CN1372338A - Process for preparing spherical nano crystal lightium nickel cobaltate for lihtium secondary cell - Google Patents

Process for preparing spherical nano crystal lightium nickel cobaltate for lihtium secondary cell Download PDF

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CN1372338A
CN1372338A CN01106257A CN01106257A CN1372338A CN 1372338 A CN1372338 A CN 1372338A CN 01106257 A CN01106257 A CN 01106257A CN 01106257 A CN01106257 A CN 01106257A CN 1372338 A CN1372338 A CN 1372338A
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nickel
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lithium
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李许明
赵泉
胡宝钢
李�杰
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李许明
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

This invention provides a method for preparing spherical nano crystal lithium nickel cobaltate for lithium sevondary cell containing to lead the nickel sall solution, alkali solution and strong ammonia solution into the reactor continuously, mix and over flow them continuously to keep the reactance unsatable to feed back the overflown materials to the reactance unsatable to feedback the overflown materials to the reactor with intermittance to modulate the rotating state of the solution with the feedback to change the time interval styed in the solution with the feed back to change the time interval styed in the reaction of the reactant material then the ege clean to produce an intermediate product NixCox(OH)2 of spherical nano crystal and to again mix the inter mediate NixCOy(OH)2, LiOH.H2O and Mx and put them into the furnace to heat to get LiNxCoyM2O2, suitable for the indus-trialized production with good electrical

Description

A kind of secondary lithium batteries ball shaped nano crystal lightium nickel cobaltate preparation method
The present invention relates to secondary lithium batteries spherical nickel-cobalt acid lithium, specifically a kind of secondary lithium batteries ball shaped nano crystal lightium nickel cobaltate preparation method.
In the prior art, lithium nickel cobalt dioxide is mainly as the positive electrode active materials of lithium secondary battery, and it has overcome shortcomings such as the synthetic difficulty of lithium nickelate and cobalt acid lithium cost an arm and a leg, and is second generation anode for lithium battery material.At present general method for making has: sintering process, soft chemical method and spray drying process etc. generally are that the prior ball milling of nickel cobalt salt is mixed sintering behind back sintering or the chemical legal system predecessor, the former composition inequality, more expensive, the complex process of latter's price.Materials such as lithium nickel cobalt dioxide that these methods obtain or cobalt acid lithium are difficult to satisfy the demand for development of modern lithium ion battery high-capacitance, and because synthesis technique is wayward, so it is synthetic back shape of product is irregular, mobile poor, the composition inequality, the pole piece uniformity of making behind the battery is poor.
Day disclosure special permission is special opens the manufacture method that flat 2-40861 has announced lithium nickel cobalt dioxide: lithium hydroxide, nickel oxide, cobalt oxide powder are mixed by a certain percentage, about 600～800 ℃ of heating under air atmosphere, in air, mix then, under this temperature, heat in the air atmosphere again then, obtain Powdered lithium nickel cobalt dioxide after the block that obtains cleaned, grinds, its discharge capacity is about 120mAh/g.The production control method complexity of this lithium nickel cobalt dioxide need be through twice calcining and mixed once, and product is irregularly shaped, and discharge capacity is low, can not satisfy the requirement of modern lithium rechargeable battery with lithium nickel cobalt dioxide.
Tsing-Hua University has announced a kind of process (spray drying process) of novel preparation anode material for lithium-ion batteries, with Li: Co mol ratio 1: 1 proportioning weighing lithium acetate and cobalt acetate, and take by weighing a certain amount of macromolecular compound polyethylene glycol (PEG), the adding deionized water is made into the solution of 0.05～1.0mol/L, resulting solution pneumatic spray drying device drying, adopt and the fluidized drying mode, atomising device adopts two streaming nozzles, feedstock solution peristaltic pump sample introduction, speed are 12～20mL/min; The orifice gas flow is controlled by compressed-air actuated pressure, produces atomizing under about 0.1MPa; The control temperature of inlet air is 300 ℃, and outlet is 100 ℃; Outlet air separates emptying through the one-level vortex, and the mixed powder of the polyethylene glycol of spray drying gained and lithium acetate, cobalt acetate promptly obtains LiCoO 800 ℃ of calcinings through 4h 2Superfine powder.Gained LiCoO 2The powder element is evenly distributed, and particle diameter is the hundreds of nanometer; Chemical property is that charging capacity is 148mAh/g, and discharge capacity is 135mAh/g.The cobalt acid lithium charge/discharge capacity that this method obtains is low, and product is irregularly shaped, and complex process, and equipment investment is big.
