CN105489886A - Nickel-cobalt-aluminum ternary cathode material with high tap-density and preparation method of nickel-cobalt-aluminum ternary cathode material - Google Patents
Nickel-cobalt-aluminum ternary cathode material with high tap-density and preparation method of nickel-cobalt-aluminum ternary cathode material Download PDFInfo
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Abstract
The invention relates to a nickel-cobalt-aluminum ternary cathode material with high tap-density and a preparation method of the nickel-cobalt-aluminum ternary cathode material. The method comprises the following steps: adding a nickel-cobalt mixed solution, a precipitant solution and a complexing agent solution to a reaction kettle in parallel flow; controlling the pH value, the temperature, the complexing agent concentration and the stirring speed in the reaction kettle, carrying out co-precipitation reaction and overflow discharge, washing slurry until the pH is smaller than 8.0, and carrying out drying and sieving to obtain spherical nickel-cobalt precursor powder; and mixing the nickel-cobalt precursor powder, an aluminum-containing compound, a doped compound and a lithium salt evenly, presintering the mixture at a low temperature, directly increasing the temperature for heat preservation, naturally cooling the mixture, and crushing an sieving the mixture to obtain the nickel-cobalt-aluminum ternary cathode material with high tap-density. Divalent metal ions are doped, so that a layered crystal structure of the material is stabilized; the content of Ni<3+> is improved; and shuffling of Li<+> and Ni<2+> ions is reduced. According to the method, continuous mass production can be achieved. The nickel-cobalt-aluminum ternary cathode material has the advantages of good rate capability, high discharge capacity, long cycle lifetime and the like.
Description
(1) technical field
The present invention relates to anode material for lithium-ion batteries technical field, nickel cobalt aluminium tertiary cathode material being specifically related to a kind of high-tap density and preparation method thereof.
(2) background technology
Positive electrode is the key components of lithium ion battery, governs its performance.The advantage such as have discharge capacity high and low temperature and good rate capability based on the nickel cobalt aluminium ternary material of nickel content, have extended cycle life, is produced by Tesla, lithium ion battery that worldwide ModelS electrocar uses, and its positive pole is nickel cobalt aluminium ternary material just.In addition, world-famous electrokinetic cell manufacturer LG, AESC, Panasonic etc. are all at the lithium ion battery that volume production is positive pole with nickel cobalt aluminium ternary material.
Although nickel cobalt aluminium ternary material obtains certain application, also there are some problems in this material.Due to Li
+and Ni
2 +radius is close, Ni
2+easily occupy Li
+position, causes ion mixing, causes active lithium to reduce and capacity reduction.In addition, the residual lithium of material pH value and surface is higher, the easy water absorbent gel of pulping process, is difficult to coating.Lithium carbonate decomposes the CO produced
2make the easy bulging of battery.For these problems, researcher has done a large amount of improvement.
Chinese invention patent CN201010594744 discloses a kind of preparation method of lithium ion battery anode material spherical aluminum-doped nickel lithium carbonate for lithium, this method adopts the method for oxidizer liquid phase coprecipitation to prepare nickel cobalt aluminium presoma, because aluminium hydroxide is amphiprotic substance, aluminium ion is difficult to generate hydroxide precursor with nickel and cobalt ions co-precipitation, the obtained actual chemical constituent of presoma and theoretical value have certain deviation, and lot stability is poor.In addition, presoma tap density is low, and it is also on the low side finally to burn the nickel cobalt aluminium positive electrode tap density.
Chinese invention patent CN201110140341 and CN201110375293 first prepares nickel cobalt binary presoma by crystallization control coprecipitation, and then with aluminium salt and precipitation reagent metallized aluminum generating nickel cobalt aluminum precipitation thing on nickel cobalt binary presoma.This method complex steps, increases cost, and can only produce single still, can not continuous operations, is unfavorable for that industrialization is produced.
