lithium carbonate and deionized water,
By Ni0.6Co0.2Mn0.2(OH)2With lithium carbonate according to Ni0.6Co0.2Mn0.2(OH)2Mol ratio with Li is 1：1.05 together add to
In stirring container, mixed while adding deionized water, obtain compound, the solid content of its compound is controlled 70%；
(b) with voltameter, above-mentioned compound is first subjected to pre-grinding using Ball-stirring mill and carries out ball milling 5kwh/kg, then using sand
Grinding machine carries out fine grinding 20kwh/kg, obtains hybrid particles A；
(c) above-mentioned hybrid particles A is spray-dried using Pressuresprayingdrier, atomizing pressure is 0.75Mpa,
EAT is 200 DEG C, and leaving air temp is 100 DEG C, obtains mixed material B；
(d) said mixture material B is sintered under the conditions of air atmosphere, gas dew point Td is controlled in -50 DEG C, gas
Body flow is 1.5L/min/kg；900 DEG C, and constant temperature 15h are first risen to 5 DEG C/min heating rate, then with 30 DEG C/min drop
Warm speed is cooled to room temperature, you can obtain nickel-cobalt-manganese ternary material.
The nickel-cobalt-manganese ternary material obtained to the embodiment of the present invention 4 carries out elementary analysis test, and test result is the nickel cobalt
The molecular formula of manganese ternary material is, Li1.05Ni0.6Co0.2Mn0.2O2.The nickel-cobalt-manganese ternary material that the embodiment of the present invention 4 is obtained enters
Row sem test, it is spherical morphology as a result to show the ternary material, is existed without fine powder and other small chips.Using shaking
The tap density for the nickel-cobalt-manganese ternary material that the real density tester test embodiment of the present invention 4 is obtained, test result is, of the invention
The tap density of obtained nickel-cobalt-manganese ternary material is 2.20g/cm3。
The nickel-cobalt-manganese ternary material that the embodiment of the present invention 4 is obtained tests its electricity as anode material for lithium-ion batteries
Chemical property.Test result is, charge voltage range is 3.0~4.25V, under conditions of charge-discharge magnification is 0.1C, at the beginning of material
Beginning discharge capacity reaches 208.8mAh/g, and capability retention is 95.6% after 50 circulations, and capability retention is after 100 circulations
94.3%, capability retention is 92.6% after 200 circulations.
Comparative example 1
A kind of preparation method of nickel-cobalt-manganese ternary material, is added without deionization in step (a) as different from Example 1
Water, by the way of dry method batch mixing, remaining step is same as Example 1.
Test result shows that the spherical morphology of scanned Electronic Speculum test analysis material is destroyed, size distribution uniformity
It is poor.Tap density is 1.78g/cm3.And its chemical property is tested, and test result is, charging/discharging voltage scope is 3.0~
4.25V, charge-discharge magnification is under conditions of 0.1C, material initial capacitance reaches 155mAh/g, and capacity is kept after 50 circulations
Rate is 93.5%, and capability retention is 92.1% after 100 circulations, and capability retention is 90.5% after 200 circulations.
Comparative example 2
A kind of preparation method of nickel-cobalt-manganese ternary material, uses common ball milling as different from Example 1 in step (b)
Machine carries out 10h, and remaining step is same as Example 1.
As shown in figure 3, test result shows, the spherical morphology of scanned Electronic Speculum test analysis material is destroyed, granularity
It is distributed uniformity poor, has more chip and foreign particle to be mixed between particle.Tap density is 2.15g/cm3.And test its electrification
Performance is learned, test result is, charging/discharging voltage scope is 3.0~4.25V, under conditions of charge-discharge magnification is 0.1C, at the beginning of material
Beginning discharge capacity reaches 150.2mAh/g, and capability retention is 86.5% after 50 circulations, and capability retention is after 100 circulations
84.2%, capability retention is 80.8% after 200 circulations.
Comparative example 3
In a kind of preparation method of nickel-cobalt-manganese ternary material, as different from Example 1 step (c), comparative example 3, omit
Fall direct sintering after step (c), i.e. ball milling, remaining step is same as Example 1.
Test result shows that the spherical morphology of scanned Electronic Speculum test analysis material is destroyed, size distribution uniformity
It is poor, granularity poor controllability.Tap density is 2.02g/cm3.And its chemical property is tested, test result is that discharge and recharge is electric
Pressure scope is 3.0~4.25V, and charge-discharge magnification is under conditions of 0.1C, material initial capacitance reaches 148.5mAh/g, 50 times
Capability retention is 85.2% after circulation, and capability retention is 83.5% after 100 circulations, capability retention after 200 circulations
For 70.4%.
