Patent Grant
10714749
The present invention is involved in a lithium cobaltate cathode material and its preparation method, especially involved in a high-rate lithium cobaltate cathode material and its preparation method.
Lithium-ion batteries are widely used in mobile/IT equipment and energy storage due to their high power density, high energy and long life. The lithium-ion battery industry developes rapidly. With the development of electronic products, higher requirements have been put forward for lithium-ion batteries, especially considering its light weight, high current discharge and safety performance.
A vigorous development momentum shown in the e-cigarettes, electronic models (car models, ship models, model aircrafts, etc.), toys, wireless power tools market require lithium-ion batteries with shorter charging times, larger discharge currents, and higher safety performance. And many small appliances are also required to be able to discharge at high rate. Therefore, it has become extremely important to develop high-rate lithium-ion battery that can be used for the above-mentioned high-power electronic devices. Lithium cobaltate cathode material is therefore widely used as a power source for e-cigarettes, electronic, models, toys, wireless power tools, and small appliances due to its high specific capacity and, compaction density, excellent cycle performance, especially high discharge capacity and high plateau when high-rate discharge.
A lithium-ion battery consists of a cathode, an anode, electrolyte, and a separator that prevents short circuit between the cathode and anode plates. During the charging and discharging process of Lithium-ion batteries, Li+ is embedded and extracted from the cathode and anode materials for energy exchange. Lithium cobaltate cathode material stores lithium in the bulk phase, Li+ diffuses from the surface through the bulk phase into the inside of the cathode material. The long diffusion path of lithium ion results in the excessive internal resistance and thus the low discharge capacity and plateau.
In addition, since the power density requirements of the power type lithium battery are continuously increased, the discharge rate is continuously increased from the early 10 C discharge to 20-30 C, and even to 50-60 C discharge for some special demands. The charge and discharge rate of the lithium-ion battery is related to the cathode and anode materials of the battery and the preparation process. The lithium cobaltate cathode material prepared by the prior art is difficult to satisfy the rate performance and cycle performance of the above battery, especially for the rate performance and cycle performance at 50-60 C discharge. Therefore, it is necessary to develop a high-rate lithium cobaltate cathode material which not only has a good capacity and plateau at high rate discharge, but also maintains excellent cycle performance to meet the needs of battery manufacturers.
The technical problem to be solved by the present invention is to overcome the deficiencies and defects mentioned in the above background art, and to provide a high-rate lithium cobaltate cathode material, and a corresponding preparation method which is fast, simple and can effectively improve the product rate performance.
In order to solve the above technical problem, the technical solution proposed by the present invention is a high-rate lithium cobaltate cathode material, which is mainly composed of lithium cobaltate. The lithium cobaltate cathode material as described contains a multi-channel network formed by fast ionic conductor LiαM′γOβ. The lithium cobaltate is melted integrally with the fast ionic conductor LiαM′γOβ in the form of primary particles, and then forms secondary particles. The lithium cobaltate is embedded in the multi-channel network mentioned above formed by fast ionic conductor LiαM′γOβ. The element M′ in LiαM′γOβ is one or more of Ti, Zr, Y, V, Nb, Mo, Sn, In, La, W, and 1≤α≤4, 1≤γ≤5, 2≤β≤12.
In the above high-rate lithium cobaltate cathode material, the lithium cobaltate cathode material contains preferably a doping element M, and is represented by a chemical formula of Li1+yCo1−xMxO2•zLiαM′γOβ. Wherein 0≤x≤0.1, −0.01≤y≤0.01, 0.005≤z≤0.01, and the element M is one or more of Mg, Al, Si, Sc, Ni, Mn, Ga, and Ge.
The outstanding characteristics of the above high-rate lithium cobaltate cathode material of the present invention is that the multi-channel network structure formed by the fast ionic conductor LiαM′γOβ is separately formed into one phase, and embedded in the lithium cobaltate phase to form a multi-dimensional channel two-phase structure with intercommunication surface.