Sichuan University's journal has been announced a kind of process (soft chemical method) of up-to-date preparation anode material for lithium-ion batteries.With Li 2CO 3With Co (NO 3) 2Li: Co=1 in molar ratio: 1 mixes, and with the least possible water-soluble solid of separating, splashes into H under the stirring 2O 2, add and the citric acid that (Li+Co) waits molal quantity, in 60 ℃ of following stir about 200min, be heated to the dried predecessor that obtains giving birth to, with the predecessor porphyrize, respectively at 500 ℃, sintering 4h under 700 ℃ and the 900 ℃ of air atmospheres obtains cobalt acid lithium in tube furnace.This product is through making battery testing, and the charge ratio capacity is 146mAh/g for the first time, and the discharge capacity after 25 weeks of circulating is 135mAhg -1, irreversible capacity loss is 7.5%.It is low that cobalt that this method obtains acid lithium has charge/discharge capacity equally, and product is a shortcoming such as irregularly shaped.
The object of the present invention is to provide a kind of suitability for industrialized production, regular shape, uniform ingredients, electric property is good, production process is convenient to control secondary lithium batteries sphere or class ball shaped nano crystal lightium nickel cobaltate preparation method be convenient to.
To achieve these goals, technical scheme of the present invention is that operating procedure is as follows:
1) reactant nickel salt solution, aqueous slkali and concentrated ammonia solution are imported reactor continuously, mix and stir, overflow from overfall continuously again, the a certain fixed value of quantity delivered stable control reacting system PH value between 11.0-12.0 by adjusting aqueous slkali in the system course of reaction, amplitude is ± 0.2, and temperature is controlled in the 50-60 ℃ of scope;
2) in described course of reaction, keeping the reaction system environment is unsteady state, again be back in reaction system with intermittent mode the partial reaction material that overflows by product pump, adjust the rotation status of material with refluxing, change the time of staying of reactant in reaction system, the control nickel hydroxide grows up to sphere or class ball shaped nano crystalline substance; Reaction is finished, and makes the brilliant hydroxide nickel of intermediate products ball shaped nano through ageing, cleaning xCo y(OH) 2, Ni wherein xThe percetage by weight that accounts for Ni and Co summation is 40～80%, Co yAccount for Ni and Co summation percetage by weight is 20～60%;
3) the brilliant nickel hydroxide cobalt of the intermediate product ball shaped nano Ni that learns from else's experience and under the unstable state equilibrium condition, produce in the reactor xCo y(OH) 2, get lithium hydroxide LiOHH again 2O (Ni 1-1.02) and M z, mix mechanical agitation;
4) the described reactant that mixes packed into heat in the incinerator, finished product lithium nickel cobalt dioxide LiNi xCo yM zO 2, in reaction system, heating rate is 5～30 ℃/min, temperature is controlled at 350～900 ℃, is incubated 5～30 hours; The rate of temperature fall of reacting rear material is at 50～200 ℃/min;
Wherein: M is one of Ti, Mg, Al, Cr or its combination in step (3), (4); The percetage by weight x value that Ni accounts for Ni, Co and M summation is 40～80%, and the percetage by weight y value that Co accounts for Ni, Co and M summation is 20～60%, and the percetage by weight z value that M accounts for Ni, Co and M summation is 0～0.01%;
Nickel salt solution is the salt-mixture of nickelous sulfate, cobaltous sulfate, zinc sulfate described in the step (1), and mole is dense at 1.9～2.0mol/l; Aqueous slkali is a sodium hydroxide solution, and its molar concentration is 8.0～9.0mom/l; Concentrated ammonia solution density is 0.890～0.910g/ml; Refluxed once in the every interval of solution that overflows in the reaction system in the step (2) in 1～5 hour, each return time is 5～30min, and back-flow velocity is 300～500L/h; The method that changes reaction system internal reaction material rotation status in the inherent feed back process of described reaction system is for adjusting mixing speed, and mixing speed was 250～350 commentaries on classics/min when promptly material did not reflux, and mixing speed is 150～250 commentaries on classics/min during feed back; Heating rate is 10～20 ℃/min in the described step (4); Temperature is controlled at 450～850 ℃, is incubated 10～20 hours.
