CN1215587C - Preparation of lithium cobaltate as anode material of lithium ion cell from nano tricobalt tetroxide - Google Patents

Preparation of lithium cobaltate as anode material of lithium ion cell from nano tricobalt tetroxide Download PDF

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CN1215587C
CN1215587C CNB031124356A CN03112435A CN1215587C CN 1215587 C CN1215587 C CN 1215587C CN B031124356 A CNB031124356 A CN B031124356A CN 03112435 A CN03112435 A CN 03112435A CN 1215587 C CN1215587 C CN 1215587C
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孙思修
张卫民
杨延钊
俞海云
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Shandong University
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Abstract

The present invention relates to a method for preparing lithium cobaltate of positive electrode material of lithium ion batteries by using nanometer cobaltosic oxide as raw material, which belongs to the technical field of chemical material. In the present invention, nanometer grade cobaltosic oxide Co3O4 powder and battery grade lithium carbonate Li2CO3 are used as raw material, a two-stage solid phase synthesis method is used for preparation, and the molar ratio Li/Co of the lithium carbonate to the nanometer cobaltosic oxide is 1.03 to 1.05. In the present invention, LiCoO2 is prepared by using nanometer Co3O4 powder as the raw material, product performance is improved, material mixing procedures are simplified, reaction temperature is reduced, and reaction time is shortened. The obtained product has the advantages of uniform pattern and little particle size range, and the charge and discharge performance is superior to that of similar products at home and abroad.

Description

With the nano-cobaltic-cobaltous oxide is the method for feedstock production lithium ion cell anode material lithium cobaltate
(1) technical field
The present invention relates to the method that two sections solid phase roasting methods prepare lithium ion cell anode material lithium cobaltate, belong to chemical material
Technical field.
(2) background technology
Cobalt acid lithium LiCoO 2Crystal belongs to the trigonal system hexagoinal lattice, and the space point group is R3m, has α-NaFeO 2The type structure.Wherein, oxonium ion adopts the cube tightly packed of distortion, and lithium ion and cobalt ions in layer alternately occupy position, octahedra hole, the CoO of stratiform 2Frame structure provides two-dimensional channel for the migration of lithium ion.Lithium ion can be at positive electrode LiCoO when serondary lithium battery discharged and recharged 2In reversibly take off embedding.During charging, lithium ion embeds negative pole by deviating from the positive electrode by electrolyte.At this moment, LiCoO 2Lattice shrinks on a direction, expands on the c direction, and lithium ion can reversibly take off embedding.During discharge, opposite process takes place.Said process is with C/LiClO 4(PC-DEC)/LiCoO 2Battery is that example is expressed as follows:
Preparation LiCoO 2Method mainly comprise high temperature solid-state method, low-temperature solid-phase method and liquid phase method etc.Solid phase reaction generally selects for use the oxygenatedchemicalss such as carbonate, nitrate, oxide and hydroxide of lithium and cobalt as lithium source and cobalt source, is heated to 600-900 ℃ even higher temperature in air, and the reaction time is longer.Sometimes in order to obtain the pure phase product, even need several days time.Nineteen ninety, the commercial secondary lithium battery positive electrode LiCoO that Energy Development Corporation of Sony releases first 2Be to have adopted the method for heating lithium hydroxide and cobalt oxide mixture to prepare.Beijing Non-Fervoous Metal Inst. is a raw material with lithium carbonate and cobalt oxide, adopts Continuous Heat mode synthetic and that product is pulverized continuously to produce the LiCoO of average grain diameter 5-10 μ m 2Its simple production technology is as follows:
Mixed oxidization cobalt and lithium carbonate → advance stove → heat up → be incubated → lower the temperature → come out of the stove → pulverizing → screening continuously → routine inspection
Because the high temperature solid phase synthesis energy consumption is very big, so people have also carried out the research of low temperature solid-phase synthesis, and has obtained progress.Gu Mao (Gummow) etc. fully mix the carbonate of cobalt, lithium according to stoichiometric proportion, are heated to 400 ℃ in air, are incubated a week, form single-phase product.The LiCoO of this method preparation 2Nearly 6% cobalt is present in the lithium layer.Because synthetic material oxidation is seldom, thus more stable in electrolyte, have the intermediate structure of desirable stratiform and spinel structure.
