CN109244431A - Nickel-cobalt-manganternary ternary anode material and its preparation method and application, lithium ion battery, electric car - Google Patents
Nickel-cobalt-manganternary ternary anode material and its preparation method and application, lithium ion battery, electric car Download PDFInfo
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention provides a kind of nickel-cobalt-manganternary ternary anode material and its preparation method and application, lithium ion battery, electric cars, belong to nickel-cobalt-manganternary ternary anode material technical field.The present invention provides a kind of nickel-cobalt-manganternary ternary anode material, nickel-cobalt-manganternary ternary anode material is core-shell structure, and stratum nucleare is the Li of hollow structure2MnO3, Shell Materials are nickel-cobalt-manganese ternary material；Wherein, in Shell Materials Mn content distribution gradient, gradually decreased from internal layer outer layers.The nickel-cobalt-manganternary ternary anode material is hollow core-shell structure, and stratum nucleare is the Li of hollow structure2MnO3, Shell Materials are nickel-cobalt-manganese ternary material, and Mn is reduced in Shell Materials gradient, and this structure shortens the diffusion path of lithium ion, improves the high rate performance of material, while maintaining the spherical morphology of material again, to the tap density of material without larger impact.
Description
Technical field
The invention belongs to nickel-cobalt-manganternary ternary anode material technical fields, and in particular to a kind of nickel-cobalt-manganternary ternary anode material and
Preparation method and application, lithium ion battery, electric car.
Background technique
In recent years, lithium ion battery is high with its operating voltage, energy density is big, have extended cycle life, operating temperature range is wide
It is rapidly developed with the advantages that safe memory-less effect.In particular with the research and development of electric car, lithium ion battery can be
It provides new power source, has further pushed the application of lithium ion battery.
However, the commercialized positive pole material of lithium cobalt acid of current lithium ion battery is due to scarcity of resources, expensive, toxicity
It is higher, make people urgently need to replace cobalt acid lithium using the novel anode material of no cobalt or few cobalt.Positive pole material phosphoric acid iron
Although lithium raw material is cheap, low in cost, the energy density of LiFePO4 has been unable to meet the requirement of new-energy automobile, ternary material
The advantages of expecting that especially high-nickel material combines three kinds of nickel, cobalt, manganese elements compares cobalt acid lithium, has advantage at low cost, compares
LiFePO4, the then advantage for having energy density high.Nickel cobalt lithium ternary material is set to become most promising positive electrode
One of.
Nickel cobalt lithium ternary material have the advantages that compared with existing positive electrode it is numerous, but in terms of chemical property
Still need to be further increased.In lithium ion battery, for ternary material since lithium ion conductivity is low, the second particle of material is larger,
Therefore lithium ion diffusion velocity is slower in charge and discharge process, is unfavorable for the raising of chemical property especially high rate performance.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The first purpose of this invention is to provide a kind of nickel-cobalt-manganternary ternary anode material, the nickel-cobalt-manganternary ternary anode material
On the basis of keeping ternary material spherical morphology, the high rate performance of material greatly improved, can overcome the above problem or
It at least is partially solved above-mentioned technical problem.
Second object of the present invention is to provide the preparation method of above-mentioned nickel-cobalt-manganternary ternary anode material, the nickel cobalt manganese three
The preparation method operating process of first positive electrode is simple, at low cost, and the structure of material will not be destroyed in subsequent sintering process.
Third object of the present invention is to provide application of the nickel-cobalt-manganternary ternary anode material in lithium ion battery, the nickel
Cobalt-manganese ternary positive electrode can shorten the diffusion path of lithium ion in lithium ion battery charge and discharge process, have excellent multiplying power
Performance.
Fourth object of the present invention is to provide a kind of lithium ion battery, including above-mentioned nickel-cobalt-manganternary ternary anode material,
Include that the lithium ion battery of above-mentioned nickel-cobalt-manganternary ternary anode material has excellent high rate performance, can be realized the quick of battery
Charging.
Of the invention the 5th is designed to provide a kind of electric car, including above-mentioned lithium ion battery, by above-mentioned lithium from
Sub- battery is used in electric car, it can be achieved that the quick charge of electric car.
First aspect according to the present invention provides a kind of nickel-cobalt-manganternary ternary anode material, the nickel-cobalt-manganese ternary anode
Material is core-shell structure, and stratum nucleare is the Li of hollow structure2MnO3, Shell Materials are nickel-cobalt-manganese ternary material；
Wherein, in Shell Materials Mn content distribution gradient, gradually decreased from internal layer outer layers.
Preferably, the chemical formula of the nickel-cobalt-manganese ternary material is LiNixCoyMn1-x-yO2, 0.33≤x≤0.92,0.05
≤ y≤0.33,0.5≤x+y < 1；
Preferably, the x value is 0.4≤x≤0.8, and y value is 0.1≤y≤0.3, and the value of x+y is 0.7≤x+y
≤0.9。
Preferably, the diameter of the core of the hollow structure is 1-8 μm, preferably 2-6 μm；
And/or the diameter of the nickel-cobalt-manganternary ternary anode material is 4-14 μm, preferably 4-10 μm.
