CN106207140A - A kind of preparation method of multi-kernel shell structure nickel cobalt aluminum complex - Google Patents
A kind of preparation method of multi-kernel shell structure nickel cobalt aluminum complex Download PDFInfo
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Abstract
The present invention provides the preparation method of a kind of multi-kernel shell structure nickel cobalt aluminum complex, comprises the following steps: first synthesizing spherical Ni (OH)2, at Ni (OH)2After the D50 of granule reaches 3um, add the nickel and cobalt solution A1B1 with concentration in gradient change and aluminum solutions C1, nickel and cobalt solution A2B2 and aluminum solutions C2 ... nickel and cobalt solution AnBn and aluminum solutions Cn, obtain multi-kernel shell structure nickel cobalt aluminum complex NixCoyAl1‑x‑y(OH)3‑x‑y.The present invention solves the difficulty of liquid phase coprecipitation synthesis NCA the most technically, and the NCA synthesized has multiple nucleocapsid feature, chemical composition is ladder distribution, the chemical composition of the nickel cobalt lithium aluminate cathode material adjacent area after high temperature sintering do not haves obvious difference, it is to avoid between common core-shell material housing and with the compositional difference of core;In charge and discharge process, granule each several part change in volume degree is close, the shortcoming overcoming common nucleocapsid structure, and the performance advantage of shell component and kernel component is also retained simultaneously, makes integral material have good cycle performance and heat stability.
Description
Technical field
The present invention relates to the preparation method of a kind of battery material presoma, particularly relate to a kind of anode material for lithium-ion batteries
Preparation method, the preparation method of a kind of multi-kernel shell structure nickel cobalt aluminum complex.
Background technology
Lithium ion battery has been widely used for the every field such as science and technology, military affairs, life at present.And positive electrode lithium from
In occupation of most important status in sub-battery product composition.The quality of positive electrode, directly determines the final performance of battery, and
And positive electrode proportion in battery cost is up to about 40%.The most conventional lithium ion anode material has LiCoO2,
LiNiO2, LiMn2O4, LiMPOx etc..LiCoO2Research the earliest, have that preparation technology is simple, stable performance, specific capacity high, well
The advantage such as cycle performance, but cobalt resource is poor, expensive and poisonous, thus its application is restricted.As an alternative
The LiNiO of material2The reversible capacity higher with it and relatively low price start to come into one's own again, but its preparation condition is harsh,
It is difficult to generate the compound with metering ratio, poor heat stability, and the structure change of active material brings ratio when discharge and recharge
The decay of energy and LiNiO2The safety high brought when overcharging limits the process that it is practical.The LiN of Co doping
i1-y CoyO2Series compound is provided simultaneously with Co system and the advantage of Ni system positive electrode, but this material there is also overcharging resisting ability
The defects such as difference, poor heat stability, first electric discharge irreversible capacity height.And the doping of aluminum can stablize the knot of nickel cobalt material further
Structure, hence it is evident that the exothermic reaction in suppression charge and discharge process, makes material circulation performance and overcharging resisting performance significantly improve.
Nickel cobalt aluminum (abbreviation NCA) ternary material, gram volume is high, and compacted density is close to 532 type ternarys NCM, to moisture environment
Very sensitive.NCA positive electrode belongs to mixes aluminium profiles nickel cobalt series positive electrode, and Chinese scholars has been carried out grinding of more than ten years
Study carefully, but in view of its synthesis restriction such as difficulty is big, technological requirement is complicated, fettered the realization of its large-scale commercial application.NCA
Material is the most quiet, but the height ratio capacity performance of NCA material still cannot be forgotten by researchers, the electric discharge of 200mAh/g
Specific capacity seems the most attractive under the demand environment of high power performance.Due to Al (OH)3Ksp=1.3*10-33With
Co(OH)2Ksp=1.6*10-15With Ni (OH)2Ksp=2.0*10-15Compare and differed 1018 times, cause in nickel cobalt unit
During element co-precipitation, aluminum ions settling velocity nickel cobalt to be significantly faster than that ion, thus it is easily formed colloid or by ultra-fine nanometer wadding
Grain is reunited and is formed blowball, and when co-precipitation, product is to precipitate in the way of cotton-shaped, has had a strong impact on the degree of crystallinity of material, thus
Reduce the physical and chemical performance of material.
