CN108110249A - A kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor - Google Patents
A kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of core-shell structure nickel cobalt aluminium ternary material precursor, nickel soluble-salt and cobalt soluble-salt are dissolved in deionized water obtain nickel and cobalt solution in proportion first, nickel and cobalt solution is added in complexing agent solution A, precipitant solution cocurrent in the reaction kettle equipped with bottom liquid and is reacted, the nuclear structure of nickel cobalt aluminium ternary material precursor is formed, the nuclear structure is nickel cobalt hydroxide；Secondly sodium aluminate solution and above-mentioned nickel and cobalt solution, complexing agent solution A, precipitant solution cocurrent are added in above-mentioned reaction kettle after reaction and reacted, nickel, cobalt, the sediment of aluminium three is made to form the shell structure of nickel cobalt aluminium ternary material precursor on nuclear structure, the shell structure is nickel cobalt aluminium hydroxide；Finally by obtained product is aged, solid-liquor separation, washing and drying, obtain the nickel cobalt aluminium ternary material precursor of nucleocapsid.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical fields, and in particular to a kind of core-shell structure nickel cobalt aluminium ternary material
The preparation method of material precursor.
Background technology
The structure of lithium ion battery includes anode, cathode, membrane, electrolyte, and positive and negative anodes infiltrate in the electrolytic solution, lithium ion
It is moved using electrolyte as medium between positive and negative anodes, realizes the charge and discharge of battery.Since its operating voltage is high, bigger than energy, again
Measure it is light, small, have extended cycle life, memory-less effect, can fast charging and discharging and the features such as non-environmental-pollution, as a new generation
Green high-capacity battery is widely used on various 3C Products and new energy power vehicle and market prospects is open.Current research
Hot spot is concentrated mainly on the power density for further improving material, energy density, cycle life and improves security performance etc..
From the point of view of lithium ion battery now used anode, transition metal oxide anode is improving battery specific energy side
Face obviously has more advantage compared with polyanion anode such as LiFePO 4, and nickel cobalt manganese, nickel cobalt aluminium etc. are main anode materials to be applied
Material.The structure of stabilized electrodes material, the exothermic reaction for increasing lithium ion diffusion coefficient, inhibiting battery material are capable of in the addition of aluminium,
So as to improve its cycle performance and overcharge resistance performance energy.
The synthetic method of ternary material is varied, is closed including sol-gel method, hydro-thermal and solvent-thermal process method, microwave
Cheng Fa, Low Temperature Solid-Phase synthetic method, rheology phase synthesi, Self- propagating Sintering Synthetic method etc., but at present be most widely used and most easily
It realizes and industrialized also belongs to coprecipitation.Chinese patent (CN 103178262B) discloses a kind of aluminum-doped nickel lithium carbonate for lithium anode material
The preparation method of material, Chinese patent (CN 102244239B) disclose a kind of preparation of lithium ion battery anode material nickel cobalt aluminium
Method is in surface alclad after nickel cobalt co-precipitation is washed, and syncretizing effect is bad during follow-up sintering, obtained product
Cycle performance is poor.Chinese patent (CN 106299347A) disclose a kind of nickel cobalt aluminium ternary precursor and preparation method thereof and
The positive electrode and method of preparation are that the solution after nickel cobalt and aluminium are complexed respectively adds in reaction kettle simultaneously, control aluminium hydroxide
Settling velocity, so as to fulfill three while precipitates, and obtains the persursor material that crystallinity is high, lattice order is strong, but by
It is better than aluminium in the complexing power of metallic nickel, cobalt and some complexing agents, when reaction grabs complex ion so that product obtained by the reaction
It differs larger with preset ratio, reduces the performance of material.
