CN107265519B - A kind of application for improving lithium ion cell positive gradient distribution material precursor and synthesizing the method and its presoma of particle size uniformity - Google Patents
A kind of application for improving lithium ion cell positive gradient distribution material precursor and synthesizing the method and its presoma of particle size uniformity Download PDFInfo
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a kind of raising lithium ion cell positive gradient distribution material precursor Ni0.6Co0.2Mn0.2(OH)2The method of particle size uniformity and its application of presoma are synthesized, the described method comprises the following steps: taking nickel salt, cobalt salt, manganese salt configuration different mol ratio example, the solution A of same concentrations, solution B and solution C first；Then the presoma that is reduced to material surface Ni:Co:Mn=1:1:1 of the core by Ni:Co:Mn=8:1:1 slowly is finally made by coprecipitation reaction in ammonia density and pH value by way of gradually mixed feeding, and in fill process synchronization modulation reaction system.Gradient distribution material precursor Ni is made in the present invention0.6Co0.2Mn0.2(OH)2, tap density is higher, and material property is excellent, and material granule is uniform.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of raising lithium ion cell positive gradient distribution materials
Material precursor Ni0.6Co0.2Mn0.2(OH)2Synthesize the method for particle size uniformity and its application of presoma.
Background technique
Present positive electrode ternary high-nickel material is the biggest problems are that its safety and capacity are kept, high-nickel material
Structure inherently shows the maximum challenge that thermal stability is bad, this kind of similar positive electrode commercialization faces.Ni4+?
It is extremely unstable when charged state, especially at high temperature, side reaction occurs with electrolyte, is shortened which results in cycle life
Main cause.High-nickel material easily generates impurity LiOH and Li in air2CO3, LiOH easily be easy with electrolyte in
LiPF6Generation side reaction, generation HF, and Li2CO3Inflatable easily occurs in charged state, leads to security risk.And in charge and discharge
Serious phase transformation occurs for high-nickel material in electric process, and irreversible capacity is caused to increase, and capacity keeps not fully up to expectations.In addition, existing
Positive gradient distribution material, little particle disintegrating slag is relatively more, and material entirety tap density is low；And the high-nickel material in little particle
Mix with low nickel material, the gradient distribution material property of formation is not very good.
Summary of the invention
In view of this, the present invention provides a kind of raising lithium ion cell positive gradient distribution material precursors
Ni0.6Co0.2Mn0.2(OH)2The method of particle size uniformity and its application of presoma are synthesized, above-mentioned technical problem is solved.
The technological means that the present invention uses is as follows: a kind of pair of lithium ion cell positive gradient distribution material Ni0.6Co0.2Mn0.2
(OH)2Synthesize the non-uniform improved method of granularity, comprising the following steps:
S1, nickel salt, cobalt salt, manganese salt configuration different mol ratio example, the solution A of same concentrations, solution B and solution C are taken, it is described
Ni:Co:Mn total moles ratio is 6:2:2 in solution A, solution B and solution C,
Ni:Co:Mn molar ratio is (9.5~7.5): (0.25~1.25): (0.25~1.25), volume in the solution A
For 0.6a~0.8a；
Ni:Co:Mn molar ratio is (1.5~0.5) in the solution C: (3~1): (3~1), volume are 0.5a~0.3a；
The bottom liquid that ammonia density is 0.7~0.5mol/L is configured simultaneously；
S2, the solution A, solution B, solution C of step S1 are respectively placed in A container, B container, in C container, by the bottom liquid
It is placed in the automatic continuous reaction kettle that volume is 5a, solution A is pumped into reaction kettle first by reaction kettle described in the A reservoir
In,
When solution A residual volume is 0.4a~0.1a, solution B is pumped into solution A, while mixed solution in A container
It is continuously pumped into reaction kettle under stiring；When solution B is pumped into solution A completely, then solution C is pumped into solution A, is kept simultaneously
Mixed solution is continuously pumped into reaction kettle in A container；Flow velocity V1 that the solution B is pumped into solution A, the solution C are pumped into molten
The flow velocity V3 that mixed solution is pumped into reaction kettle in flow velocity V2 and A container in liquid A is consistent, i.e. V1=V2=V3；
During the solution A is pumped into reaction kettle, fixed reaction condition, maintain in reaction system ammonia density be 0.7~
Definite value within the scope of 0.5mol/L, maintaining pH value of reaction system is the definite value in 11.3~11.7 ranges；
During the solution B, solution C are successively pumped into solution A, pH value of reaction system gradually declines from 11.3~11.7
To 11.0, the ammonia density of reaction system gradually drops to 0.4~0.3mol/L from 0.7~0.5mol/L；
It is 45~55 DEG C that reaction process, which controls reaction temperature, and the reaction time is 18~26 hours, most by coprecipitation reaction
The obtained presoma that is reduced to material surface Ni:Co:Mn=1:1:1 of the core by Ni:Co:Mn=8:1:1 slowly eventually.