Solid-phase synthesis exists the unmanageable shortcoming of product particle diameter, and the size of particle diameter and particle size range can directly influence the chemical property of material.Commercially available LiCoO 2It is general that what adopt is the solid-phase synthesis preparation, then through the particle of particle diameter about 10 μ m that ball-milling treatment obtains, and the LiCoO of high rigidity 2For this processing method has increased difficulty.Therefore, people have studied liquid phase synthesizing method in the hope of preparing the controlled or nano level LiCoO of particle diameter 2Mainly comprise base exchange method and sol-gel process under dynamic process method, the hydrothermal condition.
Method Tekes (D.G.Fauteux) reported a kind of fast and can produce LiCoO continuously 2Method-dynamic process method (DP).This method has not only obtained the LiCoO that particle diameter, composition, pattern and degree of crystallinity can be controlled 2, and can also be used to preparing other lithium-composite oxide of metal.This method is disperseed the presoma of final products earlier with appropriate solvent, and formation is the aerosol of carrier with the air, at high temperature carries out chemical reaction then and obtains final products.Concentration by regulating presoma, the particle size range of aerosol particle, the reactant time of staying and the reaction temperature etc. in reactor can be controlled the granularity of final products and the oxygen content of product, realizes LiCoO 2The control of material electrochemical performance.The advantage of this method is that the time of staying of reactant in reactor is short, product by very tiny loose particles combine, so reprocessing is easy, than commercially available sample more easy grinding become the particle of particle diameter less than 10 μ m.
The thorough people such as (D.Larcher) of labor has prepared LiCoO with base exchange method at low temperatures 2, electrochemical behavior, reaction mechanism and various technological factor that material has been discussed are to effect of material performance.They utilize hydrogen oxide cobalt oxide (CoOOH), the lithium hydroxide (LiOHXH of homemade pure phase 2O) and suitable quantity of water be raw material, raw mix is placed the resistance to oxidation container of autoclave, fill mist with nitrogen and oxygen (volume ratio 4/1), 160 ℃ of temperature, pressure is 160bars.React after 5 days, solution is leached, get brown ceramic powder.X-ray diffraction experiment shows, under this temperature and pressure, by H XCoO 2→ LiCoO 2Transformation mutually be completely, still, the LiCoO of crystalline condition not as preparing under the hot conditions 2Good.In addition, the LiCoO of this method preparation 2In contain a spot of Co 3O 4Dephasign.The powder of preparation is in annealing in process more than 300 ℃, the LiCoO that initial charge capacity and high temperature synthesize 2Identical, but cycle performance is relatively poor.
The key of sol-gel process is to select suitable precursor solution, controls suitable pH scope, makes precursor solution form colloidal sol under suitable temperature and humidity condition.Poplar rice (R.Yazami) etc. has again been studied another low temperature liquid phase synthetic method.Under brute force stirs, the suspension-turbid liquid of cobalt acetate is joined in the lithium acetate solution, under 550 ℃ condition, handled 2 hours the LiCoO that obtains having stoichiometric proportion then at least 2This material specific area is big, has good crystallization and monodisperse particles shape.Yao Xiou people such as (Yoshio) utilizes the organic acid cobalt complex to prepare the LiCoO with layer structure 2The discharge capacity first of material reaches 132Ah/Kg.Add organic acids such as malic acid or butanedioic acid in the solution that contains equimolar cobalt nitrate and lithium hydroxide, regulate pH value 4-8 with ammoniacal liquor, 60-150 ℃ of following reduction vaporization solution obtains the red gel of thickness.Product is gone out wherein organic substance 400 ℃ of heat treatments, compressing tablet then, 650 ℃ of preliminary treatment 6 hours.Heating 20 hours in 900 ℃, air atmosphere at last.
