CN106745338A - Tertiary cathode material and preparation method thereof - Google Patents
Tertiary cathode material and preparation method thereof Download PDFInfo
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- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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Abstract
Present invention is disclosed 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：Raw material salt is added in first part of designated solvent by the amount ratio of certain material, reaction solution A is obtained through magnetic agitation；A certain amount of organic ligand is added in the solvent described in second part, reaction solution B is obtained through magnetic agitation；According to certain volume than the reaction solution B being poured into the reaction solution A being in stirring, react certain hour, suction filtration obtains wet gel under lasting stirring；By the wet gel, in the case where atmosphere is specified, pre-sintering obtains presoma, is heat-treated in an oxidizing atmosphere after the presoma is taken out into grinding, obtains tertiary cathode material.The inventive gel preparation process used time is short, and without external heat source heating, and resulting materials are the spherical morphology of neat appearance.
Description
Technical field
The present invention relates to new energy field, a kind of tertiary cathode material and preparation method thereof is especially related to.
Background technology
In recent years, the appearance of new-energy automobile, for the development of lithium ion battery industry provides new power.And as new
The lithium-ion-power cell of energy automobile kernel component, the quality of its performance is even more and is 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 energy density higher, just gradually substitution LiFePO4 turns into new-energy automobile (particularly passenger car
Type) with the first-selected positive electrode of lithium-ion-power cell, also as 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 the uniformity of doping vario-property miscellaneous Elemental redistribution when processing, while the particle diameter for reducing material appropriate, 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-high
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 ensure well the realization of above-mentioned requirements.
In the numerous new ternary material synthetic method 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)
Course of reaction very long.Also, the product morphology for obtaining 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 are prepared
First positive electrode.
The content of the invention
The main object of the present invention is to provide a kind of method that sol-gel technology prepares tertiary cathode material, it is intended to solved
Certainly existing sol-gel preparation process needs the problem reacted for a long time in the case where external heat source is heated.
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
Reaction certain hour, suction filtration obtains wet gel；
By the wet gel, in the case where atmosphere is specified, 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 one or more in aluminium salt, zirconates, titanium salt；The aluminium salt and zirconium
Salt is respectively the one kind in villaumite, sulfate or acetate corresponding to each metal ion；The titanium salt includes titanium chloride, titanium sulfate
Or the 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 volume ratio of the reaction solution A and reaction solution B is 0.8 to 1.5.
Preferably, the solvent includes DMF, DMA, absolute ethyl alcohol, ethylene glycol
Or the 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℃
Insulation 8-15h.
The present invention also provides a kind of tertiary cathode material, and formula is LiNi(1-x-y-z)CoxMnyMzO2, wherein, x+y+z<1, x
>0, y>0, M is doped chemical, is prepared from 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, without external heat source heating, so as to effectively save energy
Amount, and the repeatable utilization of filtrate that suction filtration is obtained；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 is obtained in that regular and centralized particle diameter spherical morphology, these patterns
Feature can be remained 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 energy；Ternary material grain diameter of the invention and material
Inner element is uniformly distributed, and its gram volume can both fully played, it is also ensured that material has outstanding circulation
Stability, while the particle diameter and spherical morphology that are distributed concentration improve 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, realizes the regulation and control of the chemical constituent of positive electrode, prepares different types of tertiary cathode material；Preparation process is simple can
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 of the object of the invention, functional characteristics and advantage will be described further referring to the drawings in conjunction with the embodiments.
Specific 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 proposes 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 react certain hour under state, suction filtration obtains wet gel；
S3：By the wet gel, in the case where atmosphere is specified, 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, suction filtration
Time about 30min, much smaller than conventional sol gel method；Preparation process saves energy very much without heating；And after suction filtration
Filtrate can reuse.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 is obtained in that the spherical morphology of neat appearance and centralized particle diameter, these shapes
Looks feature can be remained 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 is added in gel preparation course, it is ensured 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 the 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 the 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 one or more in aluminium salt, zirconates, titanium salt；The aluminium salt and
Zirconates is respectively the 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 the one kind in aluminium chloride, aluminum sulfate or aluminum acetate；The zirconates bag
Include the 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.