(3) summary of the invention
In view of prior art problem, nickel cobalt aluminium tertiary cathode material that the invention provides a kind of high-tap density and preparation method thereof.The method is applicable to suitability for industrialized production, and cost is lower, and operation is less, and automaticity is high, product with stable quality.High, the good sphericity of nickel cobalt aluminium ternary material tap density of preparation, be easy to processing, battery energy density is high and durable.
The present invention is achieved through the following technical solutions:
A preparation method for the nickel cobalt aluminium tertiary cathode material of high-tap density, its special character is: comprise the following steps:
(1) preparation of nickel cobalt precursor: by nickel cobalt mixed solution, precipitant solution, enveloping agent solution stream adds in reactor, regulated by online pH automatic control system, control pH value 8.0-12.5, temperature 25-60 DEG C, complexing agent concentration 2-13g/L in reactor, coprecipitation reaction, overflow discharging, filtering stock is less than 8.0 to pH, dry, sieve and obtain spherical nickel-cobalt precursor powder, wherein, the mol ratio of nickel salt and cobalt salt is (0.75-0.95): (0.05-0.25);
(2) preparation of nickel cobalt aluminium positive electrode: by nickel cobalt precursor powder, aluminum contained compound, doped compound, lithium salts by metal ion mol ratio (0.90-0.98): (0.02-0.10): (0-0.008): (1-1.1) mixes, pre-burning a period of time at low temperatures, directly raised temperature is incubated a period of time again, naturally cool, pulverize and sieve the nickel cobalt aluminium tertiary cathode material namely obtaining high-tap density.
In step (1), described nickel salt, cobalt salt are respectively at least one of acetate, sulfate, nitrate or chlorate containing respective element; Described precipitation reagent is the mixture of one or more in NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium acid carbonate, carbonic hydroammonium; Described complexing agent is the mixture of one or more in ammoniacal liquor, EDTA, citric acid.
The concentration of nickel cobalt mixed solution is 1.0-2.5mol/L, and the concentration of precipitant solution is 1.0-10.0mol/L, and the concentration of enveloping agent solution is 0.5-12.0mol/L.
Nickel cobalt mixed solution, precipitant solution, enveloping agent solution under agitation react, and its mixing speed is 200-900rpm.
In step (2), described aluminum contained compound is the mixture of one or more in aluminium oxide, aluminium hydroxide, aluminum acetate or aluminum nitrate; Described doped compound is bivalent compound, be copper, magnesium, zinc, calcium, strontium, barium oxide, hydroxide or nitrate in the mixture of one or more, described lithium salts is the mixture of one or more in lithium carbonate, lithium nitrate, lithium hydroxide or lithium acetate.
Described low temperature refers to 300-600 DEG C, and burn-in time is 2-12 hour, and high temperature refers to 650-950 DEG C, and temperature retention time is 6-24 hour.
In step (2), calcine and carry out in oxygen-enriched atmosphere, oxygen quality mark is greater than 95%.
A kind of nickel cobalt aluminium tertiary cathode material of high-tap density, in the nickel cobalt aluminium tertiary cathode material of this high-tap density, the mol ratio of nickel, cobalt, aluminium, doped chemical, elemental lithium is (0.675-0.931): (0.045-0.245): (0.02-0.10): (0-0.008): (1-1.1), wherein, doped chemical is one or more in copper, magnesium, zinc, calcium, strontium, barium.The valence state of doped chemical is divalence.
Beneficial effect of the present invention:
1, bivalent metal ion doping, not only stable for the layered crystal structure of material, and improves Ni
3+content, reduce Li
+with Ni
2+ion mixing.
2, the nickel cobalt aluminium ternary material tap density of preparation is high, particle good sphericity, size uniformity.
3, the method technique is simple, energy consumption is low, can continuous batch production, good product consistency.Product has the large and advantage such as to have extended cycle life of good rate capability, discharge capacity.