As an overall technical concept, the present invention also provides a method for preparing the above high-rate lithium cobaltate cathode material. The lithium cobaltate cathode material is mainly obtained by uniformly mixing cobaltous oxide impregnated with a hydroxide of M′, lithium source, and an additive containing a doping element M (optional) (dry mixing according to the ratio of Li1+yCo1−xMxO2•zLiαM′γOβ), then by the sintering reaction in an air atmosphere furnace at a high temperature.
In the above method for preparing a high-rate lithium cobaltate cathode material, the cobaltous oxide impregnated with the hydroxide of M′ preferably was mainly prepared by the following steps:
The organic compound containing M was dissolved in anhydrous ethanol, the solution was then dissolved and dispersed using a disperser. After fully stirring (0.5˜1 hour) evenly, the porous cobalt oxide (Note that it is different from conventional cobalt oxide) was added and stirred for 0.5 to 1.5 hour. Then ethanol solution with a volume ratio of ethanol to water of 5 to 20 was added and stirred for 2 to 5 hours. Finally the cobaltous oxide impregnated with the hydroxide of M′ is obtained by suction filtration and drying the filter cake in an oven (preferably 50° C.-70° C.). In the preferred operation of the present invention, the hydroxide of M′ was formed by hydrolysis of an organic compound containing M′. The M′ hydroxide can be uniformly embedded in the porous cobalt oxide by the hydrolysis to provide a premise and basis for obtaining a high-rate lithium cobaltate cathode material.
In the above method for preparing a high-rate lithium cobaltate cathode material, more preferably, the organic compound containing AC as described is one or more of alkoxide of M′, alkyl compound of M′, carbonyl compound of M′, and carboxyl compound of M′. The porous cobalt oxide as described is prepared by pre-sintering the precursor. The precursor as described is CoCO3.αH2O or CoC2O4.αH2O, wherein 0≤α≤9. The average bore diameter distribution of the porous cobalt oxide as described is 100 nm to 500 nm and with the porosity of 0.5% to 5%.
In the above method for preparing a high-rate lithium cobaltate cathode material, more preferably, the porous cobalt oxide was mainly prepared by the following steps:
A small amount of precipitant solution was injected into the reaction kettle and the pH was controlled between 6 and 14. Under strong agitation and inert gas protection, cobalt salt solution, complexing agent solution and the remaining precipitant solution were simultaneously injected into the reaction kettle using parallel flow method to carry out the reaction. The pH was continuously controlled between 6 to 14 during the stirring reaction, and the temperature of the reaction kettle was controlled between 0° C. and 85° C. during the reaction. After all the cobalt salt solution was added. After aging and filtration, the filter cake was obtained, which was dried in an oven (above 100° C., 3-5 h) to obtain the precursor. The precursor was placed in an air atmosphere furnace for pre-sintering, and after sinter, sieve it to obtain the porous cobalt oxide.
In the above method for preparing a high-rate lithium cobaltate cathode material, preferably, the cobalt salt solution is a solution formed by dissolving at least one of CoCl2.bH2O, CoSO4.bH2O, Co(NO3)2.bH2O in water, wherein 0≤b≤6. The concentration of Co2+ in the cobalt salt solution is controlled at 70-200 g/L. The complexing agent solution as described is an ammonia water or an aminocarboxylate solution, and the precipitating agent solution as described is carbonate solution, oxalic acid or oxalate solution. More preferably, when selecting a carbonate solution as the precipitant solution, the chemical formula of the synthesized precursor is CoCO3.αH2O. The carbonate solution is one or more of sodium carbonate, potassium carbonate, ammonium carbonate, ammonium bicarbonate solution. When selecting an oxalate or oxalic acid solution as the precipitant solution, the chemical formula of the synthesized precursor is CoC2O4.αH2O. The oxalate solution is one or more of sodium oxalate, potassium oxalate and ammonium oxalate solution.