The amount of lithium salts, nickel salt, cobalt salt, manganese salt and the corresponding material of doped chemical salt described in the embodiment of the present invention is 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 volume ratio of the reaction solution A and reaction solution B 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 at the heat of tertiary cathode material to a certain extent
Reason 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 realizes the size controlling of tertiary cathode material；Preparation method of the present invention can be by 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, and formula is LiNi(1-x-y-z)CoxMnyMzO2, wherein, x+y
+z<1, x>0, y>0, M is doped chemical, is prepared from by above-mentioned preparation method.
The ternary material LiNi(1-x-y-z)CoxMnyMzO2It is 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 specific embodiments, further describe the embodiment of the present invention concrete operations flow and
By the chemical property of tertiary cathode material obtained in 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 the DMF of 0.5L, through the stirring of 30min, obtains reaction solution A.
Take 0.05mol terephthalic acid (TPA)s to be dissolved in the DMF of 0.5L, through the stirring of 30min, obtain anti-
Answer liquid B.
Reaction solution B is added 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 that suction filtration is obtained is recyclable.
The wet gel that will be obtained, in the nitrogen oxygen atmosphere atmosphere that nitrogen mass content is 90%, in pre-sintered at 700 DEG C
4h, after being cooled to room temperature, after taking out grinding, under oxygen atmosphere, in 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.
The tertiary cathode material that will be obtained is as positive electrode and conductive agent SP and bonding agent according to 8:1:1 mass ratio
The uniform mixing of example, is added dropwise appropriate solvent (NMP), is coated on aluminium foil after grinding to form uniform sizing material.12h is vacuum dried in 60 DEG C
Afterwards, the electrode slice of a diameter of 10mm is struck out, with metal lithium sheet as negative pole, lithium-ion battery electrolytes is 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
, up to 195.2mAh/g, 0.5C discharge current densities are up to 184.4mAh/g, 1C discharge current densities for tertiary cathode material capacity
Up to 179.9mAh/g, 5C discharge current densities are up to 169.2mAh/g.After 0.5C circulates 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, electricity 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 the DMA of 0.5L, through the stirring of 30min, obtains reaction solution A.
Take 0.1mol M-phthalic acids to be dissolved in the DMA of 0.5L, through the stirring of 30min, reacted
Liquid B.
Reaction solution B is added 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 that suction filtration is obtained is recyclable.
The wet gel that will be obtained, it is cold in pre-sintering 4h at 600 DEG C in the nitrogen oxygen atmosphere atmosphere that nitrogen content is 92%
But to after room temperature, after taking out grinding, in air atmosphere, in 12h is heat-treated at 800 DEG C, tertiary cathode material is obtained
LiNi0.6Co0.2Mn0.175Zr0.025O2。
The tertiary cathode material that will be obtained is as positive electrode and conductive agent SP and bonding agent according to 8:1:1 mass ratio
The uniform mixing of example, is added dropwise appropriate solvent (NMP), is coated on aluminium foil after grinding to form uniform sizing material.12h is vacuum dried in 60 DEG C
Afterwards, the electrode slice of a diameter of 10mm is struck out, with metal lithium sheet as negative pole, lithium-ion battery electrolytes is added, in glove box
It is assembled into CR2032 button cells.At room temperature, in 3.0-4.25V voltage ranges, this patent synthesis under 0.1C discharge current densities
Tertiary cathode material capacity up to 180.5mAh/g, 0.5C discharge current densities are up to 173.6mAh/g, and 1C discharge currents are close
, up to 170.5mAh/g, 5C discharge current densities are up to 163.7mAh/g for degree.After 0.5C circulates 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 the DMF of 1L, through the stirring of 25min, obtain reaction solution A.
Take 0.5mol trimesic acids to be dissolved in the DMF of 0.8L, through the stirring of 25min, reacted
Liquid B.
Reaction solution B is added the reaction solution A being under magnetic agitation state, after reacting 5min under lasting stirring,
Send to vacuum filtration, you can obtain wet gel, suction filtration, the filtrate for obtaining is recyclable.