The content of the invention
For nickel, three caused by cobalt differs larger and aluminum precipitation excessive velocities with the precipitation pH value of aluminium is co-precipitated simultaneously
The problems such as effect is poor, tap density is low, it is an object of the invention to provide a kind of core-shell structure nickel cobalt aluminium hydroxide presomas
Preparation method, effectively improve the tap density of presoma and the sphericity of particle.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor, comprises the following steps：
Step 1：Nickel soluble-salt and cobalt soluble-salt are dissolved in deionized water obtain nickel and cobalt solution in proportion, it will
Nickel and cobalt solution, which is added in complexing agent solution A, precipitant solution cocurrent in the reaction kettle equipped with bottom liquid, to be reacted, and forms ternary material
The nuclear structure of material precursor, the nuclear structure are nickel cobalt hydroxide；
Step 2：By sodium aluminate solution and the nickel and cobalt solution of step 1 use, complexing agent solution A, precipitant solution
Cocurrent, which is added in the reaction kettle of step 1 after reaction, is reacted, and makes nickel, cobalt, the sediment of aluminium three shape on nuclear structure
Into the shell structure of nickel cobalt aluminium ternary material precursor, the shell structure is nickel cobalt aluminium hydroxide；
Step 3：Product that step 2 is obtained is aged, solid-liquor separation, washing and drying, obtain the nickel of nucleocapsid
Cobalt aluminium ternary material precursor.
Further, the nickel soluble-salt in step 1 and cobalt soluble-salt are sulfate, nitrate, acetate and chlorination
One or more of object, total metal concentration is 1-4mol/L in nickel and cobalt solution, and the molar ratio of nickel cobalt is (75-90)：(10-
25)；Complexing agent A in step 1 is one in ammonium hydroxide, triethanolamine, ammonium fluoride, citric acid, oxalic acid, sodium ethylene diamine tetracetate
Kind is several；Precipitating reagent in step 1 is sodium hydroxide.
Further, the concentration of complexing agent solution A is 0.1-10mol/L；The concentration of precipitant solution is 0.5-10mol/
L。
Further, the concentration of complexing agent solution A is 1-6mol/L；The concentration of precipitant solution is 2-6mol/L.
Further, the bottom liquid in step 1 is that the mixing of the ammonia spirit or ammonium hydroxide and sodium hydroxide of 0.1-1mol/L is molten
Liquid.
Further, the sodium aluminate solution is dissolved in for sodium metaaluminate aqueous solution or sodium metaaluminate with complexing agent B
The mixed solution formed in deionized water；
When sodium aluminate solution is sodium metaaluminate aqueous solution, the concentration of the sodium metaaluminate aqueous solution is 0.01-1mol/
L；
When sodium aluminate solution is dissolved in the mixed solution formed in deionized water for sodium metaaluminate with complexing agent B, institute
The complexing agent B stated is sodium ethylene diamine tetracetate, sodium citrate, sodium lactate, one or more of hydrazine hydrate, the complexing agent B
Molal weight be 0.5~1.8 times of molal weight of sodium metaaluminate.
Further, the molar percentage of nickel soluble-salt, cobalt soluble-salt and sodium metaaluminate is x in step 2:y:
Z, wherein x >=80, y >=10, z≤10, and x+y+z=100.
Further, reaction temperature is 45-75 DEG C, pH value in reaction 10.5-12.8, reaction time 0.5- in step 1
40h；Reaction temperature is 45-75 DEG C, pH value in reaction 10.5-12.8, reaction time 10-70h in step 2.
Further, reaction temperature is 55-65 DEG C, pH value in reaction 10.8-11.8, reaction time 1- in step 1
20h；Reaction temperature is 55-65 DEG C, pH value in reaction 10.8-11.8, reaction time 10-50h in step 2.
Further, the digestion time in step 3 is 4h-150h, and preferably digestion time is 10h-48h.
Compared with prior art, the present invention has technique effect beneficial below：
Nickel, cobalt are first co-precipitated to obtain nuclear structure and carry out nickel, cobalt, aluminium again and be co-precipitated to obtain shell structure to avoid by the method for the present invention
Caused by aluminum precipitation is too fast easily forming core and difficulty is grown up, when material crystalline degree is relatively low and aluminium content is excessively high material tap density is small
Problem；In addition the presoma of this nucleocapsid made from the method for the present invention remains to keep nucleocapsid mechanism, material knot after sintering
Brilliant degree is high, stability is good.