In the above method for preparing a high-rate lithium cobaltate cathode material, preferably, the aging time is 4 to 8 hours, and the heating mechanism for the pre-sintering is performed by sintering at 300° C. to 500° C. for 2 to 5 hours, and then sintering at 700° C. to 800° C. for 2 to 5 hours.
In the above method for preparing a high-rate lithium cobaltate cathode material, the lithium source is preferably one or more of lithium carbonate, lithium hydroxide or lithium oxide (Li2CO3, LiOH, Li2O). The additive containing the doping element M is at least one of oxide, hydroxide, carboxy oxide, carbonate or basic carbonate of M.
The above technical solution of the present invention is mainly based on the following principles: firstly, the cobaltous oxide impregnated with the hydroxide of M′ is used as a raw material. In the sintering process of synthesizing the high-rate lithium cobaltate cathode material , since the ionic radius of M′ is much larger than that of Co3+, it is not easy to be dissolved into the cobaltate crystal structure, instead, it reacts with lithium ions to form a multi-channel network structure of LiαM′γOβ phase. Lithium cobaltate primary particles are embedded in a multi-channel network of fast ionic conductors and with which melted together to form secondary particles (see
In the prior art, the additive containing M′ was added in the synthesis step of lithium cobaltate, since the ionic radius of M′ is much larger than that of Co3+, it is not easy to be dissolved into the lithium cobaltate crystal structure, instead, it is enriched on the surface of the particle to form a fast ion conductor film. Compared with the prior art, the advantage of the present invention is that the present invention provides a porous cobalt oxide impregnation method. Lithium cobaltate is synthesized by using porous cobalt oxide as cobalt source. Lithium cobaltate particles contain multi-channel network structure of LiαM′γOβ phase. During the charging and discharging process of lithium-ion battery, this phase can be used as a fast channel for lithium ion transport, so that the lithium ion conductivity of lithium cobaltate cathode material is greatly promoted and the rate performance of the material is improved.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art description will be briefly described below. It is obvious that the drawings in the following description are some embodiments of the present invention. And those skilled in the art can obtain other drawings based on these drawings without any creative work.
In order to facilitate the understanding of the present invention, the present invention will be described more fully and detailed hereinafter in combination with drawings and preferred embodiments. But, the scope of protection of the present invention is not limited to the specific embodiments below.
Unless otherwise specified, all technical terms used hereinafter have the same meaning as commonly understood by those of the ordinary skills in the art. The terminology used herein is for describing specific embodiments, and is not intended to limit the scope of the present invention.
Unless otherwise specified, all kinds of raw materials, reagents, instruments, equipment, etc. used in the present invention can be purchased commercially or prepared by existing methods.
A high-rate lithium cobaltate cathode material mainly consists of lithium cobaltate. The lithium cobaltate cathode material contains a multi-channel network formed by fast ionic conductor Li2TiO3, and the lithium cobaltate is melted together with the fast ionic conductor Li2TiO3 in the form of primary particles to form secondary particles. The lithium cobaltate is embedded in the multi-channel network formed by the above fast ionic conductor Li2TiO3. The chemical formula of the lithium cobaltate cathode material of the present embodiment can be represented by Li0.99CoO2•0.005Li2TiO3 and it has a layered structure.
The method for preparing the high-rate lithium cobaltate cathode material of the present embodiment includes the following steps:
(1) A CoCl2 solution was prepared, the concentration of Co2+ in the solution was controlled at 110 g/L. The concentrated ammonium hydroxide and distilled water was used to form a complexing agent ammonium hydroxide solution at a volume ratio of 1:10. 1.2 mol/L sodium bicarbonate solution was used for the precipitant solution.