Summary of the invention
For solving above-mentioned technical problem, the present invention provides the preparation method of a kind of multi-kernel shell structure nickel cobalt aluminum complex,
Solve the difficulty of liquid phase coprecipitation synthesis NCA the most technically, and the NCA synthesized has multiple nucleocapsid feature, change
Learning composition to be distributed in ladder, so chemical composition of the nickel cobalt lithium aluminate cathode material adjacent area after high temperature sintering will not go out
Existing obvious difference, it is to avoid between common core-shell material housing and with the compositional difference of core.
It is an object of the invention to realize as follows:
The preparation method of a kind of multi-kernel shell structure nickel cobalt aluminum complex, comprises the following steps:
Step 1, preparation gradient solution:
Step 1.1, prepares precursor solution: by nickel source, cobalt source according to metal n (Ni2+):n(Co2+)=x:y, x+y < 1,
Being configured to certain density nickel solution A, cobalt liquor B respectively, n (Al is pressed in aluminum source3+)=(1-x-y) it is configured to aluminum together with chelating agent
Solution C;
Step 1.2, is that arithmetic progression is divided into some parts by precursor solution according to volume:
Nickel solution A is divided into n+1 part according to the volume arithmetic progression that tapers off: nickel solution A0, A1, A2 ... An;
It is that incremental arithmetic progression is divided into n part: cobalt liquor B1, B2 ... Bn by cobalt liquor B according to volume;
Nickel solution A1 and cobalt liquor B1 is uniformly mixed to form nickel cobalt mixed solution A 1B1, by nickel solution A2 and cobalt liquor B2
It is uniformly mixed to form nickel and cobalt solution A2B2 ... nickel solution An and cobalt liquor Bn is uniformly mixed to form nickel cobalt mixed solution
AnBn;
It is that incremental arithmetic progression is divided into n part: aluminum solutions C1, C2 ... Cn by aluminum C according to volume;
Step 2, synthesis granule D50 is the spherical Ni (OH) of 3um2Kernel:
Nickel solution A0 in above-mentioned steps 1 prepares the spherical Ni that granule D50 is 3um (OH) by liquid phase synthesizing method2In
Core, liquid phase method synthesizing spherical Ni (OH)2The temperature of kernel is 50-65 DEG C, and the ammonia using concentration as 4-6g/L is as end liquid, pH value
Control at 10.0-11.5;
Step 3, prepares multi-kernel shell structure nickel cobalt aluminum complex NixCoyAl1-x-y(OH)3-x-y:
Spherical Ni (OH) is prepared to above-mentioned steps 2 according to certain flow velocity2Reactor in be sequentially added in step 1
Nickel and cobalt solution A1B1 and aluminum solutions C1, nickel and cobalt solution A2B2 and aluminum solutions C2 ... nickel and cobalt solution AnBn and aluminum solutions Cn, obtain
Multi-kernel shell structure nickel cobalt aluminum complex NixCoyAl1-x-y(OH)3-x-y。
In described step 1.1, chelating agent is 1,10-orthophenanthroline, disodiumedetate, dimercaptopropanol, BAL, two mercaptos
Base propane sulfonic acid sodium, mercaptoethylmaine, TGA, thiourea, ammonium fluoride, 8-hydroxyquinoline, cyanide, acetylacetone,2,4-pentanedione, citric acid,
Tartaric acid, oxalic acid, sulfosalicylic acid, triethanolamine, ethylene glycol bis (2-amino-ethyl ether) tetraacethyl, ethylenediamine tetrapropionic acid, three
The combination of one or more in ethylene tetramine.In described step 2, nickel solution A0 is 65 DEG C in temperature, and end liquefied ammonia concentration is 6g/
L, pH value controls to prepare, by liquid phase synthesizing method, the spherical Ni (OH) that granule D50 is 3um when 11.52。
In described step 1.1, being 0.88:0.09:0.03 according to nickel cobalt al mole ratio, chelating agent mass concentration is 0.1-
10% is configured to certain density aluminum solutions C.