(4) accompanying drawing explanation
Accompanying drawing 1 is the SEM figure of the nickel cobalt aluminium ternary material of preparation in example 1;
Accompanying drawing 2 is SEM figure of the nickel cobalt aluminium ternary material of preparation in comparative example 1.
(5) embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
First, with the nickel cobalt mixed solution of nickel nitrate, cobalt nitrate preparation 1.5mol/L, wherein the mol ratio of nickel and cobalt is 0.86:0.14, the preparation sodium hydroxide solution of 3.0mol/L, the ammonia spirit of 2.0mol/L, by above-mentioned three kinds of solution and stream adds in reactor, regulated by online pH automatic control system, control pH value 11.2, temperature 50 C, ammonia concn 5g/L, mixing speed 700rpm in reactor, coprecipitation reaction, overflow discharging.Filtering stock is less than 8.0 to pH, and 150 DEG C of oven dry, sieve and obtain spherical nickel-cobalt precursor powder.
Secondly, above-mentioned nickel cobalt precursor, aluminium oxide, magnesium hydroxide, lithium hydroxide are mixed by metal ion mol ratio 0.93:0.07:0.003:1.03, the middle pre-burning of oxygen-enriched atmosphere (oxygen quality mark is greater than 95%) 6 hours at 450 DEG C, directly be elevated to 780 DEG C of insulations 12 hours again, naturally cool, pulverize and sieve the LiNi namely obtaining high-tap density
0.80co
0.13al
0.07mg
0.003o
2.Fig. 1 is its SEM photo, and can find out that material is secondary spherical or the spherical particle of primary particle composition, size is homogeneous.
Dandong Bai Te Instrument Ltd. BT-303 tap density tester is used to detect the tap density of sample, use the granularity of Britain Malvern Instr Ltd. Mastersizer3000 laser particle analyzer test sample, use the specific area of U.S. Kang Ta instrument company Nova2000e specific surface instrument test sample.By above-mentioned nickel cobalt aluminium ternary material, conductive black SuperP, electrically conductive graphite ks-6 and binding agent PVDF 88:3:3:6 in mass ratio, add appropriate 1-METHYLPYRROLIDONE solvent even, be applied on aluminium foil and make positive plate.In argon gas atmosphere dry glove box, be to electrode with metal lithium sheet, Celgard2400 perforated membrane is barrier film, LiPF
6/ EC+DMC+EMC(volume ratio 1:1:1) be electrolyte, be assembled into 2032 button cells.At 25 ± 1 DEG C, voltage range is carry out constant current charge-discharge test with the blue electric CT2001A charge-discharge test instrument in Wuhan under 3.0 ~ 4.3V.
Embodiment 2
First, with the nickel cobalt mixed solution of nickel chloride, cobaltous sulfate preparation 1.0mol/L, wherein the mol ratio of nickel and cobalt is 0.867:0.133, (wherein EDTA is 0.3mol/L for the preparation sodium carbonate liquor of 1.0mol/L, the EDTA of 0.5mol/L and ammoniacal liquor mixed solution, ammoniacal liquor is 0.2mol/L), by above-mentioned three kinds of solution and stream adds in reactor, regulated by online pH automatic control system, control pH value 8.1, temperature 25 DEG C, complexing agent concentration 2g/L, mixing speed 500rpm in reactor, coprecipitation reaction, overflow discharging.Filtering stock is less than 8.0 to pH, and 150 DEG C of oven dry, sieve and obtain spherical nickel-cobalt precursor powder.
Secondly, above-mentioned nickel cobalt precursor, aluminum nitrate, lithium carbonate are mixed by metal ion mol ratio 0.98:0.02:1.06, the middle pre-burning of oxygen-enriched atmosphere (oxygen quality mark is greater than 95%) 8 hours at 400 DEG C, directly be elevated to 850 DEG C of insulations 16 hours again, naturally cool, pulverize and sieve the LiNi namely obtaining high-tap density
0.85co
0.13al
0.02o
2.