Major advantage of the present invention is:
1. course of reaction is convenient to control, production efficiency height.The present invention can be by the computer control course of reaction, the production efficiency height, as: a 10KW calciner, daily output sphere or class ball shaped nano crystal lightium nickel cobaltate powder can reach 100kg, and its optimum point of production is 50～80kg.
2. shape of product rule, uniform ingredients, electric property is good.The perfection of nano crystal lightium nickel cobaltate powder X-ray ray (XRD) curve, spherical form rule that the present invention produced, as depicted in figs. 1 and 2, apparent density is greater than 0.9g/ml, and tap density can reach 2.0～2.5g/ml; The lithium nickel cobalt dioxide specific area that working condition of the present invention is produced (can reach 0.3～0.9m greatly 2/ g), density is big, no dephasign, and product quality is continual and steady; Raw material sources are extensive, and packed density height, discharge capacity height are made and sealed that discharge capacity surpasses 180mAh/g, average life span reached more than 500 weeks, was the positive electrode active materials that present high-capacity lithium ion cell is badly in need of behind the lithium ion battery.
3. production technology is simple, and is easy to operate.The present invention has cast aside traditional manufacture method that relies on powder metallurgy fully, the conventional sintering method is combined with soft chemical method,, adopt simple calcine technology from the brilliant nickel hydroxide cobalt of ball shaped nano, produce the product under the complex situations in the past, greatly facilitate operating process.
Fig. 1 is a ball shaped nano crystal lightium nickel cobaltate product XRD curve of the present invention.
Fig. 2 is a ball shaped nano crystal lightium nickel cobaltate product SEM photo of the present invention.
Fig. 3 is a lithium nickel cobalt dioxide product SEM photo in the prior art.
Fig. 4 is the embodiment of the invention 2 heat tracing curves.
Fig. 5 is the embodiment of the invention 3 heat tracing curves.
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
1) reactor volume 1m 3, reaction solution is the mixed sulfate of nickelous sulfate, cobaltous sulfate, zinc sulfate: molar concentration is 2.0mol/l, sodium hydroxide solution: molar concentration is 9.0mom/l, ammoniacal liquor: density is 0.910g/ml; Import reactor continuously, mix and stir, be controlled at 11.2 ± 0.2 by the stable control of the quantity delivered reacting system PH value of adjusting aqueous slkali in the system course of reaction, reaction temperature is 59 ± 1 ℃;
2) in described course of reaction, keeping the reaction system environment is unsteady state, again be back in reaction system with intermittent mode the partial reaction material that overflows by product pump, adjust the rotation status of material with refluxing, change the time of staying of reactant in reaction system, the control nickel hydroxide grows up to sphere or class sphere, is specially: with feed back once return flow was 300L/h in 3 hours at every interval in the course of reaction.In the reflux course mixing speed is adjusted to 180 commentaries on classics/min by 280 commentaries on classics/min of non-reflux state, the control nickel hydroxide grows up to sphere or class ball shaped nano crystalline substance, and its reaction time is 5 hours; After the reaction, obtain through the brilliant hydroxide nickel of the intermediate product ball shaped nano of ageing, cleaning 80Co 20(OH) 2
3) reactor volume is 0.5m 3Tube furnace, the intermediate product nanometer crystalline Ni of reaction raw materials in reactor, under the unstable state equilibrium condition, producing 0.7Co 0.3(OH) 2Average grain diameter 7～10 μ m), get LiOH.H again 2O (Li 1.02) and MgSO 4(Mg 0.008), TiOCl 4(Ti 0.002), with described mixing of materials, mechanical agitation;
4) the described reactant that mixes packed into heat in the incinerator, finished product lithium nickel cobalt dioxide LiNi 0.7Co 0.29Mg 0.008Ti 0.002O 2, in reaction system, heating rate is 5 ℃/min, temperature is controlled at 400 ℃, is incubated 30 hours; The rate of temperature fall of reacting rear material is at 100 ℃/min.
