Tertiary cathode material and preparation method thereof
Technical field
The present invention relates to new energy field, especially relates to a kind of tertiary cathode material and preparation method thereof.
Background technology
In recent years, the appearance of new-energy automobile, new power is provided for the development of lithium ion battery industry.And it is used as new
The lithium-ion-power cell of energy automobile kernel component, the quality of its performance are even more to be directly connected to the smooth of new-energy automobile
Promote, determine the future of new-energy automobile industry.And as the important component of lithium ion battery, high-performance positive electrode
Exploitation, then the lifting to performance of lithium ion battery is most important.In existing numerous positive electrodes, tertiary cathode material with
By means of its outstanding performance and higher energy density, just gradually substitution LiFePO4 turns into new-energy automobile (particularly passenger car
Type) the preferred positive electrode of lithium-ion-power cell is used, also turn into the developing focus of industrial circle at this stage.
Research shows, in order that ternary material has better performance, it is necessary to improve transition metal in ternary material
And doping vario-property handle when miscellaneous Elemental redistribution uniformity, suitably reduce material particle diameter while, improve material granule
The uniformity of particle diameter distribution.Meanwhile spheric granules pattern then contributes to positive electrode pressure in lithium ion cell positive manufacturing process
The lifting of real density, so as to improve the overall energy density of battery.But traditional ternary material synthesis technique (co-precipitation-height
Warm solid phase reaction process) in, because nickel cobalt manganese ion is not fully identical with the solubility product of hydroxide ion precipitation reaction, precipitation
The heterogeneous nucleation reaction mechanism of reaction, and the material such as ternary material and its intrinsic crystal production rule of hydroxide precursor
The presence of intrinsic property so that existing process is difficult to the realization for ensureing above-mentioned requirements well.
In numerous new ternary material synthetic methods of researcher's exploitation, sol-gel process can be very good to ensure
The uniformity of Elemental redistribution.But in common sol-gel process, needed by colloidal sol to gel (i.e. the preparation process of gel)
Very long course of reaction.Also, obtained product morphology is also very irregular, and particle diameter distribution is uneven.
Therefore, it is necessary to develop a kind of brand-new sol-gel preparation technology, spherical the three of even particle distribution is prepared
First positive electrode.
The content of the invention
The method that the main object of the present invention prepares tertiary cathode material for a kind of sol-gel technology of offer, it is intended to solve
Certainly existing sol-gel preparation process is needed reacted for a long time in the case that external heat source heats the problem of.
The present invention proposes a kind of preparation method of tertiary cathode material, wherein, the tertiary cathode material formula is
LiNi(1-x-y-z)CoxMnyMzO2, x+y+z<1, x>0, y>0, M is doped chemical, including:
Lithium salts, nickel salt, cobalt salt, manganese salt and doped chemical salt are added into first part in the amount ratio of certain material to specify
Solvent in, it is agitated to obtain reaction solution A;A certain amount of organic ligand is added in second part of solvent, agitated
To reaction solution B;
According to certain volume than pouring into the reaction solution B in the reaction solution A being in stirring, under lasting stirring
Certain time is reacted, filters, obtains wet gel;
By the wet gel, in the case where specifying atmosphere, pre-sintering obtains presoma, after the presoma is taken out into grinding, in oxygen
It is heat-treated under the property changed atmosphere, obtains tertiary cathode material.
Preferably, the lithium salts, nickel salt, cobalt salt, manganese salt are respectively villaumite, sulfate or acetic acid corresponding to each metal ion
One kind in salt.
Preferably, the doped chemical salt includes the one or more in aluminium salt, zirconates, titanium salt;The aluminium salt and zirconium
Salt is respectively one kind in villaumite, sulfate or acetate corresponding to each metal ion;The titanium salt includes titanium chloride, titanium sulfate
Or one kind in butyl titanate.
Preferably, it is described when M is Al, 0<z<0.1, when M is Zr and Ti, 0<z<0.05.
Preferably, lithium salt is 0.2-4mol/L in the reaction solution A;Organic ligand concentration is in the reaction solution B
0.05-1mol/L;The reaction solution A and reaction solution B volume ratio is 0.8 to 1.5.