Further, during the solution B, solution C are successively pumped into solution A, pH value of reaction system gradually descends the range of decrease
Degree reduced by 0.05 for each hour, and finally maintained 11.
Further, in the solution A Ni:Co:Mn molar ratio be 8:1:1, volume 0.7a,
In the solution B Ni:Co:Mn molar ratio be 4:1:1, volume 0.3a,
In the solution C Ni:Co:Mn molar ratio be 1:2:2, volume 0.4a.
Further, the nickel salt, cobalt salt, manganese salt are respectively NiSO4·6H2O、CoSO4·7H2O and MnSO4·H2O, system
The presoma chemical property obtained is higher.
Further, control is adjusted using 10mol/L NaOH solution in the pH value, can preferably adjust reactant
PH value in system, and be in progress with reaction and flexibly change, further increase the tap density of material.
Further, control is adjusted using 2.8mol/L ammonium hydroxide in the ammonia density of the bottom liquid, can preferably adjust anti-
Ammonia density in system is answered, so that reaction process flexible modulation ammonia density, has advanced optimized material morphology and its chemical property.
Further, during charging, reaction kettle stirring rate is 600~800r/min, effectively facilitates co-precipitation
Effect.
The present invention also provides a kind of ternary cathode material of lithium ion batteries, have the described in any item presomas of the present invention.
The present invention also provides a kind of preparation methods of ternary cathode material of lithium ion battery, using described in any one of the present invention
Presoma Ni0.6Co0.2Mn0.2(OH)2It is the 1:1.05 500-900 DEG C of roasting in Muffle furnace after mixing with LiOH molar ratio
5-30h is burnt, 10 DEG C/s of heating rate obtains positive electrode Li [Ni0.6Co0.2Mn0.2]O2, tested for electrode material.
Compared with prior art, the beneficial effects of the present invention are: gradient distribution material precursor produced by the present invention
Ni0.6Co0.2Mn0.2(OH)2Ni content is gradually decreased from core layer, improves the content of Co, Mn, forms similar 1:1:1 in outermost layer
Layer；Gradient distribution material obtained possesses oneself unique effect under high tension voltage, possesses higher specific capacity, and
The cyclical stability of small multiplying power or big multiplying power shows excellent；Gradient distribution material prepared by the present invention does not have in ratio conversion
Apparent interface is formed, the material of present core-shell structure is different from.Because electrochemical reaction occurs in electrode and electrolyte liquor surface, material
Expect interface situation it is just quite important, gradient distribution material solve core-shell material interfaces transition metal component mutation caused by
Structure caused by volume change in charge and discharge process mismatches, and makes Li+ lithium ion diffusion hindered, and chemical property is deteriorated.This
The gradient distribution material for inventing preparation can provide gentle transition to the diffusion of Li+ lithium ion.The gradient distribution material sintering
The XRD measured does not generate other miscellaneous phases, maintains crystal form identical with homogeneous material, and there is no because being gradient distribution material
With regard to other phase transformations occur.Preparation method of the invention is easy to operate, and can solve the low problem of high-nickel material capacity retention ratio,
It can also inhibit phase transformation of the high-nickel material in charge and discharge process, on the basis of not improving material cost, it is easy to accomplish industrialization,
Obtain more stable, the higher positive electrode of capacity.Meanwhile in reaction process of the invention, material is from core to surface layer element ratio
Example is changing, synchronous change reaction condition, so that Ni, Co, Mn hydroxide precipitate simultaneously forms solid solution, material obtained
Material granularity is more uniform, and tap density is higher, and energy density is highly improved.