Description of the drawings
Fig. 1 is the scanning electron microscope energy spectrum diagram of 1 sample cross-section of embodiment, wherein (A) is the scanning electricity for the sample being prepared
Mirror figure, (B), (C), (D) are respectively nickel, cobalt, the distribution map of three kinds of elements of aluminium, it can be seen that kernel is nickel cobalt, and shell is nickel cobalt
Aluminium；
Fig. 2 is the scanning electron microscope (SEM) photograph of 3 sample cross-section of embodiment.
Specific embodiment
Embodiments of the present invention are described in further detail below：
A kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor, comprises the following steps：
Nickel, cobalt soluble-salt are dissolved in deionized water by step 1 in proportion, with complexing agent solution A, precipitant solution
Cocurrent is added in the reaction kettle equipped with bottom liquid, sets each solution flow rate, reaction temperature, pH value in reaction and reaction time, and setting is anti-
It is 45-75 DEG C, pH value in reaction 10.5-12.8, reaction time 0.5-40h to answer temperature；Preferably, reaction temperature 55-65
DEG C, pH value in reaction 10.8-11.8, reaction time 1-20h form the nuclear structure of material；
Wherein, nickel, cobalt soluble-salt include one or more of sulfate, nitrate, acetate and chloride；Complexing
Agent A is one or more of ammonium hydroxide, triethanolamine, ammonium fluoride, citric acid, oxalic acid, sodium ethylene diamine tetracetate, and complexing agent A is molten
Liquid concentration is 0.1-10mol/L；Preferably, concentration 1-6mol/L；Precipitating reagent is sodium hydroxide, and precipitant solution concentration is
0.5-10mol/L；Preferably, concentration 2-6mol/L；The ammonia spirit or ammonium hydroxide and sodium hydroxide that bottom liquid is 0.1-1mol/L
Mixed solution；
Step 2, by sodium aluminate solution, step 1 nickel and cobalt solution, complexing agent solution A, precipitant solution cocurrent add
Enter in aforesaid reaction vessel, set each solution flow rate, reaction temperature, pH value in reaction and reaction time, make nickel, cobalt, aluminium three it is heavy
Continue to grow up on the nuclear structure that starch is formed in nickel cobalt hydroxide, set reaction temperature as 45-75 DEG C, pH value in reaction is
10.5-12.8 reaction time 10-70h；Preferably, reaction temperature is 55-65 DEG C, pH value in reaction 10.8-11.8, reaction
Time is 10-50h, forms the shell structure of material；
Wherein, the sodium aluminate solution for sodium metaaluminate aqueous solution or sodium metaaluminate and complexing agent B be dissolved in from
The mixed solution formed in sub- water, when sodium aluminate solution be sodium metaaluminate aqueous solution when, the sodium metaaluminate aqueous solution it is dense
It spends for 0.01-1mol/L；When sodium aluminate solution, for sodium metaaluminate with complexing agent B to be dissolved in the mixing formed in deionized water molten
During liquid, complexing agent B is sodium ethylene diamine tetracetate, sodium citrate, sodium lactate, one or more of hydrazine hydrate, the complexing agent B
Addition be 0.5~1.8 times of sodium metaaluminate；Nickel soluble-salt, cobalt soluble-salt, the molar percentage of sodium metaaluminate are x:
y:Z, wherein x >=80, y >=10, z≤10, and x+y+z=100；
Step 3, product that step 2 is obtained is aged, solid-liquor separation, washing, drying, digestion time arrives for 4h
150h, it is preferable that digestion time 10h-48h obtains the nickel cobalt lithium aluminate presoma of nucleocapsid.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
Step 1：The sulfate solution that total metal concentration is 2mol/L nickel cobalts is configured, the molar ratio of nickel cobalt is 85:13,
The complexing agent A ammonia spirits of 5.7mol/L, the sodium hydroxide solution of 4mol/L, cocurrent add in bottom liquid as 0.3mol/L ammonium hydroxide
In 100L reaction kettles, set reaction temperature as 60 DEG C, pH value in reaction 11.5, reaction time 3h, form the nuclear structure of material；
Step 2：Reaction in step 1 continues, and the sodium metaaluminate aqueous solution of 0.1mol/L is configured, with 25mL/min
Speed be added in reaction kettle, set reaction temperature as 60 DEG C, pH value in reaction 11.5, reaction time 45h, make nickel, cobalt, aluminium three
Continue to grow up on the nuclear structure that the sediment of person is formed in nickel cobalt hydroxide, form the shell structure of material；
Step 3：The aged 48h of product that step 2 is obtained, supernatant is removed after centrifugation, and sediment is disperseed again,
It is repeated 3 times, being put into baking oven after sulfate radical-free ion in supernatant, after sediment is taken out is dried, and obtains nucleocapsid knot
The nickel cobalt aluminium ternary material precursor of structure, electron-microscope scanning sectional view are as shown in Figure 1.