Embodiment 3
First, with the nickel cobalt mixed solution of nickel acetate, cobalt acetate preparation 2.0mol/L, wherein the mol ratio of nickel and cobalt is 0.778:0.222, the preparation sodium hydroxide solution of 8.0mol/L, the ammonia spirit of 10.0mol/L, by above-mentioned three kinds of solution and stream adds in reactor, regulated by online pH automatic control system, control pH value 12.0, temperature 60 C, ammonia concn 13g/L, mixing speed 800rpm in reactor, coprecipitation reaction, overflow discharging.Filtering stock is less than 8.0 to pH, and 120 DEG C of oven dry, sieve and obtain spherical nickel-cobalt precursor powder.
Secondly, above-mentioned nickel cobalt precursor, aluminium hydroxide, copper nitrate, lithium acetate are mixed by metal ion mol ratio 0.90:0.10:0.005:1.09, the middle pre-burning of oxygen-enriched atmosphere (oxygen quality mark is greater than 95%) 2 hours at 600 DEG C, directly be elevated to 820 DEG C of insulations 6 hours again, naturally cool, pulverize and sieve the LiNi namely obtaining high-tap density
0.7co
0.2al
0.1cu
0.005o
2.Its granularity D
10, D
50, D
90be 6.1,10.3,16.7 μm respectively, tap density is 2.71g/cm
3, specific area 0.35m
2/ g, 0.2C first discharge capacity are 185.2mAh/g, first efficiency to be 90.5%, 1C discharge capacity be 171.1mAh/g, 1C charge and discharge cycles after 110 weeks capability retention be 90.2%.
Embodiment 4
First, with the nickel cobalt mixed solution of nickelous sulfate, cobalt nitrate preparation 2.5mol/L, wherein the mol ratio of nickel and cobalt is 0.947:0.053, the citric acid solution of the preparation sodium carbonate of 1.8mol/L and carbonic hydroammonium mixed solution (sodium carbonate and carbonic hydroammonium mol ratio are 1:2), 1.0mol/L, by above-mentioned three kinds of solution and stream adds in reactor, regulated by online pH automatic control system, control pH value 8.5, temperature 40 DEG C, citric acid concentration 4g/L, mixing speed 400rpm in reactor, coprecipitation reaction, overflow discharging.Filtering stock is less than 8.0 to pH, and 110 DEG C of oven dry, sieve and obtain spherical nickel-cobalt precursor powder.
Secondly, above-mentioned nickel cobalt precursor, aluminium hydroxide, calcium oxide, zinc oxide, lithium nitrate are mixed by metal ion mol ratio 0.95:0.05:0.002:0.006:1.05, the middle pre-burning of oxygen-enriched atmosphere (oxygen quality mark is greater than 95%) 12 hours at 500 DEG C, directly be elevated to 700 DEG C of insulations 20 hours again, naturally cool, pulverize and sieve the LiNi namely obtaining high-tap density
0.90co
0.05al
0.05ca
0.002zn
0.006o
2.Its granularity D
10, D
50, D
90be 6.9,11.2,17.6 μm respectively, tap density is 2.60g/cm
3, specific area 0.44m
2/ g, 0.2C first discharge capacity are 199.7mAh/g, first efficiency to be 90.1%, 1C discharge capacity be 180.5mAh/g, 1C charge and discharge cycles after 110 weeks capability retention be 88.2%.
Embodiment 5
First, with the nickel cobalt mixed solution of nickelous sulfate, cobalt chloride preparation 1.8mol/L, wherein the mol ratio of nickel and cobalt is 0.75:0.25, potassium hydroxide solution, the ammoniacal liquor of 12.0mol/L, the EDTA mixed aqueous solution (mol ratio of ammoniacal liquor, EDTA is 1:1) of preparation 10.0mol/L, by above-mentioned three kinds of solution and stream adds in reactor, regulated by online pH automatic control system, control pH value 12.5, temperature 30 DEG C, complexing agent concentration 8g/L, mixing speed 900rpm in reactor, coprecipitation reaction, overflow discharging.Filtering stock is less than 8.0 to pH, and 105 DEG C of oven dry, sieve and obtain spherical nickel-cobalt precursor powder.