Detailed description of the invention
Fig. 1 is the SEM figure of gradient distribution materials Example 1 (a) of the present invention and comparative example 1 (b).
Fig. 2 is the 2.8-4.3V 0.2C cyclic curve figure of gradient distribution materials Example 1 and comparative example 1 of the present invention.
Specific embodiment
The principles and features of the present invention are described below, and illustrated embodiment is served only for explaining the present invention, is not intended to
It limits the scope of the invention.
Embodiment 1
A kind of raising lithium ion cell positive gradient distribution material precursor Ni0.6Co0.2Mn0.2(OH)2Synthesize epigranular
The method of property, comprising the following steps:
S1, the automatic continuous reaction kettle for getting out 5L；Take NiSO4·6H2O、CoSO4·7H2O and MnSO4·H2O is configured not
Same molar ratio, the solution A of same concentrations, solution B and solution C, Ni:Co:Mn always rubs in the solution A, solution B and solution C
Your ratio is 6:2:2,
In the solution A Ni:Co:Mn molar ratio be 8:1:1, volume 0.7L,
In the solution B Ni:Co:Mn molar ratio be 4:1:1, volume 0.3L,
In the solution C Ni:Co:Mn molar ratio be 1:2:2, volume 0.4L；
0.5mol/L ammonium hydroxide is configured simultaneously, as reaction bottom liquid；
And 10mol/L NaOH solution is configured, for adjusting pH value in control reaction system；
2.8mol/L ammonium hydroxide is configured, for adjusting ammonia density in control reaction system；
S2, the solution A, solution B, solution C of step S1 are respectively placed in A container, B container, in C container, by the bottom 1.9L liquid
It is placed in the automatic continuous reaction kettle that volume is 5L, reaction kettle described in the A reservoir, when bottom liquid and reaction kettle internal temperature
When reaching 50 DEG C, under whole nitrogen protection, solution A is pumped into reaction kettle first,
When solution A residual volume is 0.2L, solution B is pumped into solution A using a peristaltic pump, while being mixed in A container
Solution is closed to be continuously pumped into reaction kettle under stiring；When solution B is pumped into solution A completely, then solution C is pumped into solution A, together
When keep A container in mixed solution be continuously pumped into reaction kettle；The solution B is pumped into flow velocity V1 in solution A, the solution C
The flow velocity V3 that mixed solution is pumped into reaction kettle in flow velocity V2 and the A container being pumped into solution A is consistent, i.e. V1=V2=V3；
During the solution A is pumped into reaction kettle, while adjusting 2.8mol/L ammonium hydroxide, the entrance of 10mol/L NaOH solution
The flow velocity of reaction kettle, so that being capable of fixing reaction condition, maintaining ammonia density in reaction system is 0.5mol/L, maintains reaction system pH
Value is 11.5；
During the solution B, solution C are successively pumped into solution A, pH value of reaction system gradually drops to from 11.5
11.0, reduce by 0.05 within each hour, by 11.5-11.45-11.4-11.35-11.3-11.25-11.2-11.15-11, and it is final
Maintain 11.0；The ammonia density of reaction system gradually drops to 0.3mol/L from 0.5mol/L；During charging, keep anti-
Answering stirring rate in kettle is 700r/min；
It is 50 DEG C that reaction process, which controls reaction temperature, and the reaction time is 22 hours, and core is finally made by coprecipitation reaction
The heart by molar ratio Ni:Co:Mn=8:1:1 Ni0.8Co0.1Mn0.1(OH)2Slowly be reduced to material surface Ni:Co:Mn=1:
1:1Ni1/3Co1/3Mn1/3(OH)2Presoma.
Utilize above-mentioned presoma Ni0.6Co0.2Mn0.2(OH)2It is 1:1.05 after mixing in Muffle furnace with LiOH molar ratio
In 500~900 DEG C of roastings 20h, 10 DEG C/s of heating rate obtain positive electrode Li [Ni0.6Co0.2Mn0.2]O2, it is used for electrode material
Material test.