Embodiment 2
Step 1：The aqueous solution of nitric acid that total metal concentration is 2mol/L nickel cobalts is configured, the molar ratio of nickel cobalt is 82:15,
The complexing agent A sodium ethylene diamine tetracetate solution of 0.1mol/L, the sodium hydroxide solution of 10mol/L, cocurrent add in bottom liquid and are
Set in the reaction kettle of 0.2mol/L ammonium hydroxide reaction temperature as 45 DEG C, pH value in reaction 10.5, reaction time 20h, form material
Nuclear structure；
Step 2：Reaction in step 1 continues, and configures the sodium aluminate solution of 0.01mol/L, wherein meta-aluminic acid
Sodium solution is dissolved in deionized water for the mixture of sodium metaaluminate and 1.8 times of complexing agent B sodium citrates and is formed, and is added to reaction
Set in kettle reaction temperature as 45 DEG C, pH value in reaction 10.5, reaction time 10h, make nickel, cobalt, the sediment of aluminium three in nickel cobalt
Continue to grow up on the nuclear structure that hydroxide is formed, form the shell structure of material；
Step 3：The aged 4h of product that step 2 is obtained, supernatant is removed after centrifugation, and sediment is disperseed again,
It is repeated 3 times, being put into baking oven after sulfate radical-free ion in supernatant, after sediment is taken out is dried, and obtains nucleocapsid knot
The nickel cobalt aluminium ternary material precursor of structure.
Embodiment 3
The acetate aqueous solution that total metal concentration is 2mol/L nickel cobalts is configured, the molar ratio of nickel cobalt is 80:10,10mol/L
Complexing agent A triethanolamine solutions, the sodium hydroxide solution of 0.5mol/L, cocurrent add in bottom liquid be 1mol/L ammonium hydroxide reaction kettle
In, set reaction temperature as 75 DEG C, pH value in reaction 12.8, reaction time 0.5h, form the nuclear structure of material；
Step 2, the reaction in step 1 continue, and configure the sodium aluminate solution of 0.1mol/L, wherein sodium metaaluminate
Solution is dissolved in deionized water for the mixture of sodium metaaluminate and 0.5 times of complexing agent B sodium ethylene diamine tetracetate and is formed, and is added to
Set in reaction kettle reaction temperature as 75 DEG C, pH value in reaction 12.8, reaction time 50h, nickel, cobalt, the sediment of aluminium three is made to exist
Continue to grow up on the nuclear structure that nickel cobalt hydroxide is formed, form the shell structure of material；
Step 3, the aged 150h of product that step 2 is obtained, supernatant is removed after centrifugation, and sediment is divided again
It dissipates, is repeated 3 times, being put into baking oven after sulfate radical-free ion in supernatant, after sediment is taken out is dried, and obtains nucleocapsid
The nickel cobalt aluminium ternary material precursor of structure, electron-microscope scanning sectional view are as shown in Figure 2.
Embodiment 4
Step 1：The aqueous chloride solution that total metal concentration is 2mol/L nickel cobalts is configured, the molar ratio of nickel cobalt is 82:15,
The complexing agent A ammonium fluoride solutions of 10mol/L, the sodium hydroxide solution of 6mol/L, cocurrent add in bottom liquid for 0.3mol/L ammonium hydroxide with
In the reaction kettle of sodium hydroxide mixed solution, set reaction temperature as 55 DEG C, pH value in reaction 11.8, reaction time 0.5h, formed
The nuclear structure of material；
Step 2：Reaction in step 1 continues, and the sodium metaaluminate aqueous solution for configuring 0.1mol/L is added to reaction
In kettle, set reaction temperature as 55 DEG C, pH value in reaction 11.8, reaction time 70h, make nickel, cobalt, the sediment of aluminium three in nickel cobalt
Continue to grow up on the nuclear structure that hydroxide is formed, form the shell structure of material；
Step 3：The aged 10h of product that step 2 is obtained, supernatant is removed after centrifugation, and sediment is disperseed again,
It is repeated 3 times, being put into baking oven after sulfate radical-free ion in supernatant, after sediment is taken out is dried, and obtains nucleocapsid knot
The nickel cobalt aluminium ternary material precursor of structure.