Secondly, above-mentioned nickel cobalt precursor, aluminum acetate, strontium nitrate, barium nitrate, lithium acetate, lithium carbonate are mixed by metal ion mol ratio 0.90:0.10:0.002:0.002:0.8:0.3, the middle pre-burning of oxygen-enriched atmosphere (oxygen quality mark is greater than 95%) 9 hours at 300 DEG C, directly be elevated to 650 DEG C of insulations 24 hours again, naturally cool, pulverize and sieve the LiNi namely obtaining high-tap density
0.675co
0.225al
0.1sr
0.002ba
0.002o
2.Its granularity D
10, D
50, D
906.1,10.9,17.2 μm respectively, tap density 2.64g/cm
3, specific area 0.41,0.2C discharge capacity 184.1mAh/g, efficiency 90.6%, 1C discharge capacity 168.0mAh/g, 1C circulate 110 weeks conservation rates 91.9% first.
Embodiment 6
First, with the nickel cobalt mixed solution of nickel nitrate, cobalt acetate preparation 2.5mol/L, wherein the mol ratio of nickel and cobalt is 0.95:0.05, the preparation lithium hydroxide solution of 5.0mol/L, the aqueous citric acid solution of 6.0mol/L, by above-mentioned three kinds of solution and stream adds in reactor, regulated by online pH automatic control system, control pH value 10.7, temperature 45 C, citric acid concentration 6g/L, mixing speed 600rpm in reactor, coprecipitation reaction, overflow discharging.Filtering stock is less than 8.0 to pH, and 130 DEG C of oven dry, sieve and obtain spherical nickel-cobalt precursor powder.
Secondly, above-mentioned nickel cobalt precursor, aluminium hydroxide, barium monoxide, lithium hydroxide are mixed by metal ion mol ratio 0.98:0.02:0.004:1, the middle pre-burning of oxygen-enriched atmosphere (oxygen quality mark is greater than 95%) 5 hours at 450 DEG C, directly be elevated to 950 DEG C of insulations 6 hours again, naturally cool, pulverize and sieve the LiNi namely obtaining high-tap density
0.931co
0.049al
0.02ba
0.004o
2.Its granularity D
10, D
50, D
905.8,10.8,16.9 μm respectively, tap density 2.58g/cm
3, specific area 0.51,0.2C discharge capacity 203.6mAh/g, efficiency 91.5%, 1C discharge capacity 182.7mAh/g, 1C circulate 110 weeks conservation rates 84.3% first.
Embodiment 7
First, with the nickel cobalt mixed solution of nickel chloride, cobalt acetate preparation 1.0mol/L, wherein the mol ratio of nickel and cobalt is 0.85:0.15, sodium bicarbonate solution, the citric acid of 3.0mol/L, the EDTA mixed aqueous solution (citric acid, EDTA mol ratio are 1:1) of preparation 4.0mol/L, by above-mentioned three kinds of solution and stream adds in reactor, regulated by online pH automatic control system, control pH value 8.3, temperature 55 DEG C, complexing agent concentration 5g/L, mixing speed 650rpm in reactor, coprecipitation reaction, overflow discharging.Filtering stock is less than 8.0 to pH, and 140 DEG C of oven dry, sieve and obtain spherical nickel-cobalt precursor powder.
Secondly, above-mentioned nickel cobalt precursor, aluminium oxide, aluminum acetate, strontium nitrate, magnesium oxide, zinc nitrate, lithium hydroxide are mixed by metal ion mol ratio 0.94:0.03:0.03:0.002:0.002:0.004:1.05, the middle pre-burning of oxygen-enriched atmosphere (oxygen quality mark is greater than 95%) 5 hours at 600 DEG C, directly be elevated to 850 DEG C of insulations 16 hours again, naturally cool, pulverize and sieve the LiNi namely obtaining high-tap density
0.799co
0.141al
0.06sr
0.002mg
0.002zn
0.004o
2.Its granularity D
10, D
50, D
907.1,12.3,19.5 μm respectively, tap density 2.69g/cm
3, specific area 0.28,0.2C discharge capacity 191.3mAh/g, efficiency 91.1%, 1C discharge capacity 178.4mAh/g, 1C circulate 110 weeks conservation rates 90.3% first.