Although liquid phase synthesizing method has a lot of advantages, the product that it obtains often needs further high-temperature process just can show good electrochemical; In addition, this method is difficult for industrialization and has also limited liquid phase synthesizing method at LiCoO 2Application on the compound probability.
(3) summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of new industrialization LiCoO is provided 2Process for solid phase synthesis, promptly two sections solid phase roasting methods prepare the method for lithium ion cell anode material lithium cobaltate, and parameter is convenient to control, and flow process is short, and energy consumption is low, constant product quality.
The present invention utilizes the synthetic nanoscale Co of chemical precipitation-pyrolysismethod 3O 4Powder and LITHIUM BATTERY Li 2CO 3Be raw material, adopt the two-stage solid-phase synthesis to prepare lithium ion cell anode material lithium cobaltate, raw material lithium carbonate and nano-cobaltic-cobaltous oxide mol ratio Li/Co=1.03～1.05.
Raw material lithium carbonate and nano-cobaltic-cobaltous oxide fully mix according to mol ratio Li/Co=1.03～1.05, the phase I roasting, be warming up to 700 ℃～800 ℃ according to 2 ℃/min～5 ℃/min programming rate, be incubated 6 hours～8 hours, again by 2 ℃/min～5 ℃/min speed cooling, reduce to room temperature, finish one section heating; Behind the ball milling, second section roasting is warming up to 800 ℃～950 ℃ according to 2 ℃/min～5 ℃/min programming rate again, lowers the temperature after be incubated 6 hours～8 hours, obtains bulk product.After comminution by gas stream, classification are prepared cobalt acid powder for lithium.
Ball powder weight ratio 1～1.2: 1 in the above-mentioned ball mill mixing, the air pressure of product crushing and classification is 2Kg～5Kg.
The present invention compared with prior art has following excellent results:
(1) the present invention uses nano Co 3O 4Powder is feedstock production LiCoO 2, improved properties of product, reduced the production cost.The international and domestic producer that other produce cobalt acid lithium adopts the micron order raw material, and we adopt nano Co 3O 4Powder is a raw material.Micron order raw material major defect: micron order Co 3O 4The hardness height and needs before another raw material mixes to grind.We make full use of characteristics such as nano-powder density is little, hardness is little, and raw material need not grind, and has simplified the mixing of materials operation, and batch mixing is more even.
(2) nano Co 3O 4Raw material reaction is active high, has significantly reduced reaction temperature, has shortened the reaction time.
(3) adopt two sections solid phase roasting techniques, overcome defectives such as traditional solid phase reaction mass transfer velocity is slow, the product pattern is inhomogeneous, particle size range is wide.During roasting, raw material nano Co 3O 4Powder impregnated in the lithium carbonate fused solution, has further strengthened the material contact area, and mass transfer velocity is improved, and has reduced reaction temperature and time effectively, has reduced energy consumption.Simultaneously, the product pattern that obtains is even, particle size range is little, charge-discharge performance is better than similar products at home and abroad.