Preferably, the solvent includes DMF, DMA, absolute ethyl alcohol, ethylene glycol
Or one kind in acetone.
Preferably, the organic ligand includes terephthalic acid (TPA), M-phthalic acid, trimesic acid, trimellitic acid, 2-
One kind in amino terephthalic acid (TPA).
Preferably, the specified atmosphere is nitrogen oxygen atmosphere atmosphere, nitrogen mass content 90% in the nitrogen oxygen atmosphere atmosphere
To 95%, oxygen quality content is 5% to 10%.
Preferably, the pre-sintered condition is:600-700 DEG C of insulation 4-5h;The heat treatment condition is:750-850℃
It is incubated 8-15h.
The present invention also provides a kind of tertiary cathode material, formula LiNi(1-x-y-z)CoxMnyMzO2, wherein, x+y+z<1, x
>0, y>0, M is doped chemical, is prepared by above-mentioned preparation method.
Beneficial effect of the present invention:The present invention has obtained gel by very simple efficient method first, can not only protect
Being uniformly distributed for each element is demonstrate,proved, and the gel preparation course used time is short, is heated without external heat source, so as to effectively save energy
Amount, and filter the repeatable utilization of obtained filtrate;In the present invention in inert atmosphere preheating treatment procedure, the volatilization of residual solvent
And the thermal decomposition process of organic ligand ensure that material can obtain regular and centralized particle diameter spherical morphology, these patterns
Feature can remain in follow-up oxidizing atmosphere high-temperature heat treatment process, obtain spherical ternary cathode material, the present invention
Preparation method compared to existing spherical ternary cathode material can save the energy;The ternary material grain diameter and material of the present invention
Inner element is uniformly distributed, and both can be fully played its gram volume, it is also ensured that material has outstanding circulation
Stability, while it is distributed the particle diameter of concentration and spherical morphology improves the processing performance of material well.Preparation of the present invention
Transition metal, elemental lithium and doped chemical that may be present can realize atomic level in sol-gel state in method
Uniform mixing, reduction can prepare the heat treatment temperature of tertiary cathode material to a certain extent;Ternary prepared by the present invention is just
Pole material, can by changing the species of organic ligand, or under inert atmosphere the pre-heat treatment reaction condition, easily realize three
The size controlling of first positive electrode;Preparation method of the present invention can be by adjusting the addition of gel preparatory phase nickel cobalt manganese salt
Ratio, the regulation and control of the chemical constituent of positive electrode are realized, prepare different types of tertiary cathode material;Preparation technology simply may be used
OK, flow is short, is adapted to industrialized production.
Brief description of the drawings
The preparation method schematic flow sheet of tertiary cathode material in Fig. 1 one embodiment of the invention;
The SEM figures of ternary material in Fig. 2 one embodiment of the invention;
The XRD of ternary material in Fig. 3 one embodiment of the invention;
The charging and discharging curve figure of battery corresponding to ternary material in Fig. 4 one embodiment of the invention;
The cycle performance curve map of battery corresponding to ternary material in Fig. 5 one embodiment of the invention.
The realization, functional characteristics and advantage of the object of the invention will be described further referring to the drawings in conjunction with the embodiments.
Embodiment
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
Reference picture 1, the embodiment of the present invention propose a kind of preparation method of tertiary cathode material, wherein, tertiary cathode material
Formula is LiNi(1-x-y-z)CoxMnyMzO2, x+y+z<1, x>0, y>0, M is doped chemical, including:
S1:Lithium salts, nickel salt, cobalt salt, manganese salt and doped chemical salt are added to first part in the amount ratio of certain material
In the solvent specified, reaction solution A is obtained through magnetic agitation;A certain amount of organic ligand is added in second part of solvent,
Reaction solution B is obtained through magnetic agitation;
S2:According to certain volume than the reaction solution B is poured into the reaction solution A being in magnetic agitation, persistently stirring
Mix and reacted certain time under state, filter, obtain wet gel;
S3:By the wet gel, in the case where specifying atmosphere, pre-sintering obtains presoma, after the presoma is taken out into grinding,
It is heat-treated under oxidizing atmosphere, obtains tertiary cathode material.