Embodiment 5
Step 1：The aqueous chloride solution that total metal concentration is 2mol/L nickel cobalts is configured, the molar ratio of nickel cobalt is 82:15,
The complexing agent A oxalic acid solutions of 6mol/L, the sodium hydroxide solution of 2mol/L, it is 0.3mol/L ammonium hydroxide and hydrogen-oxygen that cocurrent, which adds in bottom liquid,
Change sodium mixed solution reaction kettle in, set reaction temperature as 65 DEG C, pH value in reaction 10.8, reaction time 1h, form material
Nuclear structure；
Step 2：Reaction in step 1 continues, and the sodium metaaluminate aqueous solution for configuring 1mol/L is added to reaction kettle
In, set reaction temperature as 65 DEG C, pH value in reaction 10.8, reaction time 40h, make nickel, cobalt, the sediment of aluminium three in nickel cobalt hydrogen
Continue to grow up on the nuclear structure that oxide is formed, form the shell structure of material；
Step 3：The aged 80h of product that step 2 is obtained, supernatant is removed after centrifugation, and sediment is disperseed again,
It is repeated 3 times, being put into baking oven after sulfate radical-free ion in supernatant, after sediment is taken out is dried, and obtains nucleocapsid knot
The nickel cobalt aluminium ternary material precursor of structure.
Embodiment 6
Step 1：The aqueous chloride solution that total metal concentration is 1mol/L nickel cobalts is configured, the molar ratio of nickel cobalt is 9:1,
The complexing agent A oxalic acid solutions of 6mol/L, the sodium hydroxide solution of 2mol/L, it is 0.3mol/L ammonium hydroxide and hydrogen-oxygen that cocurrent, which adds in bottom liquid,
Change sodium mixed solution reaction kettle in, set reaction temperature as 65 DEG C, pH value in reaction 10.8, reaction time 1h, form material
Nuclear structure；
Step 2：Reaction in step 1 continues, and the sodium metaaluminate aqueous solution for configuring 0.01mol/L is added to reaction
In kettle, set reaction temperature as 65 DEG C, pH value in reaction 10.8, reaction time 40h, make nickel, cobalt, the sediment of aluminium three in nickel cobalt
Continue to grow up on the nuclear structure that hydroxide is formed, form the shell structure of material；
Step 3：The aged 80h of product that step 2 is obtained, supernatant is removed after centrifugation, and sediment is disperseed again,
It is repeated 3 times, being put into baking oven after sulfate radical-free ion in supernatant, after sediment is taken out is dried, and obtains nucleocapsid knot
The nickel cobalt aluminium ternary material precursor of structure.
Embodiment 7
Step 1：The sulfate solution that total metal concentration is 4mol/L nickel cobalts is configured, the molar ratio of nickel cobalt is 75:25,
The complexing agent A ammonia spirits of 5.7mol/L, the sodium hydroxide solution of 4mol/L, cocurrent add in bottom liquid as 0.3mol/L ammonium hydroxide
In 100L reaction kettles, set reaction temperature as 60 DEG C, pH value in reaction 11.5, reaction time 3h, form the nuclear structure of material；
Step 2：Reaction in step 1 continues, and the sodium metaaluminate aqueous solution of 0.1mol/L is configured, with 25mL/min
Speed be added in reaction kettle, set reaction temperature as 60 DEG C, pH value in reaction 11.5, reaction time 45h, make nickel, cobalt, aluminium three
Continue to grow up on the nuclear structure that the sediment of person is formed in nickel cobalt hydroxide, form the shell structure of material；
Step 3：The aged 48h of product that step 2 is obtained, supernatant is removed after centrifugation, and sediment is disperseed again,
It is repeated 3 times, being put into baking oven after sulfate radical-free ion in supernatant, after sediment is taken out is dried, and obtains nucleocapsid knot
The nickel cobalt aluminium ternary material precursor of structure.