The product that adopts the inventive method to produce is sphere or class sphere, and apparent density is 0.95g/ml, and tap density is 2.3g/ml, and specific area is 0.7m 2/ g, make battery after its discharge capacity reach 185mAh/g.
Embodiment 2:
Difference from Example 1 is:
1) reactor volume is 0.5m 3Tube furnace, the product nanometer crystalline Ni of reaction raw materials in reactor, under the unstable state equilibrium condition, producing 0.60Co 0.40(OH) 2(average grain diameter 5～8 μ m) get LiOH.H again 2O is with two mixing of materials, mechanical agitation;
2) the described reactant that mixes is packed into heat in the incinerator, its heating rate is 5 ℃/min, and temperature is controlled at 350 ℃, is incubated 5 hours; The rate of temperature fall of reacting rear material gets finished product lithium nickel cobalt dioxide LiNi at 50 ℃/min 0.6Co 0.4O 2, its heat tracing curve is seen Fig. 4.
The product that employing the inventive method is produced is sphere or class sphere as shown in Figure 1, 2, and apparent density is 0.95g/ml, and tap density is 2.3g/ml, and specific area is 0.7m 2/ g, make battery after its discharge capacity reach 185mAh/g.And the product of being produced in the prior art has deficiencies such as out-of-shape, sees Fig. 3.
Embodiment 3:
Difference from Example 1 is:
1) reactor volume is 0.5m 3Tube furnace, the product nanometer crystalline Ni of reaction raw materials in reactor, under the unstable state equilibrium condition, producing 0.5Co 0.5(OH) 2(average grain diameter 7～10 μ m) get LiOH.H again 2O is with two mixing of materials, mechanical agitation;
2) the described reactant that mixes is packed into heat in the incinerator, its heating rate is 10 ℃/min, and temperature is controlled at 450 ℃, is incubated 10 hours; The rate of temperature fall of reacting rear material gets finished product lithium nickel cobalt dioxide LiNi at 100 ℃/min 0.8Co 0.29Mg 0.005Ti 0.005O 2, its heat tracing curve is seen Fig. 5.
The product that employing the inventive method is produced is sphere or class sphere as shown in Figure 1, 2, and apparent density is 0.98g/ml, and tap density is 2.45g/ml, and specific area is 0.68m 2/ g, make battery after its discharge capacity reach 1.82mAh/g.
Embodiment 4:
Difference from Example 1 is:
1) reactor volume is 0.5m 3Tube furnace, the product nanometer crystalline Ni of reaction raw materials in reactor, under the unstable state equilibrium condition, producing 0.8Co 0.2(OH) 2(average grain diameter 7～10 μ m) get LiOH.H again 2O (Li 0.01) and MgSO 4(Mg 0.008), TiOCl 4(Ti 0.002), described mixing of materials, mechanical agitation;
2) the described reactant that mixes is packed into heat in the incinerator, its heating rate is 15 ℃/min, and temperature is controlled at 550 ℃, is incubated 15 hours; The rate of temperature fall of reacting rear material gets finished product lithium nickel cobalt dioxide LiNi at 150 ℃/min 0.8Co 0.29Mg 0.008Ti 0.002O 2
The product that adopts the inventive method to produce is sphere or class sphere, and apparent density is 0.96g/ml, and tap density is 2.35g/ml, and specific area is 0.8m 2/ g, make battery after its discharge capacity reach 187mAh/g.