The preparation process of gel described in the embodiment of the present invention is very simple, and mixing time can foreshorten to 5min, filters
Time about 30min, much smaller than conventional sol gel method;Preparation process saves energy very much without heating;And after filtering
Filtrate may be reused.Wet gel in the embodiment of the present invention is pre-sintered under an inert atmosphere, the volatilization of residual solvent and
The thermal decomposition process of organic ligand ensure that material can obtain the spherical morphology of neat appearance and centralized particle diameter, these shapes
Looks feature can remain in follow-up oxidizing atmosphere high-temperature heat treatment process, obtain grain diameter and material internal element
It is uniformly distributed spherical ternary cathode material.Lithium salts needed for the embodiment of the present invention adds in gel preparation course, ensure that
Mix in the uniform of atomic level with each element, and mixed without it is possible to additionally incorporate lithium salts before heat treatment, make ternary just
The preparation technology of pole material is more simple.
Further, the lithium salts, nickel salt, cobalt salt, manganese salt are respectively villaumite, sulfate or vinegar corresponding to each metal ion
One kind in hydrochlorate.I.e. described lithium salts includes one kind in lithium chloride, lithium sulfate or lithium acetate;The nickel salt include nickel chloride,
One kind in nickel sulfate or nickel acetate;The cobalt salt includes one kind in cobalt chloride, cobaltous sulfate or cobalt acetate;The manganese salt includes
One kind in manganese chloride, manganese sulfate or manganese acetate.
Further, the doped chemical salt includes the one or more in aluminium salt, zirconates, titanium salt;The aluminium salt and
Zirconates is respectively one kind in villaumite, sulfate or acetate corresponding to each metal ion;The titanium salt includes titanium chloride, sulfuric acid
One kind in titanium or butyl titanate.I.e. described aluminium salt includes one kind in aluminium chloride, aluminum sulfate or aluminum acetate;The zirconates bag
Include one kind in zirconium chloride, zirconium sulfate or acetic acid zirconium.
Further, it is described when M is Al, 0<z<0.1, when M is Zr and Ti, 0<z<0.05.
Lithium salts described in the embodiment of the present invention, nickel salt, cobalt salt, the amount of manganese salt and material corresponding to doped chemical salt are according to mixing
The formula LiNi of miscellaneous ternary material(1-x-y-z)CoxMnyMzO2It is determined that wherein x+y+z<1, x>0, y>0;When M is Al, 0<z<
0.1;When M is Zr and Ti, 0<z<0.05;The lithium salts addition is slightly excessive on the basis of above-mentioned stoichiometric proportion, the tune
Value is had suffered between 1.05~1.15, to improve the chemical property of material.
Further, lithium salt is 0.2mol/L to 4mol/L in the reaction solution A;It is organic in the reaction solution B to match somebody with somebody
Bulk concentration is 0.05mol/L to 1mol/L;The reaction solution A and reaction solution B volume ratio is 0.8:1 to 1.5:1.
Further, the solvent includes DMF, DMA, absolute ethyl alcohol, second two
One kind in alcohol or acetone.
Further, the organic ligand include terephthalic acid (TPA), M-phthalic acid, trimesic acid, trimellitic acid,
One kind in 2- amino terephthalic acid (TPA)s.
Further, the specified atmosphere is nitrogen oxygen atmosphere atmosphere, nitrogen mass content in the nitrogen oxygen atmosphere atmosphere
90% to 95%, oxygen quality content is 5% to 10%.
Further, the pre-sintered condition is:600 DEG C to 700 DEG C insulation 4h to 5h;The heat treatment condition is:750
DEG C to 850 DEG C insulation 8h to 15h.
Transition metal, elemental lithium and doped chemical that may be present can be with preparation method described in the embodiment of the present invention
The uniform mixing of atomic level is realized in sol-gel state, reduction can be prepared to a certain extent at the heat of tertiary cathode material
Manage temperature;Tertiary cathode material prepared by the present invention, can be by changing the species of organic ligand, or under inert atmosphere at preheating
The reaction condition of reason, easily realize the size controlling of tertiary cathode material;Preparation method of the present invention can pass through adjustment
The additional proportion of gel preparatory phase nickel cobalt manganese salt, realizes the regulation and control of the chemical constituent of positive electrode, prepares different types of three
First positive electrode.