The wet gel that will be obtained, it is cold in pre-sintering 4h at 650 DEG C in the nitrogen oxygen atmosphere atmosphere that nitrogen content is 95%
But to after room temperature, after taking out grinding, under oxygen atmosphere, in 8h is heat-treated at 850 DEG C, tertiary cathode material is obtained
LiNi0.8Co0.1Mn0.08Ti0.02O2。
The tertiary cathode material that will be obtained is as positive electrode and conductive agent SP and bonding agent according to 8:1:1 mass ratio
The uniform mixing of example, is added dropwise appropriate solvent (NMP), is coated on aluminium foil after grinding to form uniform sizing material.12h is vacuum dried in 60 DEG C
Afterwards, the electrode slice of a diameter of 10mm is struck out, with metal lithium sheet as negative pole, lithium-ion battery electrolytes is added, in glove box
It is assembled into CR2032 button cells.At room temperature, in 3.0-4.25V voltage ranges, this patent synthesis under 0.1C discharge current densities
Tertiary cathode material capacity up to 210.8mAh/g, 0.5C discharge current densities are up to 198.2mAh/g, and 1C discharge currents are close
, up to 192.4mAh/g, 5C discharge current densities are up to 180.5mAh/g for degree.After 0.5C circulates 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 the DMF of 1L, through the stirring of 40min, reaction solution A is obtained.
Take 0.8mol terephthalic acid (TPA)s to be dissolved in the DMF of 1.2L, through the stirring of 40min, reacted
Liquid B.
Reaction solution B is added 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 that suction filtration is obtained is recyclable.
The wet gel that will be obtained, in the nitrogen oxygen atmosphere atmosphere that nitrogen content is 93%, in pre-sintering 4.5h at 600 DEG C,
After being cooled to room temperature, after taking out grinding, in air atmosphere, in 12h is heat-treated at 780 DEG C, tertiary cathode material is obtained
LiNi1/3Co1/3Mn0.3Zr1/30O2。
The tertiary cathode material that will be obtained is as positive electrode and conductive agent SP and bonding agent according to 8:1:1 mass ratio
The uniform mixing of example, is added dropwise appropriate solvent (NMP), is coated on aluminium foil after grinding to form uniform sizing material.12h is vacuum dried in 60 DEG C
Afterwards, the electrode slice of a diameter of 10mm is struck out, with metal lithium sheet as negative pole, lithium-ion battery electrolytes is added, in glove box
It is assembled into CR2032 button cells.At room temperature, in 3.0-4.25V voltage ranges, this patent synthesis under 0.1C discharge current densities
Tertiary cathode material capacity up to 150.1mAh/g, 0.5C discharge current densities are up to 147.1mAh/g, and 1C discharge currents are close
, up to 145.2mAh/g, 5C discharge current densities are up to 141.5mAh/g for degree.After 0.5C circulates 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 the absolute ethyl alcohol of 2L, through the stirring of 40min, obtains reaction solution A.
Take 1mol terephthalic acid (TPA)s to be dissolved in the absolute ethyl alcohol of 1.6L, through the stirring of 40min, obtain reaction solution B.
Reaction solution B is added the reaction solution A being under magnetic agitation state, after reacting 45min under lasting stirring,
Send to vacuum filtration, you can obtain wet gel, suction filtration, the filtrate for obtaining is recyclable.
The wet gel that will be obtained, it is cold in pre-sintering 5h at 700 DEG C in the nitrogen oxygen atmosphere atmosphere that nitrogen content is 91%
But to after room temperature, after taking out grinding, in air atmosphere, in 10h is heat-treated at 830 DEG C, tertiary cathode material is obtained
LiNi0.5Co0.2Mn0.29Al0.01O2。
The tertiary cathode material that will be obtained is as positive electrode and conductive agent SP and bonding agent according to 8:1:1 mass ratio
The uniform mixing of example, is added dropwise appropriate solvent (NMP), is coated on aluminium foil after grinding to form uniform sizing material.12h is vacuum dried in 60 DEG C
Afterwards, the electrode slice of a diameter of 10mm is struck out, with metal lithium sheet as negative pole, lithium-ion battery electrolytes is added, in glove box
It is assembled into CR2032 button cells.At room temperature, in 3.0-4.25V voltage ranges, this patent synthesis under 0.1C discharge current densities
Tertiary cathode material capacity up to 157.6mAh/g, 0.5C discharge current densities are up to 151.3mAh/g, and 1C discharge currents are close
, up to 146.8mAh/g, 5C discharge current densities are up to 140.4mAh/g for degree.After 0.5C circulates 100 times, capability retention is
98.5%.