About correction data tabulate as follows lattice and accompanying drawing:
Table 1:Li 2CO 3And nano Co 3O 4Mixture second stage sintering temperature and temperature retention time to the product thing mutually, the influence of granularity and charge/discharge capacity
Group 1 (a) 2 (b) 3 (c) 456 (d) 789 T 1 (℃) 750 750 750 750 750 750 750 750 750 t 1(hour) 666666666 T 2 (℃) 900 900 900 850 850 850 800 800 800 t 2(hour) 468468468 Phase ■ ● ■ ■ ■ ● ■ ● ■ ■ ● ▲ ■ ● ▲ ■ ● ▲ Granularity (μ m) ★ 6.729 9.310 8.800 Charge/discharge capacity mAh/g 162.1/152.2 160.0/139.3 154.4/144.4
★ represents meso-position radius ▲ represent Li 2CO 3Thing phase ● represent Co 3O 4Thing phase ■ represents LiCoO 2The thing phase
Table 2:Li 2CO 3And nano Co 3O 4Mixture, different warming and cooling rates are to the influence of product lithium content, charge/discharge capacity
Warming and cooling rate (℃/min) 2 10 Product contains lithium amount (wt%) 7.04 6.21 First charge-discharge capacity (mAh/g) 155.6/90 121.5/51.7 Charge/discharge capacity (mAh/g) 80.6/61.5 45.0/29.5 for the second time
(4) description of drawings
Fig. 1 is the raw material transmission electron microscope photo of cobalt acid lithium, (a) Li 2CO 3(b) micron order Co 3O 4(c) nanoscale Co 3O 4
Fig. 2 is LiCoO 2Raw mix thermogravimetric analysis result, (a) Li 2CO 3+ micron order Co 3O 4, (b) Li 2CO 3+ nanoscale Co 3O 4(10 ℃/min of programming rate, wherein Li/Co=1.05)
Fig. 3: Li 2CO 3And nano Co 3O 4Powder Different L i/Co is than the XRD for preparing product down
Fig. 4: Li under the different temperatures 2CO 3And nano Co 3O 4After mixture (Li/Co=1.05) is incubated 8 hours, the XRD analysis of product
Fig. 5: Li 2CO 3And nano Co 3O 4900 ℃ of insulations of mixture (Li/Co=1.05) different time (a, 4 hours; B, 6 hours; C, 8 hours) XRD of gained sample
Fig. 6: Li 2CO 3And nano Co 3O 4The different sintering temperature gained of mixture LiCoO 2Infared spectrum (b:900 ℃, d:850 ℃)
(5) embodiment
The invention will be further described below in conjunction with embodiment, but be not limited thereto.
Embodiment 1:
Nano-cobaltic-cobaltous oxide is by (number of patent application: 01135170.5) method preparation, granularity is 20-50nm.
Raw material Li 2CO 3And nano Co 3O 4Li/Co=1.05 fully mixes according to mol ratio, and the phase I roasting is warming up to 750 ℃ according to 2 ℃/min speed, is incubated 6 hours, by the cooling of 2 ℃/min speed, finishes one section heating again; Behind the ball milling, second section roasting is warming up to 900 ℃ according to 2 ℃/min programming rate again, is incubated cooling after 6 hours, obtains bulk product.After comminution by gas stream, classification are prepared cobalt acid powder for lithium.Ball powder weight ratio 1～1.2: 1 in the batch mixing, the air pressure of product crushing and classification is 2.5Kg.Product index:
Structure meets JCPDS standard card 16-427;
Granularity: D 50=9.046 μ m, D 5-D 95=3.30-57.09 μ m;
Specific area: 0.44m 2/ g;
Tap density: 2.53g/cm 3
Chemical composition (wt%):
Sample number into spectrum 02L3-A Li 7.05 Co 60.16 Ni 0.057 Fe 0.046 Na 0.0052
Charge/discharge capacity (mAh/g):
Sample number into spectrum 02L3-A Initial charge capacity 165.76 Discharge capacity 151.77 first Secondary discharge capacity 150.63 Three discharge capacities 149.69
Embodiment 2:
Nano-cobaltic-cobaltous oxide is by (number of patent application: 01135170.5) method preparation, granularity is 20-50nm.