Preferably, Mole percent of the manganese in nickel cobalt manganese contains in the nickel-cobalt-manganese ternary material of the innermost layer of the Shell Materials
Amount is 20%-60%；
And/or Mole percent of the manganese in nickel cobalt manganese contains in the outermost nickel-cobalt-manganese ternary material of the Shell Materials
Amount is 5%-20%.
The second aspect according to the present invention provides the preparation method of above-mentioned nickel-cobalt-manganternary ternary anode material, including following
Step:
(a) manganese salt, ammonium hydroxide and lye is added simultaneously into the solution containing ammonium hydroxide, reaction obtains manganous hydroxide suspension；
(b) into the manganous hydroxide suspension that step (a) obtains while nickel salt solution, cobalt salt solution and descending concentrations are added
Manganese salt solution carry out coprecipitation reaction, obtain the presoma of core-shell structure；
(c) presoma for obtaining step (b) is mixed with lithium source, is then sintered, and nickel-cobalt-manganternary ternary anode material is obtained.
Preferably, in step (a), the temperature of the reaction is 40-70 DEG C, and the time of the reaction is 40-80min, institute
The pH for stating reaction system is 11-12.5；
Preferably, in step (a), the manganese salt is soluble manganese salt, preferably manganese sulfate, manganese nitrate, manganese acetate, chlorination
At least one of manganese and manganese oxalate, the concentration of the manganese salt are 0.4-0.8mol/L；
Preferably, in step (a), the mass percentage of ammonia is 25%-28% in the ammonium hydroxide；
Preferably, in step (a), the lye is potassium hydroxide and/or sodium hydroxide, and the concentration of the lye is 3-
5mol/L。
Preferably, in step (b), the time of the coprecipitation reaction is 5h-60h, and the temperature of the coprecipitation reaction is
40-70 DEG C, the pH of the coprecipitation reaction system is 10.5-12.5；
Preferably, in step (b), when coprecipitation reaction starts, manganese ion rubbing in nickel ion, cobalt ions and manganese ion
Your percentage composition is 20%-60%, at the end of coprecipitation reaction, mole of the manganese ion in nickel ion, cobalt ions and manganese ion
Percentage composition is 5%-20%；
Preferably, in step (b), the nickel salt is soluble nickel salt, preferably nickel sulfate, nickel nitrate, nickel acetate, chlorination
At least one of nickel and nickel oxalate, the concentration of the nickel salt are 0.5-4mol/L；
And/or the cobalt salt is soluble cobalt, preferably cobaltous sulfate, cobalt nitrate, cobalt acetate, cobalt chloride and cobalt oxalate
At least one of；
And/or the manganese salt is soluble manganese salt, preferably manganese sulfate, manganese nitrate, manganese acetate, manganese chloride and manganese oxalate
At least one of；
Preferably, in step (c), the lithium source is at least one in lithium hydroxide, lithium carbonate, lithium acetate and lithium oxalate
Kind；
Preferably, in step (c), the molar ratio of the presoma and lithium salts is 1:1.01-1.15；
Preferably, in step (c), the temperature of the sintering is 700-1000 DEG C, preferably 850-950 DEG C；
And/or the time of the sintering is 8-24h, preferably 10-15h.
According to the present invention in terms of third, provides above-mentioned nickel-cobalt-manganternary ternary anode material or above-mentioned preparation method obtains
Application of the nickel-cobalt-manganternary ternary anode material in lithium ion battery.
4th aspect according to the present invention, provides a kind of lithium ion battery, including above-mentioned nickel-cobalt-manganternary ternary anode material
Or the nickel-cobalt-manganternary ternary anode material that above-mentioned preparation method obtains.
5th aspect according to the present invention, provides a kind of electric car, including above-mentioned lithium ion battery.
The present invention provides a kind of nickel-cobalt-manganternary ternary anode material, nickel-cobalt-manganternary ternary anode material is core-shell structure, and core is
The core of hollow structure, nuclear material Li2MnO3, Shell Materials are nickel-cobalt-manganese ternary material；Wherein, the content of Mn is in Shell Materials
Middle distribution gradient is gradually decreased from internal layer outer layers.The nickel-cobalt-manganternary ternary anode material is hollow core-shell structure, during core is
Empty Li2MnO3, core is coated with Shell Materials, and Mn is reduced in Shell Materials gradient, and this structure shortens the expansion of lithium ion
Path is dissipated, improves the high rate performance of material, while maintaining the spherical morphology of material again, to the tap density of material without larger
It influences.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the grain size distribution of nickel-cobalt-manganternary ternary anode material prepared by the embodiment of the present invention 1.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
First aspect according to the present invention provides a kind of nickel-cobalt-manganternary ternary anode material, nickel-cobalt-manganternary ternary anode material
For core-shell structure, stratum nucleare is the Li of hollow structure2MnO3, Shell Materials are nickel-cobalt-manganese ternary material；
Wherein, in Shell Materials Mn content distribution gradient, gradually decreased from internal layer outer layers.