Embodiment 2
A kind of raising lithium ion cell positive gradient distribution material precursor Ni0.6Co0.2Mn0.2(OH)2Synthesize epigranular
The method of property, comprising the following steps:
S1, the automatic continuous reaction kettle for getting out 5L；Take NiSO4·6H2O、CoSO4·7H2O and MnSO4·H2O is configured not
Same molar ratio, the solution A of same concentrations, solution B and solution C, Ni:Co:Mn always rubs in the solution A, solution B and solution C
Your ratio is 6:2:2,
In the solution A Ni:Co:Mn molar ratio be 9.5:0.25:0.25, volume 0.6L,
In the solution B Ni:Co:Mn molar ratio be 2.62:1:1, volume 0.3L,
In the solution C Ni:Co:Mn molar ratio be 0.5:1:1, volume 0.5L；
0.7mol/L ammonium hydroxide is configured simultaneously, as reaction bottom liquid；
And 10mol/L NaOH solution is configured, for adjusting pH value in control reaction system；
2.8mol/L ammonium hydroxide is configured, for adjusting ammonia density in control reaction system；
S2, the solution A, solution B, solution C of step S1 are respectively placed in A container, B container, in C container, by the bottom 1.9L liquid
It is placed in the automatic continuous reaction kettle that volume is 5L, reaction kettle described in the A reservoir, when bottom liquid and reaction kettle internal temperature
When reaching 45 DEG C, under whole nitrogen protection, solution A is pumped into reaction kettle first,
When solution A residual volume is 0.1L, solution B is pumped into solution A using a peristaltic pump, while being mixed in A container
Solution is closed to be continuously pumped into reaction kettle under stiring；When solution B is pumped into solution A completely, then solution C is pumped into solution A, together
When keep A container in mixed solution be continuously pumped into reaction kettle；The solution B is pumped into flow velocity V1 in solution A, the solution C
The flow velocity V3 that mixed solution is pumped into reaction kettle in flow velocity V2 and the A container being pumped into solution A is consistent, i.e. V1=V2=V3；
During the solution A is pumped into reaction kettle, while adjusting 2.8mol/L ammonium hydroxide, the entrance of 10mol/L NaOH solution
The flow velocity of reaction kettle, so that being capable of fixing reaction condition, maintaining ammonia density in reaction system is 0.7mol/L, maintains reaction system pH
Value is 11.7 ranges；
During the solution B, solution C are successively pumped into solution A, pH value of reaction system gradually drops to from 11.7
11.0,0.05 is reduced, and finally maintains 11.0 within each hour；The ammonia density of reaction system gradually drops to from 0.7mol/L
0.4mol/L；During charging, keeping stirring rate in reaction kettle is 600r/min；
It is 45 DEG C that reaction process, which controls reaction temperature, and the reaction time is 18 hours, and core is finally made by coprecipitation reaction
The heart by molar ratio Ni:Co:Mn=9.5:0.25:0.25 Ni0.95Co0.025Mn0.025(OH)2Slowly be reduced to material surface
Ni:Co:Mn=1:1:1Ni1/3Co1/3Mn1/3(OH)2Presoma.
Utilize above-mentioned presoma Ni0.6Co0.2Mn0.2(OH)2It is 1:1.05 after mixing in Muffle furnace with LiOH molar ratio
In 500~900 DEG C of roastings 5h, 10 DEG C/s of heating rate obtain positive electrode Li [Ni0.6Co0.2Mn0.2]O2, it is used for electrode material
Test.