(2) A volume of ⅓ of the precipitant solution was injected into a 25 L reaction kettle, the pH of the solution was controlled at 6.0 to 8.0. Under the strong agitation and inert gas protection, the CoCl2 solution above-mentioned, ammonium hydroxide solution and sodium bicarbonate solution were simultaneously injected into the reaction kettle by a parallel flow method to carry out the reaction, and the pH was controlled to be 6.0-8.0 during the stirring reaction, the reaction kettle temperature was controlled at 70° C. to 80° C. After the CoCl2 solution was completely injected, a filter cake was obtained by aging for 4-8 hours, and then filtration
(3) The filter cake obtained in the above step (2) in an oven at 120° C. for 3 h was dried to obtain cobaltous carbonate (particle size of 5.5 μm).
(4) The cobaltous carbonate obtained in the above step (3) was pre-sintered at 400° C. for 3 h, and then sintered at 750° C. for 3 h to obtain porous cobalt oxide (particle size of 5.0 μm), numbered PC-1 (see
(5) 42 g of butyl titanate solution was dissolved in 500 g of anhydrous ethanol, and stirred for 0.5 h, 3000 g of porous cobalt oxide PC-1 obtained in the step (4) under vigorous stirring of a disperser was added, stirred for 0.5 h. Then ethanol solution was added, the volume ratio of ethanol to water was 6, and stirred for another 3 h. The filter cake was suction filtered, and dried in an oven to obtain cobalt oxide impregnated with Ti(OH)4, numbered as PC-2 (see
(6) 920 g of lithium carbonate and 2000 g of cobalt oxide PC-2 obtained in the above step (5) were dry-mixed uniformly to obtain a mixture.
(7) The mixture obtained in the above step (6) in an air atmosphere furnace was sintered at 950° C. for 10 h. After cooling, the universal pulverizer was pulverized for 20 s, and the particle size was controlled at 5.5 to 6.0 μm to obtain the high-rate lithium cobaltate cathode material (numbered LCO-1, see
A high-rate lithium cobaltate cathode material mainly consists of lithium cobaltate. The lithium cobaltate cathode material contains a multi-channel network formed by fast ionic conductor Li2TiO3, and the lithium cobaltate is melted together with the fast ionic conductor Li2TiO3 in the form of primary particles to form secondary particles. The lithium cobaltate is embedded in the multi-channel network formed by the aforementioned fast ionic conductor Li2TiO3. The chemical formula of the lithium cobaltate cathode material of the present embodiment can be represented by Li1.00Co0.99Mg0.005Al0.005O2•0.005Li2TiO3 and it has a layered structure.
The method for preparing the high-rate lithium cobaltate cathode material of the present embodiment includes the following steps:
(1)-(5): steps (1)-(5) of the present embodiment are the same as those of the embodiment 1.
(6) 936 g of lithium carbonate, 2000 g of cobalt oxide PC-2 obtained in the above embodiment 1, 5 g of magnesium oxide and 6.5 g of aluminium oxide were dry-mixed uniformly to obtain a mixture.
(7) The mixture obtained in the above step (6) was sintered in an air atmosphere furnace at 000° C. for 10 h. After cooling, the universal pulverizer was pulverized for 20 s, and the particle size was controlled at 5.5 to 6.0 μm to obtain the high-rate lithium cobaltate cathode material (numbered LCO-2).
A lithium cobaltate cathode material with a chemical formula of Li0.99CoO2•0.005Li2TiO3 has a layered structure, wherein the existing form of Li2TiO3 is mainly enriched on the surface of the particles. The preparation method of the lithium cobaltate cathode material of the present control embodiment specifically includes the following steps:
(1) 920 g of lithium carbonate, 2000 g of PC-1 (synthesized in embodiment 1) and 10 g, of titanium dioxide were dry-mixed uniformly to obtain a mixture.
(2) The mixture obtained in the above step (1) was sintered in an air atmosphere furnace at 950° C. for 10 h. After cooling, the universal pulverizer was pulverized for 20 s, and the particle size was controlled at 5.5 to 6.0 μm to obtain the lithium cobaltate cathode material (numbered LCO-0).