In described step 1.1, chelating agent by disodiumedetate, ethylene glycol bis (2-amino-ethyl ether) tetraacethyl with
The amount of material mixes than 1:1.
The D50 of presoma is when 4-6um, and nickel content accounts for the 99.5-98% of total metal contents in soil, and cobalt accounts for total metal contents in soil and (rubs
Your percentage ratio) 0.5-1.9%, aluminum accounts for the 0-0.1% of total metal contents in soil, and temperature raises along with the growth of D50, and D50 is at 4-
During 6um, temperature is 65-70 DEG C, and pH value reduces along with the growth of D50, and D50 is in the range of when 4-6um, pH value is down to 11-11.3;
The D50 of presoma is when 6-9um, and nickel content accounts for the 98-96% of total metal contents in soil, and cobalt accounts for the 1.9-of total metal contents in soil
3.7%, aluminum accounts for the 0.1-0.3% of total metal contents in soil, and temperature raises along with the growth of D50, and D50 temperature when 6-9um is 68-
75 DEG C, pH value reduces along with the growth of D50, and D50 is in the range of when 4-9um, pH value is down to 10.9-11.1;
The D50 of presoma is when 9-13um, and nickel content accounts for the 96-92% of total metal contents in soil, and cobalt accounts for total metal contents in soil
3.7-7.4%, aluminum accounts for the 0.3-0.6% of total metal contents in soil, and temperature raises along with the growth of D50, and D50 is temperature when 9-13um
For 70-82 DEG C, pH value reduces along with the growth of D50, and D50 is in the range of when 9-13um, pH value is down to 10.5-10.9;
The D50 of presoma is when 13-19um, and nickel content accounts for the 92-88% of total metal contents in soil, and cobalt accounts for total metal contents in soil
7.4-9%, aluminum accounts for the 0.6-3% of total metal contents in soil, and temperature raises along with the growth of D50, and D50 temperature when 13-19um is
78-90 DEG C, pH value reduces along with the growth of D50, and D50 is in the range of when 13-19um, pH value is down to 10-10.85;
Above synthetic method follows a principle, and nickel content high-temperature is low, pH value is high, D50 is little.
Compared with prior art, the present invention solves the difficulty of liquid phase coprecipitation synthesis NCA technically, synthesizes
NCA chemical composition has depth-graded feature, the chemical composition of adjacent area does not haves obvious difference, it is to avoid nucleocapsid material
Between material housing and with the compositional difference of core.In charge and discharge process, granule each several part change in volume degree phase
Closely, the shortcoming overcoming common nucleocapsid structure, the performance advantage of shell component and kernel component is also retained simultaneously, makes entirety
Material has good cycle performance and heat stability.This invention synthesis technique is simple to operation, and pattern and chemical composition are controlled.
Accompanying drawing explanation
Fig. 1 is the electron microscopic picture that embodiment 1 synthesizes multi-kernel shell structure nickel cobalt aluminum complex.
Detailed description of the invention
Below by specific embodiment, the invention will be further described.