Embodiment 8
First, with nickelous sulfate, the nickel cobalt mixed solution of cobaltous sulfate preparation 1.8mol/L, wherein the mol ratio of nickel and cobalt is 0.80:0.20, the sodium acid carbonate of preparation 3.0mol/L, sodium carbonate mixed aqueous solution (sodium acid carbonate, the mol ratio of sodium carbonate is 1:1), the citric acid of 2.5mol/L, EDTA mixed aqueous solution (citric acid, EDTA mol ratio is 1:2), by above-mentioned three kinds of solution and stream adds in reactor, regulated by online pH automatic control system, control pH value 8.0 in reactor, temperature 60 C, complexing agent concentration 10g/L, mixing speed 650rpm, coprecipitation reaction, overflow discharging.Filtering stock is less than 8.0 to pH, and 100 DEG C of oven dry, sieve and obtain spherical nickel-cobalt precursor powder.
Secondly, above-mentioned nickel cobalt precursor, aluminum nitrate, magnesium hydroxide, calcium hydroxide, cupric oxide, zinc nitrate, lithium hydroxide are mixed by metal ion mol ratio 0.92:0.08:0.002:0.001:0.002:0.002:1.07, the middle pre-burning of oxygen-enriched atmosphere (oxygen quality mark is greater than 95%) 7 hours at 500 DEG C, directly be elevated to 900 DEG C of insulations 8 hours again, naturally cool, pulverize and sieve the LiNi namely obtaining high-tap density
0.736co
0.184al
0.08mg
0.002ca
0.001cu
0.002zn
0.002o
2.Its granularity D
10, D
50, D
906.6,12.0,18.3 μm respectively, tap density 2.65g/cm
3, specific area 0.36,0.2C discharge capacity 186.5mAh/g, efficiency 89.9%, 1C discharge capacity 174.7mAh/g, 1C circulate 110 weeks conservation rates 91.6% first.
Causing the difference of the various materialization of material and battery performance in order to compare distinct methods, adopting traditional nickel cobalt aluminium element coprecipitation to prepare presoma, then preparing nickel cobalt aluminium ternary material with lithium salts mixed sintering.Concrete steps are as follows:
Comparative example 1
First, with the nickel cobalt aluminium mixed solution of nickel nitrate, cobalt nitrate, aluminum nitrate preparation 1.5mol/L, wherein the mol ratio of nickel, cobalt, aluminium is 0.80:0.13:0.07, the preparation sodium hydroxide solution of 3.0mol/L, the ammonia spirit of 2.0mol/L, by above-mentioned three kinds of solution and stream adds in reactor, regulated by online pH automatic control system, control pH value 11.2, temperature 50 C, ammonia concn 5g/L, mixing speed 700rpm in reactor, coprecipitation reaction, overflow discharging.Filtering stock is less than 8.0 to pH, and 150 DEG C of oven dry, sieve and obtain spherical nickel-cobalt precursor powder.
Secondly, above-mentioned nickel cobalt aluminium presoma, magnesium hydroxide, lithium hydroxide are mixed by metal ion mol ratio 1:0.003:1.03, the middle pre-burning of oxygen-enriched atmosphere (oxygen quality mark is greater than 95%) 6 hours at 450 DEG C, directly be elevated to 780 DEG C of insulations 12 hours again, naturally cool, pulverize and sieve the LiNi namely obtaining high-tap density
0.8co
0.13al
0.07mg
0.003o
2.Fig. 2 is its SEM photo, although material is also secondary spherical or the spherical particle of primary particle composition, its primary particle is tiny, spherical not of uniform size, has more granule.