Claims (10)
1. a kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor, which is characterized in that comprise the following steps：
Step 1：Nickel soluble-salt and cobalt soluble-salt are dissolved in deionized water obtain nickel and cobalt solution in proportion, by nickel cobalt
Solution, which is added in complexing agent solution A, precipitant solution cocurrent in the reaction kettle equipped with bottom liquid, to be reacted, before forming ternary material
The nuclear structure of body is driven, the nuclear structure is nickel cobalt hydroxide；
Step 2：By sodium aluminate solution and the nickel and cobalt solution of step 1 use, complexing agent solution A, precipitant solution cocurrent
It adds in the reaction kettle of step 1 after reaction and is reacted, nickel, cobalt, the sediment of aluminium three is made to form nickel on nuclear structure
The shell structure of cobalt aluminium ternary material precursor, the shell structure are nickel cobalt aluminium hydroxide；
Step 3：Product that step 2 is obtained is aged, solid-liquor separation, washing and drying, obtain the nickel cobalt aluminium of nucleocapsid
Ternary material precursor.
2. a kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor according to claim 1, feature exist
In nickel soluble-salt and cobalt soluble-salt in step 1 are one kind or several in sulfate, nitrate, acetate and chloride
Kind, total metal concentration is 1-4mol/L in nickel and cobalt solution, and the molar ratio of nickel cobalt is (75-90)：(10-25)；In step 1
Complexing agent A is one or more of ammonium hydroxide, triethanolamine, ammonium fluoride, citric acid, oxalic acid, sodium ethylene diamine tetracetate；Step 1
In precipitating reagent be sodium hydroxide.
3. a kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor according to claim 2, feature exist
In the concentration of complexing agent solution A is 0.1-10mol/L；The concentration of precipitant solution is 0.5-10mol/L.
4. a kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor according to claim 2, feature exist
In the concentration of complexing agent solution A is 1-6mol/L；The concentration of precipitant solution is 2-6mol/L.
5. a kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor according to claim 1, feature exist
In the bottom liquid in step 1 is the ammonia spirit of 0.1-1mol/L or the mixed solution of ammonium hydroxide and sodium hydroxide.
6. a kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor according to claim 1, feature exist
In the sodium aluminate solution is dissolved in deionized water with complexing agent B and is formed for sodium metaaluminate aqueous solution or sodium metaaluminate
Mixed solution；
When sodium aluminate solution is sodium metaaluminate aqueous solution, the concentration of the sodium metaaluminate aqueous solution is 0.01-1mol/L；
It is described when sodium aluminate solution is dissolved in the mixed solution formed in deionized water for sodium metaaluminate with complexing agent B
Complexing agent B is one or more of sodium ethylene diamine tetracetate, sodium citrate, sodium lactate, hydrazine hydrate, and the complexing agent B's rubs
Your quality is 0.5~1.8 times of the molal weight of sodium metaaluminate.
7. a kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor according to claim 1, feature exist
In the molar percentage of nickel soluble-salt, cobalt soluble-salt and sodium metaaluminate is x in step 2:y:Z, wherein x >=80, y >=
10th, z≤10, and x+y+z=100.
8. a kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor according to claim 1, feature exist
In reaction temperature is 45-75 DEG C, pH value in reaction 10.5-12.8, reaction time 0.5-40h in step 1；It is anti-in step 2
It is 45-75 DEG C, pH value in reaction 10.5-12.8, reaction time 10-70h to answer temperature.
9. a kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor according to claim 1, feature exist
In reaction temperature is 55-65 DEG C, pH value in reaction 10.8-11.8, reaction time 1-20h in step 1；It is reacted in step 2
Temperature is 55-65 DEG C, pH value in reaction 10.8-11.8, reaction time 10-50h.
10. a kind of preparation method of core-shell structure nickel cobalt aluminium ternary material precursor according to claim 1, feature exist
In the digestion time in step 3 is 4h-150h, and preferably digestion time is 10h-48h.
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