A high-rate lithium cobaltate cathode material mainly consists of lithium cobaltate. The lithium cobaltate cathode material contains a multi-channel network formed by fast ionic conductor LiNbO3, and the lithium cobaltate is melted together with the fast ionic conductor LiNbO3 in the form of primary particles to form secondary particles. The lithium cobaltate is embedded in the multi-channel network formed by the aforementioned fast ionic conductor LiNbO3. The chemical formula of the lithium cobaltate cathode material of the present embodiment can be represented by Li1.01CoO2•0.001LiNbO3 and it has a layered structure.
The method for preparing the high-rate lithium cobaltate cathode material of the present embodiment includes the following steps:
(1) A CoSO4 solution was prepared, the concentration of Co2+ in the solution was controlled at 150 g/L. The concentrated ammonium hydroxide and distilled water was used to form a complexing agent solution at a volume ratio of 1:10. 1.5 mol/L ammonium oxalate solution was used for the precipitant solution.
(2) A volume of ⅓ of the precipitant solution was injected into a 25 L reaction kettle. Under the strong agitation and inert gas protection, the CoSO4 solution above-mentioned, ammonium hydroxide solution and ammonium oxalate solution were simultaneously injected into the reaction kettle by a parallel flow method to carry out the reaction, and the pH was controlled to be 6.0-7.0 during the stirring reaction, the reaction kettle temperature was controlled at 25° C. After the CoSO4 solution was completely injected, a filter cake was obtained by aging: for 4-8 h, and then filtration.
(3) The filter cake obtained in the above step (2) was dried in an oven at 120° C. for 3 h to obtain cobalt oxalate (particle size of 7.5 μm).
(4) The cobalt oxalate obtained in the above step (3) was pre-sintered at 300° C. for 2 h, and then sinter at 700° C. for 5 h to obtain porous cobalt oxide (particle size of 6.5 μm), numbered PC-3, with the average pore diameter of 500 nm and the porosity of 5%.
(5) 120 g of niobium ethoxide solution was dissolved in 2000 g of anhydrous ethanol, stirred for 0.5 h. 3000 g of porous cobalt oxide PC-3 obtained in the step (4) under vigorous stirring of a disperser was added, stirred for 1.0 h. Then ethanol solution was added, the volume ratio of ethanol to water was 20, and stirred for another 5 h. The cobalt oxide impregnated with Nb(OH)5, numbered as PC-4 was obtained by suction filtration, and drying the filter cake in an oven to obtain.
(6) 938 g of lithium carbonate and 2000 g of cobalt oxide PC-4 which was obtained in the above step (5) were dry-mixed uniformly to obtain a mixture.
(7) The mixture obtained in the above step (6) was sintered in an air atmosphere furnace at 900° C. for 10 h. After cooling, the universal pulverizer was pulverized for 20 s, and the particle size was controlled at 6.5 to 7.0 μm to obtain the high-rate lithium cobaltate cathode material, numbered as LCO-3.
A high-rate lithium cobaltate cathode material mainly consists of lithium cobaltate. The lithium cobaltate cathode material contains a multi-channel network formed by fast ionic conductor Li2WO4, and the lithium cobaltate is melted together with the fast ionic conductor Li2WO4 in the form of primary particles to form secondary particles. The lithium cobaltate is embedded in the multi-channel network formed by the aforementioned fast ionic conductor Li2WO4. The chemical formula of the lithium cobaltate cathode material of the present embodiment can be represented by Li1.00CoO2•0.008Li2WO4 and it has a layered structure.
The method for preparing the high-rate lithium cobaltate cathode material of the present embodiment includes the following steps:
(1) A Co(NO3)2 solution was prepared, the concentration of Co2+ in the solution was controlled at 100 g/L. The concentrated ammonium hydroxide and distilled water was used to form a complexing agent solution at a volume ratio of 1:10. 1.5 mol/L ammonium oxalate solution was used for the precipitant solution.