The nickel-cobalt-manganternary ternary anode material is hollow core-shell structure, and core is hollow Li2MnO3, core is coated with shell
Material, and Mn is reduced in Shell Materials gradient, this structure shortens the diffusion path of lithium ion, improves the forthright again of material
Can, while the spherical morphology of material is maintained again, to the tap density of material without larger impact.
It should be understood that the content of Ni, Co and Mn distribution gradient in Shell Materials, the content of Mn are outside from internal layer
Layer gradually decreases, and the content of Ni and Co are gradually increased from internal layer outer layers.
As further preferred technical solution, the chemical formula of nickel-cobalt-manganese ternary material is LiNixCoyMn1-x-yO2, 0.33
≤ x≤0.92,0.05≤y≤0.33,0.5≤x+y < 1.It is typical but non-limiting, x value be 0.33,0.35,0.4,
0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85 or 0.92；It is typical but non-limiting, y value be 0.05,
0.08,0.1,0.12,0.14,0.16,0.18,0.2,0.22,0.24,0.26,0.28,0.3,0.32 or 0.33.It is preferred at this
Embodiment in, chemical formula LiNixCoyMn1-x-yO2Nickel-cobalt-manganese ternary material comprehensive utilization nickel, cobalt, manganese three kinds of metals
Synergistic effect, nickel ion therein are main active constituents, and cobalt ions not only conducts electricity very well, and cobalt ions also with manganese from
The structure of sub mutually collaboration stabilizing material.
It should be noted that " chemical formula of nickel-cobalt-manganese ternary material is LiNixCoyMn1-x-yO2, 0.33≤x≤0.92,
0.05≤y≤0.33,0.5≤x+y < 1 " refer to that the average molar ratio of nickel in Shell Materials, cobalt and manganese is x:y:1-x-y.Example
Such as, 0.4 x, when y is 0.15, Shell Materials LiNi0.4Co0.15Mn0.45O2, at this point, nickel, cobalt and manganese in Shell Materials
Average molar ratio is 0.4:0.15:0.45, and content of the manganese in Shell Materials is gradually decreased from internal layer outer layers, i.e. Shell Materials
Molar average percentage composition of the middle manganese in nickel, cobalt and manganese is 45%, manganese rubbing in nickel, cobalt and manganese in the internal layer of Shell Materials
Your percentage composition be greater than 45%, in the outer layer of Shell Materials molar content of the manganese in nickel, cobalt and manganese be less than 45%,
And closer to the internal layer of Shell Materials, molar content of the manganese in nickel, cobalt and manganese is bigger, closer to the outer of Shell Materials
Layer, molar content of the manganese in nickel, cobalt and manganese are smaller.
As further preferred technical solution, x value is 0.4≤x≤0.8, and y value is 0.1≤y≤0.3, x+y's
Value is 0.7≤x+y≤0.9.
As further preferred technical solution, the diameter of the core of hollow structure is 1-8 μm；And/or nickel-cobalt-manganese ternary is just
The diameter of pole material is 4-14 μm.The typical but non-limiting diameter of the core of hollow structure is 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μ
M, 7 μm or 8 μm, the diameter of nickel-cobalt-manganternary ternary anode material is 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm,
13 μm or 14 μm.In the preferred embodiment, by the diameter and nickel-cobalt-manganternary ternary anode material that reasonably adjust core
Diameter enables nickel-cobalt-manganternary ternary anode material to effectively reduce the path of lithium, if the diameter of core crosses conference, will reduce material
Tap density is easily broken in battery core preparation process if the thickness of shell is too small.
It should be understood that the diameter of the core of the diameter and hollow structure of nickel-cobalt-manganternary ternary anode material meets with ShiShimonoseki
System: the diameter of nickel-cobalt-manganternary ternary anode material is greater than the diameter of the core of hollow structure.
It should be noted that the diameter of the core of hollow structure and the diameter of nickel-cobalt-manganternary ternary anode material can be under
The method of stating is calculated, and after terminating manganous hydroxide precipitating, can test its particle diameter distribution, obtain hollow knot with D50 data approximation
The average grain diameter of the core of structure, the as diameter of the core of hollow structure, to entire coprecipitation reaction after, measure its partial size again
Distribution, obtains the average grain diameter of nickel-cobalt-manganternary ternary anode material with D50 data approximation, as nickel-cobalt-manganternary ternary anode material is straight
Diameter.
As further preferred technical solution, the diameter of the core of hollow structure is 2-6 μm；And/or the nickel cobalt manganese three
The diameter of first positive electrode is 4-10 μm.
As further preferred technical solution, manganese is in nickel cobalt manganese in the nickel-cobalt-manganese ternary material of the innermost layer of Shell Materials
In molar content be 20%-60%；And/or in the outermost nickel-cobalt-manganese ternary material of Shell Materials manganese in nickel cobalt
Molar content in manganese is 5%-20%；In the preferred embodiment, by controlling manganese in the nickel cobalt of Shell Materials
Molar content in manganese makes it from inside to outside, and molar content of the manganese in nickel cobalt manganese is decremented to by 20%-60%
5%-20%, so that the content of manganese is successively decreased from inside to outside in the Shell Materials of obtained tertiary cathode material, the concentration gradients of manganese
Successively decrease and be more conducive to being formed complete sphere, otherwise in coprecipitation process by internal manganous hydroxide directly to the nickel of low manganese
Cobalt manganese hydroxide lacks transition, it is difficult to grow up.