Embodiment one
Equivalent certain density nickel solution A, cobalt liquor B is prepared respectively than Ni:Co=0.88:0.09 with the amount of material;Will
Nickel solution A is divided into 5 parts, respectively 30% (A0) of the total volume, 25% (A1), 20% (A2), 15% (A3), 10% (A4);
Cobalt liquor B is divided into 4 parts, respectively 19% (B1) of the total volume, 23% (B2), 27% (B3), 31% (B4);
Nickel solution A1 and cobalt liquor B1 is uniformly mixed to form nickel cobalt mixed solution A 1B1, by nickel solution A2 and cobalt liquor B2
It is uniformly mixed to form nickel and cobalt solution A2B2, nickel solution A3 and cobalt liquor B3 is uniformly mixed to form nickel and cobalt solution A3B3, nickel is molten
Liquid A4 and cobalt liquor B4 is uniformly mixed to form nickel cobalt mixed solution A 4B4;
Being 0.88:0.09:0.03 according to nickel cobalt al mole ratio, chelating agent mass concentration is 0.5% to be configured to finite concentration
Aluminum solutions C, chelating agent is by disodiumedetate, and ethylene glycol bis (2-amino-ethyl ether) tetraacethyl is with the amount ratio 1 of material:
1 mixes;C solution is divided into 4 parts, respectively 4% (C1) of the total volume, 18% (C2), 32% (C3), 46% (C4);
Being 65 DEG C by above-mentioned A0 nickel solution in temperature, the ammonia using concentration as 6g/L is as end liquid, and pH value controls 11.5,
The spherical Ni (OH) that granule D50 is 3um is prepared by liquid phase synthesizing method2Kernel;
Then coutroi velocity is passed through A1B1, C1 solution, and granularity D50 of presoma grows into 6um, and nickel content accounts for total metal and contains
The 98% of amount, cobalt accounts for the 1.9% of total metal contents in soil (molar percentage), and aluminum accounts for the 0.1% of total metal contents in soil, and temperature is along with D50
Growth and raise, D50 temperature when 6um is 65-70 DEG C, and pH value reduces along with the growth of D50, D50 when 6um pH value fall
To 11-11.3;
Continuing to be passed through A2B2, C2 solution, the D50 of presoma grows into 9um, and nickel content accounts for the 96% of total metal contents in soil, cobalt
Accounting for the 3.7% of total metal contents in soil, aluminum accounts for the 0.3% of total metal contents in soil, and temperature raises along with the growth of D50, and D50 is when 9um
Temperature is 75 DEG C, and pH value reduces along with the growth of D50, and D50 is in the range of when 9um, pH value is down to 10.9-11.1;
Continuing to be passed through A3B3, solution C3, when the D50 of presoma grows into 13um, nickel content accounts for the 92% of total metal contents in soil,
Cobalt accounts for the 7.4% of total metal contents in soil, and aluminum accounts for the 0.6% of total metal contents in soil, and temperature raises along with the growth of D50, and D50 is at 13um
Shi Wendu is 82 DEG C, and pH value reduces along with the growth of D50, and D50 is in the range of when 9-13um, pH value is down to 10.5-10.9;
Continuing to be passed through A4B4, C4 solution, when the D50 of presoma grows into 19um, nickel content accounts for the 88% of total metal contents in soil,
Cobalt accounts for the 9% of total metal contents in soil, and aluminum accounts for the 3% of total metal contents in soil, and temperature raises along with the growth of D50, and D50 grows into 19um
Shi Wendu is 85-90 DEG C, and pH value reduces along with the growth of D50, and D50 is in the range of when 13-19um, pH value is down to 10-10.85.
Finally giving multi-kernel shell structure nickel cobalt aluminum complex, Fig. 1 is the multi-kernel shell structure nickel cobalt aluminum complex electron microscopic picture of synthesis.