Embodiment 5:
Difference from Example 1 is:
1) reactor volume is 0.5m 3Tube furnace, the product nanometer crystalline Ni of reaction raw materials in reactor, under the unstable state equilibrium condition, producing 0.40Co 0.60(OH) 2(average grain diameter 7～10 μ m) get LiOH.H again 2O and Al (OH) 3(Al 0.004), described mixing of materials molar ratio is: (Ni+Co+Al): Li=1: 1.1, with its mixing, mechanical agitation;
2) the described reactant that mixes is packed into heat in the incinerator, its heating rate is 25 ℃/min, and temperature is controlled at 850 ℃, is incubated 20 hours; The rate of temperature fall of reacting rear material gets finished product lithium nickel cobalt dioxide LiNi at 180 ℃/min 0.4Co 0.596Al 0.004O 2
The product that adopts the inventive method to produce is sphere or class sphere, and apparent density is 0.98g/ml, and tap density is 2.45g/ml, and specific area is 0.68m 2/ g, make battery after its discharge capacity reach 189mAh/g.
Embodiment 6:
Difference from Example 1 is:
1) reactor volume is the 0.5m3 tube furnace, the product nanometer crystalline Ni of reaction raw materials for producing under the unstable state equilibrium condition in reactor 0.69Co 0.31(OH) 2(average grain diameter 7～10 μ m) get LiOH.H again 2O and Cr (OH) 3(Cr 0.001), with described mixing of materials, mechanical agitation;
2) the described reactant that mixes is packed into heat in the incinerator, its heating rate is 25 ℃/min, and temperature is controlled at 650 ℃, is incubated 30 hours; The rate of temperature fall of reacting rear material gets finished product lithium nickel cobalt dioxide LiNi at 200 ℃/min 0.69Co 0.399Cr 0.001O 2
The product that adopts the inventive method to produce is sphere or class sphere, and apparent density is 0.97g/ml, and tap density is 2.25g/ml, and specific area is 0.9m 2/ g, make battery after its discharge capacity reach 189mAh/g.
Embodiment 7:
Difference from Example 1 is:
1) reactor volume is the 0.5m3 tube furnace, the product nanometer crystalline Ni of reaction raw materials for producing under the unstable state equilibrium condition in reactor 0.7Co 0.3(OH) 2(average grain diameter 7～10 μ m) get LiOH.H again 2O and Cr (OH) 3(Cr 0.005), Al (OH) 3(Al 0.005), described mixing of materials molar ratio is: (Ni+Co+Cr+Al): Li=1: 1.09, with its mixing, mechanical agitation;
2) the described reactant that mixes is packed into heat in the incinerator, its heating rate is 30 ℃/min, and temperature is controlled at 750 ℃, is incubated 25 hours; The rate of temperature fall of reacting rear material gets finished product lithium nickel cobalt dioxide LiNi at 180 ℃/min 0.7Co 0.29Cr 0.005Al 0.005O 2
The product that adopts the inventive method to produce is sphere or class sphere, and apparent density is 0.95g/ml, and tap density is 2.4g/ml, and specific area is 0.7m 2/ g, make battery after its discharge capacity reach 186mAh/g.

Claims (5)

1. secondary lithium batteries ball shaped nano crystal lightium nickel cobaltate preparation method is characterized in that operating procedure is as follows:
1) reactant nickel salt solution, aqueous slkali and concentrated ammonia solution are imported reactor continuously, mix and stir, overflow from overfall continuously again, the a certain fixed value of quantity delivered stable control reacting system PH value between 11.0-12.0 by adjusting aqueous slkali in the system course of reaction, amplitude is ± 0.2, and temperature is controlled in the 50-60 ℃ of scope;
2) in described course of reaction, keeping the reaction system environment is unsteady state, again be back in reaction system with intermittent mode the partial reaction material that overflows by product pump, adjust the rotation status of material with refluxing, change the time of staying of reactant in reaction system, the control nickel hydroxide grows up to sphere or class ball shaped nano crystalline substance; Reaction is finished, and makes the brilliant hydroxide nickel of intermediate products ball shaped nano through ageing, cleaning xCo y(OH) 2, Ni wherein xThe percetage by weight that accounts for Ni and Co summation is 40～80%, Co yAccount for Ni and Co summation percetage by weight is 20～60%;
3) the brilliant nickel hydroxide cobalt of the intermediate product ball shaped nano Ni that learns from else's experience and under the unstable state equilibrium condition, produce in the reactor xCo y(OH) 2, get lithium hydroxide LiOHH again 2O (Ni 1-1.02) and M z, mix mechanical agitation;
4) the described reactant that mixes packed into heat in the incinerator, finished product lithium nickel cobalt dioxide LiNi xCo yM zO 2, in reaction system, heating rate is 5～30 ℃/min, temperature is controlled at 350～900 ℃, is incubated 5～30 hours; The rate of temperature fall of reacting rear material is at 50～200 ℃/min;
Wherein: M is one of Ti, Mg, Al, Cr or its combination in step (3), (4); The percetage by weight x value that Ni accounts for Ni, Co and M summation is 40～80%, and the percetage by weight y value that Co accounts for Ni, Co and M summation is 20～60%, and the percetage by weight z value that M accounts for Ni, Co and M summation is 0～0.01%.