(2) A volume of ⅓ of the precipitant solution was injected into a 25 L reaction kettle. Under the strong agitation and inert gas protection, the Co(NO3)2 solution above-mentioned, ammonium hydroxide solution and ammonium oxalate solution were simultaneously injected into the reaction kettle by a parallel flow method to carry out the reaction, and the pH was controlled to be 6.0-7.0 during the stirring reaction, the reaction kettle temperature was controlled at 25° C. After the Co(NO3)2 solution was completely injected, a filter cake was obtained by aging for 4-8 h, and then filtration.
(3) The filter cake obtained in the above step (2) was dried in an oven at 120° C. for 3 h to obtain cobalt oxalate (particle size of 7.0 μm).
(4) The cobalt oxalate obtained in the above step (3) was pre-sintered at 500° C. for 3 h, and then was sintered at 800° C. for 5 h to obtain porous cobalt oxide (particle size of 6.5 μm), numbered PC-5, with the average pore diameter of 200 nm and the porosity of 1%. p (5) 135 g of tungsten ethanol solution was dissolved in 2500 g of anhydrous ethanol, stirred for 0.5 h. 3000 g of porous cobalt oxide PC-5 obtained in the step (4) under vigorous stirring of a disperser was added, stirred for 1.5 h. Then ethanol solution was added, the volume ratio of ethanol to water is 15, and stirred for another 4 h. The cobalt oxide impregnated with W(OH)6, numbered as PC-6 was obtained by suction filtration, and drying the filter cake in an oven.
(6) 928 g of lithium carbonate and 2000 g of cobalt oxide PC-6 which was obtained in the above step (5) were dry-mixed an to obtain a mixture.
(7) The mixture obtained in the above step (6) was sintered in an air atmosphere furnace at 1000° C. for 10 h. After cooling, the universal pulverizer was pulverized for 20 s, and the particle size was controlled at 6.5 to 7.0 μm to obtain the high-rate lithium cobaltate cathode material, numbered as LCO-4.
The electrochemical properties of the five products obtained in the above Embodiment 1, 2, 3, 4 and control embodiment 1 were tested. The test methods are described below.
Assembly of 063048 type square battery: the active admixture, PVDF and conductive carbon black was mixed in a mass ratio of 95.4:2.5:2.1, then NMP was added and the mixture was stirred to prepare a slurry. The slurry was applied onto an aluminum foil, and dried at 120° C. to obtain a cathode sheet. Then anode sheet, separator, electrolyte, etc were assembled into a 063048 type battery. The charge and discharge performance test of the battery is carried out at room temperature, and the battery is charged by constant current and then constant voltage. When the charge cut-off voltage is 4.2V or 4.35V, using constant current discharge, when the cut-off voltage is 3.0V and the charging current density is 0.5 C, the discharge current density is 0.2 C/1 C/10 C/20 C/50 C.
Table 1. shows the rate performance of the LCO-0/1/2/3/4 tested at different voltages.
As seen from Table 1 above, the capacity retention rate and plateau at 50 C rate of LCO-1/2/3/4 prepared by cobalt oxide impregnated with butyl titanate in the 4.2 V test are both significantly higher than in the control embodiment LCO-0. This indicates that the existence of the LCO-1/2/3/4 multi-channel network structure of fast tome conductor greatly increases the lithium ion transmission rate and effectively increases the discharge capacity and plateau of the material. When LCO-2 is tested at 4.35V, the capacity retention rate and plateau at 50 C rate are significantly higher than those of LCO-1, LCO-3 and LCO-4 in the embodiments. This is caused by that for the 4.35V high-voltage material, Mg and Al doping can effectively improve the structural stability of the material, and thus the rate performance at high voltage is excellent.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2016 1 0381625 | Jun 2016 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2017/082231 | 4/27/2017 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2017/206633 | 12/7/2017 | WO | A |
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| Number | Date | Country | |
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| 20190140277 A1 | May 2019 | US |