The embodiment of the present invention also provides a kind of tertiary cathode material, formula LiNi(1-x-y-z)CoxMnyMzO2, wherein, x+y
+z<1, x>0, y>0, M is doped chemical, is prepared by above-mentioned preparation method.
The ternary material LiNi(1-x-y-z)CoxMnyMzO2For neat appearance and the spherical shape of centralized particle diameter
Looks.Lithium ion battery using the tertiary cathode material and the lithium ion battery phase using conventional three-way positive electrode
Than:Cycle performance gets a promotion;Gram volume also gets a promotion.
Below by way of several embodiments, be further described the embodiment of the present invention concrete operations flow and
Pass through the chemical property of tertiary cathode material made from preparation method described in the embodiment of the present invention.
Embodiment one:
Take 1.10mol lithium chlorides, 0.75mol nickel chlorides, 0.1mol cobalt chlorides, 0.1mol manganese chlorides and 0.05mol chlorinations
Aluminium is dissolved in 0.5L DMF, the stirring through 30min, obtains reaction solution A.
Take 0.05mol terephthalic acid (TPA)s to be dissolved in 0.5L DMF, the stirring through 30min, obtain anti-
Answer liquid B.
Reaction solution B is added to the reaction solution A being under magnetic agitation state, after reacting 10min under lasting stirring,
Send to vacuum filtration, you can obtain wet gel, the filtrate for filtering to obtain is recyclable.
The wet gel that will be obtained, it is pre-sintered at 700 DEG C in the nitrogen oxygen atmosphere atmosphere that nitrogen mass content is 90%
4h, after being cooled to room temperature, after taking out grinding, under oxygen atmosphere, 15h is heat-treated at 750 DEG C, obtains tertiary cathode material
LiNi0.75Co0.1Mn0.1Al0.05O2.Its pattern is as shown in Fig. 2 XRD is as shown in Figure 3.
Using obtained tertiary cathode material as positive electrode and conductive agent SP and bonding agent according to 8:1:1 mass ratio
Example uniformly mixing, is added dropwise appropriate solvent (NMP), is ground into after uniform sizing material coated on aluminium foil.12h is dried in vacuo in 60 DEG C
Afterwards, a diameter of 10mm electrode slice is struck out, using metal lithium sheet as negative pole, lithium-ion battery electrolytes are added, in glove box
It is assembled into CR2032 button cells.At room temperature, in 3.0-4.25V voltage ranges, the present embodiment under 0.1C discharge current densities
Tertiary cathode material capacity is up to 195.2mAh/g, and 0.5C discharge current densities are up to 184.4mAh/g, 1C discharge current densities
Up to 179.9mAh/g, 5C discharge current densities are up to 169.2mAh/g.After 0.5C is circulated 100 times, capability retention is
97.4%.The 0.1C charging and discharging curve figures of battery corresponding to the ternary material are as shown in figure 4, electric corresponding to the ternary material
The cycle performance curve map in pond is as shown in Figure 5.
Embodiment two:
Take 1.075mol lithium sulfates, 1.2mol nickel sulfates, 0.4mol cobaltous sulfates, 0.35mol manganese sulfates and 0.05mol sulfuric acid
Zirconium is dissolved in 0.5L DMA, the stirring through 30min, obtains reaction solution A.
Take 0.1mol M-phthalic acids to be dissolved in 0.5L DMA, the stirring through 30min, reacted
Liquid B.
Reaction solution B is added to the reaction solution A being under magnetic agitation state, after reacting 15min under lasting stirring,
Send to vacuum filtration, you can obtain wet gel, the filtrate for filtering to obtain is recyclable.