Raw material Li 2CO 3And nano Co 3O 4Li/Co=1.03 fully mixes according to mol ratio, and the phase I roasting is warming up to 750 ℃ according to 4 ℃/min speed, is incubated 6 hours, by the cooling of 4 ℃/min speed, finishes one section heating again; Behind the ball milling, second section roasting is warming up to 900 ℃ according to 4 ℃/min programming rate again, is incubated cooling after 6 hours, obtains bulk product.After comminution by gas stream, classification are prepared cobalt acid powder for lithium.Ball powder weight ratio 1～1.2: 1 in the batch mixing, the air pressure of product crushing and classification is 2.5Kg.Product index:
Structure meets JCPDS standard card 16-427;
Granularity: D 50=8.406 μ m, D 5-D 95=3.35-21.24 μ m;
Specific area: 0.49n 2/ g;
Tap density: 2.64g/cm 3
Chemical composition (wt%):
Sample number into spectrum 02L3-B Li 7.00 Co 60.75 Ni 0.035 Fe 0.009 Na 0.009
Charge/discharge capacity (mAh/g):
Sample number into spectrum 02L3-B Initial charge capacity 158.46 Discharge capacity 150.74 first Secondary discharge capacity 141.57
Embodiment 3:
Nano-cobaltic-cobaltous oxide is by (number of patent application: 01135170.5) method preparation, granularity is 20-50nm.
Raw material Li 2CO 3And nano Co 3O 4Li/Co=1.05 fully mixes according to mol ratio, and the phase I roasting is warming up to 750 ℃ according to 5 ℃/min speed, is incubated 6 hours, by the cooling of 5 ℃/min speed, finishes one section heating again; Behind the ball milling, second section roasting is warming up to 900 ℃ according to 5 ℃/min programming rate again, is incubated cooling after 8 hours, obtains bulk product.After comminution by gas stream, classification are prepared cobalt acid powder for lithium.Ball powder weight ratio 1～1.2: 1 in the batch mixing, the air pressure of product crushing and classification is 2.5Kg.Product index:
Structure meets JCPDS standard card 16-427;
Granularity: D 50=10.495 μ m, D 5-D 95=3.11-34.95 μ m;
Specific area: 0.37m 2/ g;
Tap density: 2.426g/cm 3
Chemical composition (wt%):
Sample number into spectrum 02L2 Li 7.54 Co 61.64 Ni 0.035 Fe 0.009 Na 0.009
Charge/discharge capacity (mAh/g):
Sample number into spectrum 02L2 Initial charge capacity 157.53 Discharge capacity 140.64 first Secondary discharge capacity 140.57
Comparative Examples 1:
Select the micron cobaltosic oxide to prepare LiCoO 2, granularity is 1-2 μ m.
Raw material Li 2CO 3With micron Co 3O 4Li/Co=1.05 fully mixes according to mol ratio, and the phase I roasting is warming up to 750 ℃ according to 2 ℃/min speed, is incubated 6 hours, by the cooling of 2 ℃/min speed, finishes one section heating again; Behind the ball milling, second section roasting is warming up to 900 ℃ according to 2 ℃/min programming rate again, is incubated cooling after 6 hours, obtains bulk product.After comminution by gas stream, classification are prepared cobalt acid powder for lithium.Ball powder weight ratio 1～1.2: 1 in the batch mixing, the air pressure of product crushing and classification is 2.5Kg.Product index:
Structure meets JCPDS standard card 16-427;
Charge/discharge capacity (mAh/g):
Sample number into spectrum Co-54 Initial charge capacity 149.6 Discharge capacity 139.3 first Secondary discharge capacity 134.1 Three discharge capacities 129.0
Comparative Examples 2:
Select the micron cobaltosic oxide to prepare LiCoO 2, granularity is 1-2 μ m.
Raw material Li 2CO 3With micron Co 3O 4Li/Co=1.05 fully mixes according to mol ratio, and the phase I roasting is warming up to 750 ℃ according to 2 ℃/min speed, is incubated 6 hours, by the cooling of 2 ℃/min speed, finishes one section heating again; Behind the ball milling, second section roasting is warming up to 900 ℃ according to 2 ℃/min programming rate again, is incubated cooling after 8 hours, obtains bulk product.After comminution by gas stream, classification are prepared cobalt acid powder for lithium.Ball powder weight ratio 1～1.2: 1 in the batch mixing, the air pressure of product crushing and classification is 2.5Kg.Product index:
Structure meets JCPDS standard card 16-427;
Charge/discharge capacity (mAh/g):
Sample number into spectrum Co-51 Initial charge capacity 153.6 Discharge capacity 138.2 first Secondary discharge capacity 128.5 Three discharge capacities 121.9
Comparative Examples 3:
Select the micron cobaltosic oxide to prepare LiCoO 2, granularity is 1-2 μ m.