Embodiment 3
A kind of raising lithium ion cell positive gradient distribution material precursor Ni0.6Co0.2Mn0.2(OH)2Synthesize epigranular
The method of property, comprising the following steps:
S1, the automatic continuous reaction kettle for getting out 5L；Take NiSO4·6H2O、CoSO4·7H2O and MnSO4·H2O is configured not
Same molar ratio, the solution A of same concentrations, solution B and solution C, Ni:Co:Mn always rubs in the solution A, solution B and solution C
Your ratio is 6:2:2,
In the solution A Ni:Co:Mn molar ratio be 7.5:1.25:1.25, volume 0.8L,
In the solution B Ni:Co:Mn molar ratio be 3:1:1, volume 0.3L,
In the solution C Ni:Co:Mn molar ratio be 1.5:3:3, volume 0.3L；
0.6mol/L ammonium hydroxide is configured simultaneously, as reaction bottom liquid；
And 10mol/L NaOH solution is configured, for adjusting pH value in control reaction system；
2.8mol/L ammonium hydroxide is configured, for adjusting ammonia density in control reaction system；
S2, the solution A, solution B, solution C of step S1 are respectively placed in A container, B container, in C container, by the bottom 1.9L liquid
It is placed in the automatic continuous reaction kettle that volume is 5L, reaction kettle described in the A reservoir, when bottom liquid and reaction kettle internal temperature
When reaching 55 DEG C, under whole nitrogen protection, solution A is pumped into reaction kettle first,
When solution A residual volume is 0.4L, solution B is pumped into solution A using a peristaltic pump, while being mixed in A container
Solution is closed to be continuously pumped into reaction kettle under stiring；When solution B is pumped into solution A completely, then solution C is pumped into solution A, together
When keep A container in mixed solution be continuously pumped into reaction kettle；The solution B is pumped into flow velocity V1 in solution A, the solution C
The flow velocity V3 that mixed solution is pumped into reaction kettle in flow velocity V2 and the A container being pumped into solution A is consistent, i.e. V1=V2=V3；
During the solution A is pumped into reaction kettle, while adjusting 2.8mol/L ammonium hydroxide, the entrance of 10mol/L NaOH solution
The flow velocity of reaction kettle, so that being capable of fixing reaction condition, maintaining ammonia density in reaction system is 0.6mol/L, maintains reaction system pH
Value is 11.3；
During the solution B, solution C are successively pumped into solution A, pH value of reaction system gradually drops to from 11.3
11.0,0.05 is reduced, and finally maintains 11.0 within each hour；The ammonia density of reaction system gradually drops to from 0.6mol/L
0.35mol/L；During charging, keeping stirring rate in reaction kettle is 800r/min；
It is 55 DEG C that reaction process, which controls reaction temperature, and the reaction time is 26 hours, and core is finally made by coprecipitation reaction
The heart by molar ratio Ni:Co:Mn=7.5:1.25:1.25 Ni0.75Co0.125Mn0.125(OH)2Slowly be reduced to material surface
Ni:Co:Mn=1:1:1Ni1/3Co1/3Mn1/3(OH)2Presoma.
Utilize above-mentioned presoma Ni0.6Co0.2Mn0.2(OH)2It is 1:1.05 after mixing in Muffle furnace with LiOH molar ratio
In 500~900 DEG C of roastings 30h, 10 DEG C/s of heating rate obtain positive electrode Li [Ni0.6Co0.2Mn0.2]O2, it is used for electrode material
Material test.
Comparative example 1
This comparative example the difference from embodiment 1 is that, reaction process control reaction condition it is constant, maintain reaction system in ammonia
Concentration is 0.5mol/L, and maintaining pH value of reaction system is 11.5.
Comparative example 2
This comparative example the difference from embodiment 1 is that, take nickel salt, cobalt salt, manganese salt configuration solution D, Ni in the solution D:
Co:Mn total moles ratio is 6:2:2, solution D is added to the automatic continuous reaction kettle for being equipped with the bottom 1.9L liquid, by coprecipitation reaction system
Obtain the Ni uniform to surface layer Elemental redistribution from core0.6Co0.2Mn0.2(OH)2Presoma.
Comparative example 3
This comparative example the difference from embodiment 1 is that, the reaction time be 15 hours.
Comparative example 4
This comparative example the difference from embodiment 1 is that, the reaction time be 30 hours.
Comparative example 5
This comparative example the difference from embodiment 1 is that, reaction temperature be 60 DEG C.
One, that embodiment 1 is compared result with comparative example 1 is as follows:
As shown in Fig. 1~2, Fig. 1 is the SEM of gradient distribution material and comparative example 1 (b) made from the embodiment of the present invention 1 (a)
Figure, material change presoma such as figure, comparative example 1 (b) the various fragmentary little particles that technique obtains during synthesis and fill
Denounce whole system, the particle that embodiment 1 (a) change reaction process materials synthesis goes out is more uniform, and tap density is by 1.74g/cm3
(comparative example 1) rises to 1.97g/cm3 (embodiment 1), few granular primary particles.