It should be noted that " molar content of the manganese in nickel cobalt manganese is 20%-60% " refers to manganese in nickel, cobalt and manganese
Molar content in three kinds of elements is 20%-60%.
It should be noted that manganese molar content shared in nickel, cobalt and manganese is greater than etc. in the internal layer of Shell Materials
The manganese molar content shared in nickel, cobalt and manganese in the outer layer of Shell Materials, i.e., from inside to outside, manganese exists Shell Materials
Shared molar content gradually decreases in nickel, cobalt and manganese.
The second aspect according to the present invention provides the preparation method of above-mentioned nickel-cobalt-manganternary ternary anode material, including following
Step:
(a) manganese salt, ammonium hydroxide and lye is added simultaneously into the solution containing ammonium hydroxide, reaction obtains manganous hydroxide suspension；
(b) into the manganous hydroxide suspension that step (a) obtains while nickel salt solution, cobalt salt solution and descending concentrations are added
Manganese salt solution carry out coprecipitation reaction, obtain the presoma of core-shell structure；
(c) presoma for obtaining step (b) is mixed with lithium source, is then sintered, and nickel-cobalt-manganternary ternary anode material is obtained.
The present invention is coprecipitated nickel hydroxide, cobalt, manganese on this basis by being first settled out manganous hydroxide as core, and manganese is kept to exist
Concentration gradient reduces from inside to outside in coprecipitation process, obtains presoma, is then sintered, in sintering process, manganous hydroxide
Generate Li2MnO3, at this point, the diffusion coefficient due to manganese is higher, internal manganese will be to external diffusion, and being formed internal has
The core of hollow structure.Manganese gradient is reduced in the Shell Materials of resulting hollow nickel-cobalt-manganternary ternary anode material, shortens lithium ion
Diffusion path, improve the high rate performance of material, while maintaining the spherical morphology of material again, to the tap density of material without
Larger impact.
It is template that the present invention, which is using manganous hydroxide, and is settled out outer low manganese, the gradient nickel cobalt of interior Gao Meng based on this
Manganese precursor obtains the spherical ternary cathode material of inner hollow by sintering, so as to improve the high rate performance of material, operated
Journey is simple, at low cost, while will not influence the structure of material in subsequent sintering process.
The manganous hydroxide that step (a) of the present invention is prepared is complete spherical morphology, and the presence of ammonium hydroxide has conducive to hydrogen-oxygen
Change the generation and growth of manganese spherical structure.
It should be understood that in step (b), be added simultaneously into manganous hydroxide suspension nickel salt solution, cobalt salt solution and
The manganese salt solution of descending concentrations, the manganese salt solution that can be nickel salt solution, cobalt salt solution and descending concentrations pass through three pumps respectively
It is pumped into manganous hydroxide suspension simultaneously.It is also possible to be added in manganous hydroxide suspension by two pumps, nickel salt solution, cobalt salt
The mixed solution of solution is added in manganous hydroxide suspension by a pump, and the manganese salt solution of descending concentrations is pumped by another
It is added in manganous hydroxide suspension.
Uniformly successively decrease it should be understood that the descending concentrations in the manganese salt solution of descending concentrations can be, is also possible to
It is heterogeneous to successively decrease.
It should be understood that in step (a) and step (b), in order to enable solution is uniformly mixed, it can be normal using this field
The laboratory facilities of rule, such as can use peristaltic pump.Presoma in step (b) have passed through this field conventional treatment, such as wash
It washs, dry.
It should be understood that obtained presoma is core-shell structure, and core layer material is manganous hydroxide, shell in step (b)
Material is the nickel cobalt manganese of manganese gradient reduction.The average molar ratio and nickel cobalt of nickel, cobalt and manganese in the Shell Materials of obtained presoma
The molar ratio of nickel cobalt manganese in manganese ternary material is corresponding.
As further preferred technical solution, in step (a), the temperature of reaction is 40-70 DEG C, and the time of reaction is
40-80min, the pH of reaction system are 11-12.5.React typical but non-limiting temperature be 40 DEG C, 42 DEG C, 44 DEG C, 46 DEG C,
48 DEG C, 50 DEG C, 52 DEG C, 54 DEG C, 56 DEG C, 58 DEG C, 60 DEG C, 62 DEG C, 64 DEG C, 66 DEG C, 68 DEG C or 70 DEG C, reaction is typical but unrestricted
Property time be 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min or 80min, reaction system is typical
But unrestricted pH be 11,11.1,11.2,11.3,11.4,11.5,11.6,11.7,11.8,11.9,12.0,12.1,
12.2,12.3,12.4 or 12.5.In the preferred embodiment, by reasonably adjusting the temperature during preparing manganous hydroxide
Degree, pH control the reaction time, manganous hydroxide suspension have successfully been prepared.