Raw material Li 2CO 3With micron Co 3O 4Li/Co=1.05 fully mixes according to mol ratio, and the phase I roasting is warming up to 750 ℃ according to 5 ℃/min speed, is incubated 6 hours, by the cooling of 5 ℃/min speed, finishes one section heating again; Behind the ball milling, second section roasting is warming up to 900 ℃ according to 5 ℃/min programming rate again, is incubated cooling after 8 hours, obtains bulk product.After comminution by gas stream, classification are prepared cobalt acid powder for lithium.Ball powder weight ratio 1～1.2: 1 in the batch mixing, the air pressure of product crushing and classification is 2.5Kg.Product index:
Structure meets JCPDS standard card 16-427;
Charge/discharge capacity (mAh/g):
Sample number into spectrum Co-52 Initial charge capacity 151.5 Discharge capacity 134.4 first Secondary discharge capacity 127.0 Three discharge capacities 122.1
Comparative Examples 4:
Select the micron cobaltosic oxide to prepare LiCoO 2, granularity is 1-2 μ m.
Raw material Li 2CO 3With micron Co 2O 4Li/Co=1.05 fully mixes according to mol ratio, and the phase I roasting is warming up to 750 ℃ according to 10 ℃/min speed, is incubated 6 hours, by the cooling of 10 ℃/min speed, finishes one section heating again; Behind the ball milling, second section roasting is warming up to 900 ℃ according to 10 ℃/min programming rate again, is incubated cooling after 8 hours, obtains bulk product.After comminution by gas stream, classification are prepared cobalt acid powder for lithium.Ball powder weight ratio 1～1.2: 1 in the batch mixing, the air pressure of product crushing and classification is 2.5Kg.Product index:
Structure meets JCPDS standard card 16-427;
Charge/discharge capacity (mAh/g):
Sample number into spectrum Co-53 Initial charge capacity 138.4 Discharge capacity 125.1 first Secondary discharge capacity 121.7 Three discharge capacities 117.1

Claims (3)

1. a method for preparing lithium ion cell anode material lithium cobaltate is characterized in that, with 20-50nm cobaltosic oxide Co 3O 4Powder and battery-level lithium carbonate Li 2CO 3Be raw material, adopt two-stage solid-phase synthesis preparation, lithium carbonate and nano-cobaltic-cobaltous oxide mol ratio Li/Co=1.03～1.05; Described two-stage solid-phase synthesis step is as follows:
Raw material lithium carbonate and nano-cobaltic-cobaltous oxide fully mix according to mol ratio Li/Co=1.03-1.05; The phase I roasting is warming up to 700 ℃～800 ℃ according to 2～5 ℃/min programming rate, is incubated 6 hours～8 hours, by the cooling of 2～5 ℃/min speed, reduces to room temperature again, finishes one section heating; Behind the ball mill mixing, second section roasting is warming up to 800 ℃～950 ℃ according to 2 ℃/min～5 ℃/min programming rate again, lowers the temperature after be incubated 6 hours～8 hours, obtains bulk product; After comminution by gas stream, classification are prepared cobalt acid powder for lithium.
2. the method for preparing lithium ion cell anode material lithium cobaltate as claimed in claim 1 is characterized in that, the ball powder weight ratio 1～1.2: 1 in the described ball mill mixing.
3. the method for preparing lithium ion cell anode material lithium cobaltate as claimed in claim 1 is characterized in that, the air pressure of described product crushing and classification is 2Kg～5Kg.
CNB031124356A 2003-06-20 2003-06-20 Preparation of lithium cobaltate as anode material of lithium ion cell from nano tricobalt tetroxide Expired - Fee Related CN1215587C (en)

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