The nickel-cobalt-manganese ternary material particle size provided by the above embodiments and the test result of comparative example, the present invention
Controllability is good, and tap density is high, and specific capacity is high, and stability is good, with excellent chemical property.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, or which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
1. a kind of preparation method of nickel-cobalt-manganese ternary material, it is characterised in that comprise the following steps：
(a) ternary material precursor, lithium compound and solvent are mixed, obtains compound；
(b) compound is subjected to ball milling, obtains hybrid particles A；
(c) the hybrid particles A is spray-dried, obtains mixed material B；
(d) the mixed material B is sintered, obtains nickel-cobalt-manganese ternary material.
2. the preparation method of nickel-cobalt-manganese ternary material according to claim 1, it is characterised in that in the step (a), institute
The chemical formula for stating ternary material precursor is NixCoyMnz(OH)2, wherein 0.3≤x≤1,0≤y≤0.3,0≤z≤0.3, and x
+ y+z=1.
3. the preparation method of nickel-cobalt-manganese ternary material according to claim 2, it is characterised in that in the step (a), institute
The mol ratio for stating ternary material precursor and Li in lithium compound is 1：1~1：1.07；
The solid content of the compound is controlled between 10%~70%.
4. the preparation method of nickel-cobalt-manganese ternary material according to claim 1, it is characterised in that in the step (b), ball
The mode of mill is first using Ball-stirring mill progress pre-grinding, then use sand mill to carry out fine grinding；
Preferably, the time that Ball-stirring mill carries out pre-grinding is used for 0.5h~10h, uses sand mill to carry out the time of fine grinding for 0.5h
~20h；
Or, with voltameter, pre-grinding 0.1kwh/kg~20kwh/kg is carried out using Ball-stirring mill, fine grinding is carried out using sand mill
0.5kwh/kg~20kwh/kg.
5. the preparation method of nickel-cobalt-manganese ternary material according to claim 1, it is characterised in that in the step (c), adopt
It is spray-dried with drying machine with centrifugal spray, the rotating speed of atomizer is 5000rpm~30000rpm；Or, sprayed using pressure
Mist drying machine is spray-dried, and atomizing pressure is 0.05Mpa~0.75MPa；
Preferably, the EAT of the spray drying is 100 DEG C~350 DEG C, and leaving air temp is 60 DEG C~160 DEG C.
6. the preparation method of nickel-cobalt-manganese ternary material according to claim 1, it is characterised in that in the step (d), institute
The sintering temperature stated is 750 DEG C~1200 DEG C, and sintering time is 2h~20h；
Preferably, in described sintering process, 750 DEG C~1200 DEG C are risen to 2 DEG C/min~20 DEG C/min heating rate, and
Constant temperature 2h~15h, then room temperature is cooled to 5 DEG C/min~100 DEG C/min rate of temperature fall；
Preferably, in described sintering process, gas dew point Td is controlled between -100 DEG C~-5 DEG C, and gas flow is
0.1L/min/kg~2L/min/kg；
Preferably, described sintering atmosphere is the one or more in oxygen, air or compressed air.
7. the preparation method of the nickel-cobalt-manganese ternary material according to any one of claim 1~6, it is characterised in that the lithium
Compound includes one kind or several in oxide, halide, hydroxide, carbonate, nitrate, acetate and the oxalates of lithium
Kind；
Preferably, the solvent is deionized water or ethanol water.
8. a kind of anode material for lithium-ion batteries, it is characterised in that by the preparation side according to any one of claim 1~7
The nickel-cobalt-manganese ternary material that method is obtained is as anode material for lithium-ion batteries.
9. anode material for lithium-ion batteries according to claim 8, it is characterised in that described nickel-cobalt-manganese ternary material
Chemical formula is LiαNixCoyMnzO2, wherein 1≤α≤1.07,0.3≤x≤1,0≤y≤0.3,0≤z≤0.3, and x+y+z=1；
In ball-type and/or class ball-type.
10. a kind of lithium ion battery, it is characterised in that including housing, the positive pole being placed in housing, negative pole, barrier film and electrolyte,
The barrier film is located between the positive pole and negative pole, and the positive pole includes the anode material for lithium-ion batteries described in claim 8.
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Application publication date: 20170926 |