Embodiment two
Equivalent certain density nickel solution A, cobalt liquor B is prepared respectively than Ni:Co=0.88:0.09 with the amount of material;Will
Nickel solution A is divided into 5 parts, respectively 30% (A0) of the total volume, 25% (A1), 20% (A2), 15% (A3), 10% (A4);
Cobalt liquor B is divided into 4 parts, respectively 19% (B1) of the total volume, 23% (B2), 27% (B3), 31% (B4);
Nickel solution A1 and cobalt liquor B1 is uniformly mixed to form nickel cobalt mixed solution A 1B1, by nickel solution A2 and cobalt liquor B2
It is uniformly mixed to form nickel and cobalt solution A2B2, nickel solution A3 and cobalt liquor B3 is uniformly mixed to form nickel and cobalt solution A3B3, nickel is molten
Liquid A4 and cobalt liquor B4 is uniformly mixed to form nickel cobalt mixed solution A 4B4;
Be 0.88:0.09:0.03 according to nickel cobalt al mole ratio, chelating agent mass concentration be 1% be configured to certain density
Aluminum solutions C, chelating agent is compared 1:1 by disodiumedetate, ethylene glycol bis (2-amino-ethyl ether) tetraacethyl with the amount of material
Mix;C solution is divided into 4 parts, respectively 4% (C1) of the total volume, 18% (C2), 32% (C3), 46% (C4);
Being 65 DEG C by above-mentioned A0 nickel solution in temperature, the ammonia using concentration as 6g/L is as end liquid, and pH value controls 11.5,
The spherical Ni (OH) that granule D50 is 3.2um is prepared by liquid phase synthesizing method2Kernel;
Then coutroi velocity is passed through A1B1, C1 solution, and granularity D50 of presoma grows into 6.4um, and nickel content accounts for total metal
The 98% of content, cobalt accounts for the 1.9% of total metal contents in soil (molar percentage), and aluminum accounts for the 0.1% of total metal contents in soil, temperature along with
The growth of D50 and raise, D50 temperature when 6.4um is 65-70 DEG C, and pH value reduces along with the growth of D50, and D50 is at 6.4um
Time in the range of pH value is down to 11-11.3;
Continuing to be passed through A2B2, C2 solution, the D50 of presoma grows into 9.6um, and nickel content accounts for the 96% of total metal contents in soil,
Cobalt accounts for the 3.7% of total metal contents in soil, and aluminum accounts for the 0.3% of total metal contents in soil, and temperature raises along with the growth of D50, and D50 exists
During 9.6um, temperature is 75 DEG C, and pH value reduces along with the growth of D50, and D50 pH value when 9.6um is down to 10.9-11.1 scope
In;
Continuing to be passed through A3B3, solution C3, when the D50 of presoma grows into 13.9um, nickel content accounts for total metal contents in soil
92%, cobalt accounts for the 7.4% of total metal contents in soil, and aluminum accounts for the 0.6% of total metal contents in soil, and temperature raises along with the growth of D50, D50
When 13.9um, temperature is 82 DEG C, and pH value reduces along with the growth of D50, and D50 pH value when 9.6-13.9um is down to 10.5-
In the range of 10.9;
Continuing to be passed through A4B4, C4 solution, when the D50 of presoma grows into 18.5um, nickel content accounts for total metal contents in soil
88%, cobalt accounts for the 9% of total metal contents in soil, and aluminum accounts for the 3% of total metal contents in soil, and temperature raises along with the growth of D50, and D50 grows
Being 85-90 DEG C to temperature during 18.5um, pH value reduces along with the growth of D50, and D50 pH value when 13.9-18.5um is down to 10-
In the range of 10.85, finally give multi-kernel shell structure nickel cobalt aluminum complex.