As further preferred technical solution, in step (a), manganese salt is soluble manganese salt, and the concentration of manganese salt is 0.4-
0.8mol/L；In the preferred embodiment, by selection soluble manganese salt and reasonable manganese salt concentration, be conducive to react
Go on smoothly.
As further preferred technical solution, in step (a), manganese salt is manganese sulfate, manganese nitrate, manganese acetate, manganese chloride
At least one of with manganese oxalate.
As further preferred technical solution, in step (a), the mass percentage of ammonia is 25%-28% in ammonium hydroxide；
In the preferred embodiment, ammonia is conducive to prepare manganous hydroxide.
As further preferred technical solution, in step (a), lye is potassium hydroxide and/or sodium hydroxide, lye
Concentration is 3-5mol/L；In the preferred embodiment, by reasonably adjusting the concentration of lye, closed so that reaction system has
Suitable pH, to be conducive to going on smoothly for reaction.
As further preferred technical solution, in step (b), the time of reaction is 5h-60h, and the temperature of reaction is 40-
70 DEG C, the pH of reaction system is 10.5-12.5；In the preferred embodiment, by the temperature, the time that reasonably adjust reaction
And pH, the presoma of core-shell structure has successfully been prepared.
As further preferred technical solution, in step (b), when coprecipitation reaction starts, manganese ion is in nickel ion, cobalt
Molar content in ion and manganese ion is 20%-60%, at the end of coprecipitation reaction, manganese ion nickel ion, cobalt from
Molar content in son and manganese ion is 5%-20%；In the preferred embodiment, by reasonably adjusting co-precipitation
When reaction starts at the end of, molar content of the manganese ion in nickel ion, cobalt ions and manganese ion, so that manganese ion exists
When co-precipitation, content is successively decreased, so that the content of manganese is successively decreased from inside to outside in the Shell Materials of obtained presoma.
It should be understood that manganese ion is in nickel ion, cobalt ions due to the descending concentrations of manganese salt solution in coprecipitation process
5%-20% is decremented to by 20%-60% with the molar content in manganese ion, during this, manganese ion is in nickel ion, cobalt
The decline rate of molar content in ion and manganese ion can be constant speed, be also possible to non-constant speed.
As further preferred technical solution, in step (b), nickel salt is soluble nickel salt, and the concentration of nickel salt is 0.5-
4mol/L；And/or cobalt salt is soluble cobalt；And/or manganese salt is soluble manganese salt.
As further preferred technical solution, in step (b), nickel salt is nickel sulfate, nickel nitrate, nickel acetate, nickel chloride
At least one of with nickel oxalate；And/or cobalt salt be cobaltous sulfate, cobalt nitrate, cobalt acetate, cobalt chloride and cobalt oxalate at least
It is a kind of；And/or manganese salt is at least one of manganese sulfate, manganese nitrate, manganese acetate, manganese chloride and manganese oxalate；In the preferred reality
It applies in mode, the corresponding sulfate of nickel cobalt manganese, nitrate, acetate, chlorate and oxalates all have solubility, are conducive to nickel
Cobalt manganese is deposited on manganous hydroxide nuclear structure.
As further preferred technical solution, in step (c), lithium source is lithium hydroxide, lithium carbonate, lithium acetate and oxalic acid
At least one of lithium；In the preferred embodiment, lithium hydroxide, lithium carbonate, lithium acetate and lithium oxalate provide elemental lithium.
As further preferred technical solution, in step (c), the molar ratio of presoma and lithium salts is 1:1.01-1.15；
In the preferred embodiment, by reasonably adjusting the dosage of elemental lithium in presoma and lithium salts, so that finally obtained nickel
Shell Materials in cobalt-manganese ternary positive electrode are LiNixCoyMn1-x-yO2。
As further preferred technical solution, in step (c), the temperature of sintering is 700-1000 DEG C；And/or sintering
Time be 8-24h；In the preferred embodiment, by reasonably adjusting the temperature and time of sintering, so that in presoma
Core manganous hydroxide be changed into Li2MnO3, while the Li higher, internal using the diffusion coefficient of manganese2MnO3To external diffusion, formed
Inside has the core of hollow structure.
As further preferred technical solution, in step (c), the temperature of sintering is 850-950 DEG C；And/or sintering
Time is 10-15h；In the preferred embodiment, by reasonably adjusting the temperature and time of sintering, obtain that there is hollow knot
The core of structure.
According to the present invention in terms of third, provides above-mentioned nickel-cobalt-manganternary ternary anode material or above-mentioned preparation method obtains
Application of the nickel-cobalt-manganternary ternary anode material in lithium ion battery.
The nickel-cobalt-manganternary ternary anode material can shorten the diffusion path of lithium ion in lithium ion battery charge and discharge process, tool
There is excellent high rate performance.
4th aspect according to the present invention, provides a kind of lithium ion battery, including above-mentioned nickel-cobalt-manganternary ternary anode material
Or the nickel-cobalt-manganternary ternary anode material that above-mentioned preparation method obtains.
Include that the lithium ion battery of above-mentioned nickel-cobalt-manganternary ternary anode material has excellent high rate performance, can be realized fast
Speed charging.