Comparative example 2
First, with the nickel cobalt aluminium mixed solution of nickel chloride, cobaltous sulfate, aluminum nitrate preparation 1.0mol/L, wherein the mol ratio of nickel, cobalt, aluminium is 0.85:0.13:0.02, (wherein EDTA is 0.3mol/L for the preparation sodium carbonate liquor of 1.0mol/L, the EDTA of 0.5mol/L and ammoniacal liquor mixed solution, ammoniacal liquor is 0.2mol/L), by above-mentioned three kinds of solution and stream adds in reactor, regulated by online pH automatic control system, control pH value 8.1, temperature 25 DEG C, complexing agent concentration 2g/L, mixing speed 500rpm in reactor, coprecipitation reaction, overflow discharging.Filtering stock is less than 8.0 to pH, and 150 DEG C of oven dry, sieve and obtain spherical nickel-cobalt precursor powder.
Secondly, above-mentioned nickel cobalt aluminium presoma, lithium carbonate are mixed by metal ion mol ratio 1:1.06, the middle pre-burning of oxygen-enriched atmosphere (oxygen quality mark is greater than 95%) 8 hours at 400 DEG C, directly be elevated to 850 DEG C of insulations 16 hours again, naturally cool, pulverize and sieve the LiNi namely obtaining high-tap density
0.85co
0.13al
0.02o
2.
In table 1 example and comparative example sample physico-chemical parameter and buckle electric data
| Sample | Granularity (μm) D 10，D 50，D 90 | Tap density (g/cm 3） | Specific area (m 2/g） | 0.2C discharge capacity (mAh/g) | Efficiency (%) first | 1C discharge capacity (mAh/g) | 1C circulates 110 weeks conservation rates (%) |
| Example 1 | 6.5，10.6，16.9 | 2.52 | 0.41 | 187.0 | 88.2 | 173.0 | 87.5 |
| Comparative example 1 | 5.9，10.5，17.3 | 2.21 | 0.67 | 189.6 | 88.9 | 178.0 | 77.3 |
| Example 2 | 6.3，10.8，17.2 | 2.48 | 0.39 | 193.8 | 88.7 | 174.2 | 83.2 |
| Comparative example 2 | 6.7，11.3，18.8 | 2.19 | 0.80 | 191.9 | 91.4 | 177.5 | 70.8 |
Table 1 lists the physico-chemical parameter of sample in example and comparative example and buckles electric data, and wherein the granularity of four samples relatively, D
50between 10.5-11.5 μm, tap density example 1 is suitable with example 2, all higher than comparative example 1 and comparative example 2.Specific area is just in time contrary, and example 1 and example 2 are all lower than comparative example 1 and comparative example 2.
Example 1 under 0.2C first discharge capacity be 187.0mAh/g, initial coulomb efficiency is that under 88.2%, 1C, discharge capacity is 173.0mAh/g first.And the 0.2C capacity of comparative example 1,1C capacity and coulombic efficiency are all a little more than example 1, but 1C circulation conservation rate is lower than example 1, and after 110 weeks, residual capacity is 77.3%.
The 0.2C capacity of example 2 and comparative example 2,1C capacity, coulombic efficiency are close, but 1C cycle performance example 2 is better than comparative example 2, and after 110 weeks, conservation rate is 83.2%.In addition, due to divalence Mg
2+doping, stabilizes the layer structure of nickel cobalt aluminium ternary material, reduces Li
+with Ni
2+ion mixing, example 1 is higher than the circulation volume of example 2.
To sum up, sample materialization prepared by the present invention and battery performance are all better than sample prepared by conventional method, this sample good sphericity, particle is homogeneous, tap density is large, specific area is little, discharge capacity is high, have extended cycle life, and the method is simple, equipment requirement is low, product batches is stablized, be easy to high-volume produce.