The wet gel that will be obtained, in the nitrogen oxygen atmosphere atmosphere that nitrogen content is 92%, pre-sintered 4h, cold at 600 DEG C
But to after room temperature, after taking out grinding, in air atmosphere, 12h is heat-treated at 800 DEG C, obtains tertiary cathode material
LiNi0.6Co0.2Mn0.175Zr0.025O2。
Using obtained tertiary cathode material as positive electrode and conductive agent SP and bonding agent according to 8:1:1 mass ratio
Example uniformly mixing, is added dropwise appropriate solvent (NMP), is ground into after uniform sizing material coated on aluminium foil.12h is dried in vacuo in 60 DEG C
Afterwards, a diameter of 10mm electrode slice is struck out, using metal lithium sheet as negative pole, lithium-ion battery electrolytes are added, in glove box
It is assembled into CR2032 button cells.At room temperature, in 3.0-4.25V voltage ranges, this patent synthesizes under 0.1C discharge current densities
Tertiary cathode material capacity it is close up to 173.6mAh/g, 1C discharge currents up to 180.5mAh/g, 0.5C discharge current densities
Degree is up to 170.5mAh/g, and 5C discharge current densities are up to 163.7mAh/g.After 0.5C is circulated 100 times, capability retention is
98.1%.
Embodiment three:
Take 0.575mol lithium chlorides, 0.4mol nickel chlorides, 0.05mol cobalt chlorides, 0.04mol manganese chlorides and 0.01mol chlorine
Change titanium to be dissolved in 1L DMF, the stirring through 25min, obtain reaction solution A.
Take 0.5mol trimesic acids to be dissolved in 0.8L DMF, the stirring through 25min, reacted
Liquid B.
Reaction solution B is added to the reaction solution A being under magnetic agitation state, after reacting 5min under lasting stirring,
Send to vacuum filtration, you can obtain wet gel, filter, obtained filtrate is recyclable.
The wet gel that will be obtained, in the nitrogen oxygen atmosphere atmosphere that nitrogen content is 95%, pre-sintered 4h, cold at 650 DEG C
But to after room temperature, after taking out grinding, under oxygen atmosphere, 8h is heat-treated at 850 DEG C, obtains tertiary cathode material
LiNi0.8Co0.1Mn0.08Ti0.02O2。
Using obtained tertiary cathode material as positive electrode and conductive agent SP and bonding agent according to 8:1:1 mass ratio
Example uniformly mixing, is added dropwise appropriate solvent (NMP), is ground into after uniform sizing material coated on aluminium foil.12h is dried in vacuo in 60 DEG C
Afterwards, a diameter of 10mm electrode slice is struck out, using metal lithium sheet as negative pole, lithium-ion battery electrolytes are added, in glove box
It is assembled into CR2032 button cells.At room temperature, in 3.0-4.25V voltage ranges, this patent synthesizes under 0.1C discharge current densities
Tertiary cathode material capacity it is close up to 198.2mAh/g, 1C discharge currents up to 210.8mAh/g, 0.5C discharge current densities
Degree is up to 192.4mAh/g, and 5C discharge current densities are up to 180.5mAh/g.After 0.5C is circulated 100 times, capability retention is
96.8%.
Example IV:
1.575mol lithium acetates, 1mol nickel acetates, 1mol cobalt acetates, 0.9mol manganese acetates and 0.1mol acetic acid zirconiums is taken to be dissolved in
In 1L DMF, the stirring through 40min, reaction solution A is obtained.
Take 0.8mol terephthalic acid (TPA)s to be dissolved in 1.2L DMF, the stirring through 40min, reacted
Liquid B.
Reaction solution B is added to the reaction solution A being under magnetic agitation state, after reacting 30min under lasting stirring,
Send to vacuum filtration, you can obtain wet gel, the filtrate for filtering to obtain is recyclable.
The wet gel that will be obtained, in the nitrogen oxygen atmosphere atmosphere that nitrogen content is 93%, the pre-sintered 4.5h at 600 DEG C,
After being cooled to room temperature, after taking out grinding, in air atmosphere, 12h is heat-treated at 780 DEG C, obtains tertiary cathode material
LiNi1/3Co1/3Mn0.3Zr1/30O2。
Using obtained tertiary cathode material as positive electrode and conductive agent SP and bonding agent according to 8:1:1 mass ratio
Example uniformly mixing, is added dropwise appropriate solvent (NMP), is ground into after uniform sizing material coated on aluminium foil.12h is dried in vacuo in 60 DEG C
Afterwards, a diameter of 10mm electrode slice is struck out, using metal lithium sheet as negative pole, lithium-ion battery electrolytes are added, in glove box
It is assembled into CR2032 button cells.At room temperature, in 3.0-4.25V voltage ranges, this patent synthesizes under 0.1C discharge current densities
Tertiary cathode material capacity it is close up to 147.1mAh/g, 1C discharge currents up to 150.1mAh/g, 0.5C discharge current densities
Degree is up to 145.2mAh/g, and 5C discharge current densities are up to 141.5mAh/g.After 0.5C is circulated 100 times, capability retention is
98.8%.