5th aspect according to the present invention, provides a kind of electric car, including above-mentioned lithium ion battery.
Above-mentioned lithium ion battery is used in electric car the quick charge, it can be achieved that electric car.
Technical solution of the present invention is described further below in conjunction with embodiment and comparative example.
Embodiment 1
1, nickel-cobalt-manganternary ternary anode material
A kind of nickel-cobalt-manganternary ternary anode material, the nickel-cobalt-manganternary ternary anode material are core-shell structure, and core is hollow structure
Core, nuclear material Li2MnO3, Shell Materials LiNi0.5Co0.2Mn0.3O2；
Wherein, the content of the content of Ni, Co and Mn distribution gradient in Shell Materials, Mn is gradually dropped from internal layer outer layers
Low, the content of Ni and Co are gradually increased from internal layer outer layers.
The diameter of the core of hollow structure is 2 μm, 5.6 μm of obtained nickel-cobalt-manganternary ternary anode material.
Molar content of the manganese in nickel cobalt manganese is 50% in the nickel-cobalt-manganese ternary material of the innermost layer of Shell Materials, shell
Molar content of the manganese in nickel cobalt manganese is 10% in the outermost nickel-cobalt-manganese ternary material of layer material.
2, the preparation of nickel-cobalt-manganternary ternary anode material
(1) at 50 DEG C, concentrated ammonia liquor, 4mol/L sodium hydroxide, 0.6mol/L manganese sulfate solution are passed through into peristaltic pump cocurrent
It is added in reaction kettle, keeping PH in reaction kettle is that 11.7-11.8 obtains manganous hydroxide suspension after reacting 1h.
(2) by the mixed solution of nickel sulfate and lithium sulfate, (concentration of nickel ion is 1mol/L in mixed solution, cobalt ions
Concentration is 0.4mol/L) be added to the flow velocity of 10ml/min in the reaction kettle of step (1), while by manganese sulfate solution with
The flow velocity of 10ml/min is added in reaction kettle, and the concentration gradient of manganese ion is reduced in manganese sulfate solution, and initial concentration is
1.4mol/L, ultimate density 0.155mol/L, keeping PH in reaction kettle is 11-11.1, obtains the presoma of core-shell structure, preceding
The nuclear material for driving body is manganous hydroxide, and the Shell Materials of presoma are the nickel cobalt manganese of manganese gradient reduction.
The concentration gradient reduction of manganese ion is controlled in the following manner in manganese sulfate solution: being by initial concentration
The manganese sulfate solution of 1.4mol/L is added in reaction kettle with the flow velocity of 10ml/min, during which by peristaltic pump with 0.5ml/min
Flow velocity pure water is added into manganese sulfate solution so that the ultimate density of manganese sulfate be 0.155mol/L.
(3) precursor is mixed with lithium carbonate with the weight ratio of 1:1.05, is sintered 12h at a temperature of 900 DEG C, obtains hollow
Manganese gradient distribution nickel-cobalt-manganternary ternary anode material.
3, the grain size distribution for the nickel-cobalt-manganternary ternary anode material that embodiment 1 obtains is as shown in Figure 1, in Fig. 1, D50 is
5.572 μm, with D50 data be approximately average grain diameter to get the nickel-cobalt-manganternary ternary anode material arrived average grain diameter for 5.572 μ
M, D10 are 3.982 μm, and D90 is 7.811 μm, and the narrow particle diameter distribution to get the nickel-cobalt-manganternary ternary anode material arrived of particle diameter distribution is equal
One.
Embodiment 2
1, nickel-cobalt-manganternary ternary anode material
A kind of nickel-cobalt-manganternary ternary anode material, the nickel-cobalt-manganternary ternary anode material are core-shell structure, and core is hollow structure
Core, nuclear material Li2MnO3, Shell Materials LiNi0.5Co0.2Mn0.3O2；
Wherein, the content of the content of Ni, Co and Mn distribution gradient in Shell Materials, Mn is gradually dropped from internal layer outer layers
Low, the content of Ni and Co are gradually increased from internal layer outer layers.
The diameter of the core of hollow structure is 2 μm, 5.6 μm of obtained nickel-cobalt-manganternary ternary anode material.
Molar content of the manganese in nickel cobalt manganese is 50% in the nickel-cobalt-manganese ternary material of the innermost layer of Shell Materials, shell
Molar content of the manganese in nickel cobalt manganese is 10% in the outermost nickel-cobalt-manganese ternary material of layer material.
2, the preparation of nickel-cobalt-manganternary ternary anode material
(1) at 50 DEG C, concentrated ammonia liquor, 4mol/L sodium hydroxide, 0.6mol/L manganese sulfate solution are passed through into peristaltic pump cocurrent
It is added in reaction kettle, keeping PH in reaction kettle is that 11-11.1 obtains manganous hydroxide suspension after reacting 1h.