Claims (9)
1. a preparation method for the nickel cobalt aluminium tertiary cathode material of high-tap density, is characterized in that: comprise the following steps:
(1) preparation of nickel cobalt precursor: by nickel cobalt mixed solution, precipitant solution, enveloping agent solution stream adds in reactor, regulated by online pH automatic control system, control pH value 8.0-12.5, temperature 25-60 DEG C, complexing agent concentration 2-13g/L in reactor, coprecipitation reaction, overflow discharging, filtering stock is less than 8.0 to pH, dry, sieve and obtain spherical nickel-cobalt precursor powder, wherein, the mol ratio of nickel salt and cobalt salt is (0.75-0.95): (0.05-0.25);
(2) preparation of nickel cobalt aluminium positive electrode: by nickel cobalt precursor powder, aluminum contained compound, doped compound, lithium salts by metal ion mol ratio (0.90-0.98): (0.02-0.10): (0-0.008): (1-1.1) mixes, pre-burning a period of time at low temperatures, directly raised temperature is incubated a period of time again, naturally cool, pulverize and sieve the nickel cobalt aluminium tertiary cathode material namely obtaining high-tap density.
2. the preparation method of the nickel cobalt aluminium tertiary cathode material of a kind of high-tap density according to claim 1, it is characterized in that: in step (1), described nickel salt, cobalt salt are respectively at least one of acetate, sulfate, nitrate or chlorate containing respective element; Described precipitation reagent is the mixture of one or more in NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium acid carbonate, carbonic hydroammonium; Described complexing agent is the mixture of one or more in ammoniacal liquor, EDTA, citric acid.
3. the preparation method of the nickel cobalt aluminium tertiary cathode material of a kind of high-tap density according to claim 1, it is characterized in that: in step (2), described aluminum contained compound is the mixture of one or more in aluminium oxide, aluminium hydroxide, aluminum acetate or aluminum nitrate; Described doped compound is bivalent compound, be the mixture of one or more in copper, magnesium, zinc, calcium, strontium, the oxide of barium, hydroxide or nitrate, described lithium salts is the mixture of one or more in lithium carbonate, lithium nitrate, lithium hydroxide or lithium acetate.
4. the preparation method of the nickel cobalt aluminium tertiary cathode material of a kind of high-tap density according to claim 1, it is characterized in that: in step (2), described low temperature refers to 300-600 DEG C, burn-in time is 2-12 hour, high temperature refers to 650-950 DEG C, and temperature retention time is 6-24 hour.
5. the preparation method of the nickel cobalt aluminium tertiary cathode material of high-tap density according to claim 1, it is characterized in that: in step (1), the concentration of nickel cobalt mixed solution is 1.0-2.5mol/L, the concentration of precipitant solution is 1.0-10.0mol/L, and the concentration of enveloping agent solution is 0.5-12.0mol/L.
6. the preparation method of the nickel cobalt aluminium tertiary cathode material of a kind of high-tap density according to claim 5, it is characterized in that: nickel cobalt mixed solution, precipitant solution, enveloping agent solution under agitation react, its mixing speed is 200-900rpm.
7. the preparation method of the nickel cobalt aluminium tertiary cathode material of a kind of high-tap density according to claim 1, is characterized in that: in step (2), calcine and carry out in oxygen-enriched atmosphere, oxygen quality mark is greater than 95%.
8. the nickel cobalt aluminium tertiary cathode material of a high-tap density, it is characterized in that: in the nickel cobalt aluminium tertiary cathode material of this high-tap density, the mol ratio of nickel, cobalt, aluminium, doped chemical, elemental lithium is (0.675-0.931): (0.045-0.245): (0.02-0.10): (0-0.008): (1-1.1), wherein, doped chemical is one or more in copper, magnesium, zinc, calcium, strontium, barium.
9. the nickel cobalt aluminium tertiary cathode material of a kind of high-tap density according to claim 8, is characterized in that: the valence state of doped chemical is divalence.
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