Embodiment five:
Take 4.24mol lithium chlorides, 2mol nickel chlorides, 0.8mol cobalt chlorides, 1.16mol manganese chlorides and 0.04mol aluminium chloride
It is dissolved in 2L absolute ethyl alcohol, the stirring through 40min, obtains reaction solution A.
Take 1mol terephthalic acid (TPA)s to be dissolved in 1.6L absolute ethyl alcohol, the stirring through 40min, obtain reaction solution B.
Reaction solution B is added to the reaction solution A being under magnetic agitation state, after reacting 45min under lasting stirring,
Send to vacuum filtration, you can obtain wet gel, filter, obtained filtrate is recyclable.
The wet gel that will be obtained, in the nitrogen oxygen atmosphere atmosphere that nitrogen content is 91%, pre-sintered 5h, cold at 700 DEG C
But to after room temperature, after taking out grinding, in air atmosphere, 10h is heat-treated at 830 DEG C, obtains tertiary cathode material
LiNi0.5Co0.2Mn0.29Al0.01O2。
Using obtained tertiary cathode material as positive electrode and conductive agent SP and bonding agent according to 8:1:1 mass ratio
Example uniformly mixing, is added dropwise appropriate solvent (NMP), is ground into after uniform sizing material coated on aluminium foil.12h is dried in vacuo in 60 DEG C
Afterwards, a diameter of 10mm electrode slice is struck out, using metal lithium sheet as negative pole, lithium-ion battery electrolytes are added, in glove box
It is assembled into CR2032 button cells.At room temperature, in 3.0-4.25V voltage ranges, this patent synthesizes under 0.1C discharge current densities
Tertiary cathode material capacity it is close up to 151.3mAh/g, 1C discharge currents up to 157.6mAh/g, 0.5C discharge current densities
Degree is up to 146.8mAh/g, and 5C discharge current densities are up to 140.4mAh/g.After 0.5C is circulated 100 times, capability retention is
98.5%.
Gel has been obtained by very simple efficient method first in the embodiment of the present invention, can not only ensure each member
Element is uniformly distributed, and the gel preparation course used time is short, is heated without external heat source, so as to effectively save energy, and is taken out
Filter the repeatable utilization of obtained filtrate;In the embodiment of the present invention in inert atmosphere preheating treatment procedure, the volatilization of residual solvent and
The thermal decomposition process of organic ligand ensure that material can obtain regular and centralized particle diameter spherical morphology, and these patterns are special
Sign can remain in follow-up oxidizing atmosphere high-temperature heat treatment process, obtain spherical ternary cathode material.It is of the invention real
The spherical ternary cathode material of example preparation is applied, gram volume can be fully played, it is also ensured that material has outstanding follow
Ring stability, while it is distributed the particle diameter of concentration and spherical morphology also improves the processing characteristics of material.Institute in the embodiment of the present invention
Original can be realized in sol-gel state by stating transition metal in preparation method, elemental lithium and doped chemical that may be present
The uniform mixing of sub- rank, reduction the heat treatment temperature of tertiary cathode material can be prepared to a certain extent, while can passed through
Change the species of organic ligand, or under inert atmosphere the pre-heat treatment reaction condition, easily realize the grain of tertiary cathode material
Footpath controls;By adjusting the additional proportion of gel preparatory phase nickel cobalt manganese salt, the regulation and control of the chemical constituent of positive electrode are realized.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the scope of the invention, every utilization
The equivalent structure or equivalent flow conversion that description of the invention and accompanying drawing content are made, or directly or indirectly it is used in other correlations
Technical field, be included within the scope of the present invention.