Claims (5)
1. the preparation method of a multi-kernel shell structure nickel cobalt aluminum complex, it is characterised in that comprise the following steps:
Step 1, preparation gradient solution:
Step 1.1, prepares precursor solution: by nickel source, cobalt source according to metal n (Ni2+):n(Co2+)=x:y, x+y < 1, respectively
Being configured to certain density nickel solution A, cobalt liquor B, n (Al is pressed in aluminum source3+)=(1-x-y) it is configured to aluminum solutions together with chelating agent
C;
Step 1.2, is that arithmetic progression is divided into some parts by precursor solution according to volume:
Nickel solution A is divided into n+1 part according to the volume arithmetic progression that tapers off: nickel solution A0, A1, A2 ... An;
It is that incremental arithmetic progression is divided into n part: cobalt liquor B1, B2 ... Bn by cobalt liquor B according to volume;
Nickel solution A1 and cobalt liquor B1 is uniformly mixed to form nickel cobalt mixed solution A 1B1, by uniform with cobalt liquor B2 for nickel solution A2
It is mixed to form nickel and cobalt solution A2B2 ... nickel solution An and cobalt liquor Bn is uniformly mixed to form nickel cobalt mixed solution A nBn;
It is that incremental arithmetic progression is divided into n part: aluminum solutions C1, C2 ... Cn by aluminum C according to volume;
Step 2, synthesis granule D50 is the spherical Ni (OH) of 3um2Kernel:
Nickel solution A0 in above-mentioned steps 1 prepares the spherical Ni that granule D50 is 3um (OH) by liquid phase synthesizing method2Kernel, liquid
Phase method synthesizing spherical Ni (OH)2The temperature of kernel is 50-65 DEG C, and the ammonia using concentration as 4-6g/L controls as end liquid, pH value
At 10.0-11.5;
Step 3, prepares multi-kernel shell structure nickel cobalt aluminum complex NixCoyAl1-x-y(OH)3-x-y:
Spherical Ni (OH) is prepared to above-mentioned steps 2 according to certain flow velocity2Reactor in the nickel cobalt that is sequentially added in step 1
Solution A 1B1 and aluminum solutions C1, nickel and cobalt solution A2B2 and aluminum solutions C2 ... nickel and cobalt solution AnBn and aluminum solutions Cn, obtain multiple
Nucleocapsid structure nickel cobalt aluminum complex NixCoyAl1-x-y(OH)3-x-y。
2. the preparation method of multi-kernel shell structure nickel cobalt aluminum complex as claimed in claim 1, it is characterised in that:
In described step 1.1, chelating agent is 1,10-orthophenanthroline, disodiumedetate, dimercaptopropanol, BAL, dimercapto third
Alkyl sulfonic acid sodium, mercaptoethylmaine, TGA, thiourea, ammonium fluoride, 8-hydroxyquinoline, cyanide, acetylacetone,2,4-pentanedione, citric acid, winestone
Acid, oxalic acid, sulfosalicylic acid, triethanolamine, ethylene glycol bis (2-amino-ethyl ether) tetraacethyl, ethylenediamine tetrapropionic acid, three ethylenes
The combination of one or more in tetramine.
3. the preparation method of multi-kernel shell structure nickel cobalt aluminum complex as claimed in claim 1 or 2, it is characterised in that:
In described step 2, nickel solution A0 is 65 DEG C in temperature, and end liquefied ammonia concentration is 6g/L, and pH value controls to pass through liquid when 11.5
Phase synthesi prepares the spherical Ni (OH) that granule D50 is 3um2。
4. the preparation method of multi-kernel shell structure nickel cobalt aluminum complex as claimed in claim 1 or 2, it is characterised in that:
In described step 1.1, being 0.88:0.09:0.03 according to nickel cobalt al mole ratio, chelating agent mass concentration is that 0.1-10% joins
It is set to certain density aluminum solutions C.
5. the preparation method of multi-kernel shell structure nickel cobalt aluminum complex as claimed in claim 4, it is characterised in that:
Chelating agent is mixed than 1:1 with the amount of material by disodiumedetate, ethylene glycol bis (2-amino-ethyl ether) tetraacethyl
Form.
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CN108417826A (en) * | 2018-02-02 | 2018-08-17 | 昆明理工大学 | A kind of preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution |
CN110828804A (en) * | 2019-11-13 | 2020-02-21 | 广东省稀有金属研究所 | Multi-shell-layer precursor, gradient-content cathode material and preparation method thereof |
RU2751079C1 (en) * | 2018-06-11 | 2021-07-09 | Микроваст Пауэр Системс Ко., Лтд. | Method for production of precursor particles and precursor particle produced by this method |
CN114408987A (en) * | 2022-03-30 | 2022-04-29 | 宜宾锂宝新材料有限公司 | Nickel-cobalt-manganese precursor, ternary cathode material and preparation method thereof |
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