Gel is obtained by very simple efficient method first in the embodiment of the present invention, can not only ensure each yuan
Plain is uniformly distributed, and the gel preparation course used time is short, without external heat source heating, so as to effectively save energy, and takes out
The repeatable utilization of filtrate that filter is obtained；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 is obtained in that regular and centralized particle diameter spherical morphology, and these patterns are special
Levying 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 following
Ring stability, while the particle diameter and spherical morphology that are distributed concentration also improve the processing characteristics of material.Institute in the embodiment of the present invention
Transition metal, elemental lithium and doped chemical that may be present can realize original in sol-gel state in stating preparation method
The uniform mixing of sub- rank, reduction can prepare the heat treatment temperature of tertiary cathode material, while can pass through to a certain extent
Change organic ligand species, 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, the scope of the claims of the invention, every utilization is not thereby limited
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.
Claims (10)
1. 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, it is characterised in that including：
By lithium salts, nickel salt, cobalt salt, manganese salt and doped chemical salt in the amount ratio of certain material be added to first part specify it is molten
It is agitated to obtain reaction solution A in agent；A certain amount of organic ligand is added in second part of solvent, it is agitated to obtain anti-
Answer liquid B；
According to certain volume than pouring into the reaction solution B in the reaction solution A being in stirring, reacted under lasting stirring
Certain hour, suction filtration obtains wet gel；
By the wet gel, in the case where atmosphere is specified, pre-sintering obtains presoma, after the presoma is taken out into grinding, in oxidisability
It is heat-treated under atmosphere, obtains tertiary cathode material.
2. the preparation method of tertiary cathode material as claimed in claim 1, it is characterised in that the lithium salts, nickel salt, cobalt salt,
Manganese salt is respectively the one kind in villaumite, sulfate or acetate corresponding to each metal ion.
3. the preparation method of tertiary cathode material as claimed in claim 1, it is characterised in that the doped chemical salt includes
One or more in aluminium salt, zirconates, titanium salt；The aluminium salt and zirconates are respectively villaumite, sulfate corresponding to each metal ion
Or the one kind in acetate；The titanium salt includes the one kind in titanium chloride, titanium sulfate or butyl titanate.
4. the preparation method of tertiary cathode material as claimed in claim 1, it is characterised in that when the M is Al, 0<z<0.1,
When M is Zr and Ti, 0<z<0.05.
5. the preparation method of tertiary cathode material as claimed in claim 1, it is characterised in that lithium salts is dense in the reaction solution A
Spend for 0.2mol/L to 4mol/L；Organic ligand concentration is 0.05mol/L to 1mol/L in the reaction solution B；The reaction solution A
It is 0.8 with the volume ratio of reaction solution B:1 to 1.5:1.
6. the preparation method of tertiary cathode material as claimed in claim 1, it is characterised in that the solvent includes N, N- diformazans
One kind in base formamide, DMAC N,N' dimethyl acetamide, absolute ethyl alcohol, ethylene glycol or acetone.
7. the preparation method of tertiary cathode material as claimed in claim 1, it is characterised in that the organic ligand is included to benzene
One kind in dioctyl phthalate, M-phthalic acid, trimesic acid, trimellitic acid, 2- amino terephthalic acid (TPA)s.
8. the preparation method of tertiary cathode material as claimed in claim 1, it is characterised in that the specified atmosphere is mixed for nitrogen oxygen
Atmosphere, nitrogen mass content 90% to 95% in the nitrogen oxygen atmosphere atmosphere are closed, oxygen quality content is 5% to 10%.
9. the preparation method of tertiary cathode material as claimed in claim 1, it is characterised in that 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.
10. a kind of tertiary cathode material, formula is LiNi(1-x-y-z)CoxMnyMzO2, wherein, x+y+z<1, x>0, y>0, M is doping
Element, it is characterised in that the preparation method any one of claim 1-9 is prepared from.
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