Fig. 2 is the 2.8-4.3V 0.2C cyclic curve of gradient distribution material made from the embodiment of the present invention 1 Yu comparative example 1
Figure, the head of embodiment 1 are put as 173.9mAh/g, 100 enclose after residue 168.1mAh/g conservation rate be 96.7%, 1 head of comparative example
170.9mAh/g is put, 100 circle residue 158.8mAh/g conservation rates are 93%.Embodiment 1 has than 1 capacity of comparative example to be mentioned a little
It rises.
Two, gradient distribution material made from Examples 1 to 3 and comparative example 2~5 is tested for the property, in 2.8-
The condition test of 4.4V 1C (1C=200mA/g), test result is as follows:
As shown above, gradient distribution material made from Examples 1 to 3, tap density is strong, and discharge capacity is higher for the first time,
50 circulation volume conservation rates, 100 circulation volume conservation rates are excellent.The present invention is by changing the reaction item in synthesis process
Part keeps materials synthesis more uniform, reduces the generation of granular residue, keeps each material granule uniform, reduces material interface effect
It answers, improves material tap density；Capacity also improves to some extent.
The comparison of comparative example 2 and embodiment 1, the particle uniformity of comparative example 2, tap density, for the first time discharge capacity, 50 times
Circulation volume conservation rate, 100 circulation volume conservation rates are poor with respect to embodiment 1.The material of the uniform 6:2:2 ratio of comparative example 2
Material, itself belongs to high-nickel material, and thermally labile caused by this body structure of material is easy to form impurity on the surface of the material, causes material
Expect that capacity is not high and stability is bad.
The comparison of comparative example 3~4 and embodiment 1, the particle uniformity of comparative example 3~4, tap density, electric discharge is held for the first time
Amount, 50 circulation volume conservation rates, 100 circulation volume conservation rates are poor with respect to embodiment 1；Reaction time is too low, reaction
Not exclusively, the high microballoon presoma of close tap density cannot be formed, the reaction time is too long, not for material molding exercising result
It is so obvious, oversized particles can be formed on the basis of original instead, cause material homogeneity bad.The present invention controls the reaction time
It is 18~26 hours, gradient distribution material obtained forms the high microballoon presoma of close tap density, improves the equal of material
Even property.
The comparison of comparative example 5 and embodiment 1, the particle uniformity of comparative example 5, tap density, for the first time discharge capacity, 50 times
Circulation volume conservation rate, 100 circulation volume conservation rates are poor with respect to embodiment 1；The solubility product of three kinds of transition metal has difference
It is different, the sequencing for having precipitating during precipitating is reacted at normal temperature, and the mesh for preparing ternary solid solution structure is not achieved
, increasing temperature keeps three's solubility product close, enables when precipitating almost simultaneously, to generate solid solution and precipitate, temperature is excessively high
Also it falls flat.It is 45~55 DEG C that the present invention, which controls reaction temperature, is co-precipitated excellent effect.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent substitution, improvement and etc. done be should be included within the scope of the present invention.
Claims (9)
1. a kind of raising lithium ion cell positive gradient distribution material precursor Ni0.6Co0.2Mn0.2(OH)2Synthesize particle size uniformity
Method, which comprises the following steps:
S1, nickel salt, cobalt salt, manganese salt configuration different mol ratio example, the solution A of same concentrations, solution B and solution C, the solution are taken
A, Ni:Co:Mn total moles ratio is 6:2:2 in solution B and solution C,
Ni:Co:Mn molar ratio is (9.5 ~ 7.5): (0.25 ~ 1.25): (0.25 ~ 1.25), volume 0.6a in the solution A
~0.8a；
Ni:Co:Mn molar ratio is (1.5 ~ 0.5) in the solution C: (3 ~ 1): (3 ~ 1), volume are 0.5a ~ 0.3a；
The bottom liquid that ammonia density is 0.7 ~ 0.5 mol/L is configured simultaneously；
S2, the solution A, solution B, solution C of step S1 are respectively placed in A container, B container, in C container, the bottom liquid is placed in
In automatic continuous reaction kettle, solution A is pumped into reaction kettle by reaction kettle described in the A reservoir first,
When solution A residual volume is 0.4a ~ 0.1a, solution B is pumped into solution A, while mixed solution is stirring in A container
Under be continuously pumped into reaction kettle；When solution B is pumped into solution A completely, then solution C is pumped into solution A, while keeping A container
Middle mixed solution is continuously pumped into reaction kettle；Flow velocity V1 that the solution B is pumped into solution A, the solution C are pumped into solution A
Flow velocity V2 and A container in mixed solution be pumped into the flow velocity V3 of reaction kettle and be consistent；
During the solution A is pumped into reaction kettle, fixed reaction condition, maintaining ammonia density in reaction system is 0.7 ~ 0.5
Definite value within the scope of mol/L, maintaining pH value of reaction system is the definite value in 11.3 ~ 11.7 ranges；
During the solution B, solution C are successively pumped into solution A, pH value of reaction system gradually drops to from 11.3 ~ 11.7
11.0, the ammonia density of reaction system gradually drops to 0.4 ~ 0.3 mol/L from 0.7 ~ 0.5 mol/L；
It is 45 ~ 55 DEG C that reaction process, which controls reaction temperature, and the reaction time is 18 ~ 26 hours, is finally made by coprecipitation reaction
Core is reduced to the presoma of material surface Ni:Co:Mn=1:1:1 by Ni:Co:Mn=8:1:1 at leisure.