(2) by the mixed solution of nickel sulfate and lithium sulfate, (concentration of nickel ion is 1mol/L in mixed solution, cobalt ions
Concentration is 0.4mol/L) be added to the flow velocity of 10ml/min in the reaction kettle of step (1), while by manganese sulfate solution with
The flow velocity of 10ml/min is added in reaction kettle, and the concentration gradient of manganese ion is reduced in manganese sulfate solution, and initial concentration is
1.4mol/L, ultimate density 0.155mol/L, keeping PH in reaction kettle is 10.5-10.6, obtains the presoma of core-shell structure,
The nuclear material of presoma is manganous hydroxide, and the Shell Materials of presoma are the nickel cobalt manganese of manganese gradient reduction.
The concentration gradient reduction of manganese ion is controlled in the following manner in manganese sulfate solution: being by initial concentration
The manganese sulfate solution of 0.6mol/L is added in reaction kettle with the flow velocity of 10ml/min, during which by peristaltic pump with 0.5ml/min
Flow velocity pure water is added into manganese sulfate solution so that the ultimate density of manganese sulfate be 0.155mol/L.
(3) precursor is mixed with lithium carbonate with the weight ratio of 1:1.05, is sintered 12h at a temperature of 900 DEG C, obtains hollow
Manganese gradient distribution nickel-cobalt-manganternary ternary anode material.
Embodiment 3
Embodiment 3 difference from example 1 is that, Shell Materials LiNi0.34Co0.2Mn0.46O2。
Embodiment 4
Embodiment 4 difference from example 1 is that, Shell Materials LiNi0.8Co0.1Mn0.1O2。
Embodiment 5
Embodiment 5 difference from example 1 is that, Shell Materials LiNi0.5Co0.3Mn0.2O2。
Embodiment 6
Embodiment 6 difference from example 1 is that, Shell Materials LiNi0.35Co0.5Mn0.15O2。
Embodiment 7
Embodiment 8 difference from example 1 is that, Shell Materials LiNi0.2Co0.5Mn0.3O2。
Embodiment 8-11
Embodiment 8-11 difference from example 1 is that, the diameter and shell of the core of nickel-cobalt-manganternary ternary anode material
Thickness, it is specific as shown in table 1.
The diameter and shell thickness of the core of 1 embodiment 8-11 nickel-cobalt-manganternary ternary anode material of table
In table 1, "-" indicates same as Example 1.
Comparative example 1
Comparative example 1 difference from example 1 is that, the content of manganese remains unchanged in the Shell Materials in comparative example 1,
I.e. from inside to outside with Shell Materials, the content of manganese is completely the same.
Comparative example 2
Comparative example 2 difference from example 1 is that, the changes of contents trend of manganese in the Shell Materials in comparative example 2
In difference, with embodiment 1 variation tendency of manganese just on the contrary, in 1 Shell Materials outermost layer of comparative example manganese content Yu embodiment 1
The content of manganese is the same in Shell Materials innermost layer, likewise, in 1 Shell Materials innermost layer of comparative example manganese content Yu embodiment 1
The content of manganese is the same in Shell Materials outermost layer, i.e., from inside to outside with Shell Materials, the content of manganese is gradually increased.
Comparative example 3
Comparative example 3 difference from example 1 is that, core in comparative example 3 is solid Li2MnO3, i.e. documents
3 core is not hollow.
Test example 1
The nickel-cobalt-manganternary ternary anode material obtained using embodiment 1-11 and comparative example 1-3 is as the anode of lithium ion battery
Material carries out charge-discharge test under 1C, 5C, 10C (1C=160mAh/g) multiplying power, obtained specific capacity (mAh/g) such as 2 institute of table
Show.
The performance for the lithium ion battery that 2 nickel-cobalt-manganternary ternary anode material of table obtains
| 1C | 5C | 10C | |
| Embodiment 1 | 160 | 144 | 122 |
| Embodiment 2 | 159 | 141 | 123 |
| Embodiment 3 | 149 | 132 | 110 |
| Embodiment 4 | 185 | 162 | 147 |
| Embodiment 5 | 163 | 143 | 125 |
| Embodiment 6 | 152 | 136 | 117 |
| Embodiment 7 | 140 | 119 | 99 |
| Embodiment 8 | 155 | 134 | 113 |
| Embodiment 9 | 163 | 147 | 126 |
| Embodiment 10 | 160 | 144 | 125 |
| Embodiment 11 | 154 | 138 | 115 |
| Comparative example 1 | 130 | 108 | 86 |
| Comparative example 2 | 125 | 104 | 78 |
| Comparative example 3 | 115 | 101 | 75 |
Test result shows that the stratum nucleare of embodiment 1-11 nickel-cobalt-manganternary ternary anode material is the Li of hollow structure2MnO3, shell
Layer material is nickel-cobalt-manganese ternary material, and the content of Mn is gradually decreased from internal layer outer layers in Shell Materials.Embodiment 1-11 nickel cobalt
Manganese tertiary cathode material carries out charge-discharge test under 1C, 5C, 10C (1C=160mAh/g) multiplying power, obtained specific capacity compared with
Greatly, high rate performance is excellent.The content of manganese remains unchanged in the Shell Materials of comparative example 1, manganese in the Shell Materials of comparative example 2
Content gradually rises from inside to outside, and the core of comparative example 3 is solid Li2MnO3, nickel-cobalt-manganese ternary that comparative example 1-3 is obtained anode
The high rate performance of material is poor, is nothing like embodiment 1-11.