2. according to the described preparation method of claim 1, it is characterized in that: nickel salt solution is the salt-mixture of nickelous sulfate, cobaltous sulfate, zinc sulfate described in the step (1), and mole is dense at 1.9～2.0mol/l; Aqueous slkali is a sodium hydroxide solution, and its molar concentration is 8.0～9.0mom/l; Concentrated ammonia solution density is 0.890～0.910g/ml.
3. according to the described preparation method of claim 1, it is characterized in that: refluxed once in the every interval of solution that overflows in the reaction system in the step (2) in 1～5 hour, and each return time is 5～30min, and back-flow velocity is 300～500L/h.
4. according to the described preparation method of claim 3, it is characterized in that: the method that changes reaction system internal reaction material rotation status in the inherent feed back process of described reaction system is for adjusting mixing speed, be material when not refluxing mixing speed be 250～350 commentaries on classics/min, mixing speed is 150～250 commentaries on classics/min during feed back.
5. according to the described preparation method of claim 1, it is characterized in that: heating rate is 10～20 ℃/min in the described step (4); Temperature is controlled at 450～850 ℃, is incubated 10～20 hours.
CN01106257A 2001-02-28 2001-02-28 Process for preparing spherical nano crystal lightium nickel cobaltate for lihtium secondary cell Pending CN1372338A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1843930B (en) * 2006-04-30 2010-06-23 中国科学院成都有机化学有限公司 Method for preparing LiNi1-XCOXO2 of anode material of lithium ion secondary battery
CN101465418B (en) * 2007-12-19 2011-06-15 比亚迪股份有限公司 Method for preparing composite material for lithium ion secondary battery anode
CN104332623A (en) * 2014-09-09 2015-02-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of lithium ion secondary battery negative material manganese cobalt oxide
CN104661963A (en) * 2012-09-28 2015-05-27 住友金属矿山株式会社 Nickel-cobalt compound hydroxide and method and device for producing same, positive electrode active substance for nonaqueous electrolyte secondary cell and method for producing same, and nonaqueous electrolyte secondary cell
CN111009646A (en) * 2019-12-09 2020-04-14 宁波容百新能源科技股份有限公司 High-rate monocrystal-like nickel-cobalt lithium aluminate cathode material with coating layer and preparation method thereof
CN117305604A (en) * 2023-11-29 2023-12-29 湖南五创循环科技股份有限公司 Method for recovering valuable metals in lithium cobalt oxide battery by cooperation of reduction gasification and continuous membrane separation technology

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1843930B (en) * 2006-04-30 2010-06-23 中国科学院成都有机化学有限公司 Method for preparing LiNi1-XCOXO2 of anode material of lithium ion secondary battery
CN101465418B (en) * 2007-12-19 2011-06-15 比亚迪股份有限公司 Method for preparing composite material for lithium ion secondary battery anode
CN104661963A (en) * 2012-09-28 2015-05-27 住友金属矿山株式会社 Nickel-cobalt compound hydroxide and method and device for producing same, positive electrode active substance for nonaqueous electrolyte secondary cell and method for producing same, and nonaqueous electrolyte secondary cell
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