2. raising lithium ion cell positive gradient distribution material precursor Ni according to claim 10.6Co0.2Mn0.2
(OH)2The method for synthesizing particle size uniformity, which is characterized in that during the solution B, solution C are successively pumped into solution A, instead
Answering system pH, gradually fall is to reduce by 0.05 within each hour, and finally maintain 11.0.
3. raising lithium ion cell positive gradient distribution material precursor Ni according to claim 10.6Co0.2Mn0.2
(OH)2The method for synthesizing particle size uniformity, which is characterized in that
In the solution A Ni:Co:Mn molar ratio be 8:1:1, volume 0.7a,
In the solution B Ni:Co:Mn molar ratio be 4:1:1, volume 0.3a,
In the solution C Ni:Co:Mn molar ratio be 1:2:2, volume 0.4a.
4. raising lithium ion cell positive gradient distribution material precursor Ni according to claim 10.6Co0.2Mn0.2
(OH)2The method for synthesizing particle size uniformity, which is characterized in that the nickel salt, cobalt salt, manganese salt are respectively NiSO4·6H2O、
CoSO4·7H2O and MnSO4·H2O。
5. raising lithium ion cell positive gradient distribution material precursor Ni according to claim 10.6Co0.2Mn0.2
(OH)2The method for synthesizing particle size uniformity, which is characterized in that control is adjusted using 10 mol/L NaOH solutions in the pH value
System.
6. raising lithium ion cell positive gradient distribution material precursor Ni according to claim 10.6Co0.2Mn0.2
(OH)2The method for synthesizing particle size uniformity, which is characterized in that the ammonia density of the bottom liquid is adjusted using 2.8 mol/L ammonium hydroxide
Section control.
7. raising lithium ion cell positive gradient distribution material precursor Ni according to claim 10.6Co0.2Mn0.2
(OH)2The method for synthesizing particle size uniformity, which is characterized in that during charging, reaction kettle stirring rate is 600 ~ 800
r/min。
8. a kind of ternary cathode material of lithium ion battery, which is characterized in that have the method preparation of any one of claim 1 ~ 7
Obtained presoma.
9. a kind of preparation method of ternary cathode material of lithium ion battery, which is characterized in that utilize any one of claim 1 ~ 7 institute
The presoma Ni that the method for stating is prepared0.6Co0.2Mn0.2(OH)2It is 1:1.05 after mixing in Muffle with LiOH molar ratio
500 ~ 900 DEG C of roastings 5 ~ 30h, 10 DEG C/s of heating rate obtain positive electrode Li [Ni in furnace0.6Co0.2Mn0.2]O2。
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| CN112624207A (en) * | 2020-11-23 | 2021-04-09 | 中国科学院过程工程研究所 | Full-concentration gradient-distributed lithium-rich manganese-based lithium cathode material and preparation method and application thereof |
| CN114229919A (en) * | 2021-12-20 | 2022-03-25 | 湖北亿纬动力有限公司 | Gradient ternary precursor, preparation method and application thereof |
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