The kernel of positive electrode is bigger, and shell is smaller, then its high rate performance is better.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of nickel-cobalt-manganternary ternary anode material, which is characterized in that the nickel-cobalt-manganternary ternary anode material is core-shell structure, stratum nucleare
For the Li of hollow structure2MnO3, Shell Materials are nickel-cobalt-manganese ternary material；
Wherein, in Shell Materials Mn content distribution gradient, gradually decreased from internal layer outer layers.
2. nickel-cobalt-manganternary ternary anode material according to claim 1, which is characterized in that the change of the nickel-cobalt-manganese ternary material
Formula is LiNixCoyMn1-x-yO2, 0.33≤x≤0.92,0.05≤y≤0.33,0.5≤x+y < 1；
Preferably, the x value is 0.4≤x≤0.8, and y value is 0.1≤y≤0.3, the value of x+y be 0.7≤x+y≤
0.9。
3. nickel-cobalt-manganternary ternary anode material according to claim 1 or 2, which is characterized in that the core of the hollow structure
Diameter is 1-8 μm, preferably 2-6 μm；
And/or the diameter of the nickel-cobalt-manganternary ternary anode material is 4-14 μm, preferably 4-10 μm.
4. nickel-cobalt-manganternary ternary anode material according to claim 1 or 2, which is characterized in that the Shell Materials it is most interior
Molar content of the manganese in nickel cobalt manganese is 20%-60% in the nickel-cobalt-manganese ternary material of layer；
And/or molar content of the manganese in nickel cobalt manganese is in the outermost nickel-cobalt-manganese ternary material of the Shell Materials
5%-20%.
5. the preparation method of the described in any item nickel-cobalt-manganternary ternary anode materials of claim 1-4, which is characterized in that including following
Step:
(a) manganese salt, ammonium hydroxide and lye is added simultaneously into the solution containing ammonium hydroxide, reaction obtains manganous hydroxide suspension；
(b) into the manganous hydroxide suspension that step (a) obtains while the manganese of nickel salt solution, cobalt salt solution and descending concentrations is added
Salting liquid carries out coprecipitation reaction, obtains the presoma of core-shell structure；
(c) presoma for obtaining step (b) is mixed with lithium source, is then sintered, and nickel-cobalt-manganternary ternary anode material is obtained.
6. preparation method according to claim 5, which is characterized in that in step (a), the temperature of the reaction is 40-70
DEG C, the time of the reaction is 40-80min, and the pH of the reaction system is 11-12.5；
Preferably, in step (a), the manganese salt is soluble manganese salt, preferably manganese sulfate, manganese nitrate, manganese acetate, manganese chloride and
At least one of manganese oxalate, the concentration of the manganese salt are 0.4-0.8mol/L；
Preferably, in step (a), the mass percentage of ammonia is 25%-28% in the ammonium hydroxide；
Preferably, in step (a), the lye is potassium hydroxide and/or sodium hydroxide, and the concentration of the lye is 3-5mol/
L。
7. preparation method according to claim 5, which is characterized in that in step (b), the time of the coprecipitation reaction is
5h-60h, the temperature of the coprecipitation reaction are 40-70 DEG C, and the pH of the coprecipitation reaction system is 10.5-12.5；
Preferably, in step (b), when coprecipitation reaction starts, manganese ion in nickel ion, cobalt ions and manganese ion moles hundred
Divide content for 20%-60%, at the end of coprecipitation reaction, Mole percent of the manganese ion in nickel ion, cobalt ions and manganese ion
Content is 5%-20%,
Preferably, in step (b), the nickel salt be soluble nickel salt, preferably nickel sulfate, nickel nitrate, nickel acetate, nickel chloride and
At least one of nickel oxalate, the concentration of the nickel salt are 0.5-4mol/L；
And/or the cobalt salt is soluble cobalt, preferably in cobaltous sulfate, cobalt nitrate, cobalt acetate, cobalt chloride and cobalt oxalate
It is at least one；
And/or the manganese salt is soluble manganese salt, preferably in manganese sulfate, manganese nitrate, manganese acetate, manganese chloride and manganese oxalate
It is at least one；
Preferably, in step (c), the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium acetate and lithium oxalate；
Preferably, in step (c), the molar ratio of the presoma and lithium salts is 1:1.01-1.15；
Preferably, in step (c), the temperature of the sintering is 700-1000 DEG C, preferably 850-950 DEG C；
And/or the time of the sintering is 8-24h, preferably 10-15h.
8. the described in any item nickel-cobalt-manganternary ternary anode materials of claim 1-4 or the described in any item preparations of claim 5-7
Application of the nickel-cobalt-manganternary ternary anode material that method obtains in lithium ion battery.
9. a kind of lithium ion battery, which is characterized in that including the described in any item nickel-cobalt-manganternary ternary anode materials of claim 1-4
Or the nickel-cobalt-manganternary ternary anode material that the described in any item preparation methods of claim 5-7 obtain.
10. a kind of electric car, which is characterized in that including lithium ion battery as claimed in claim 9.
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