CN101445278B - Method for preparing anode material lithium cobalt oxide used by lithium ion battery - Google Patents
Method for preparing anode material lithium cobalt oxide used by lithium ion battery Download PDFInfo
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- CN101445278B CN101445278B CN2007101781963A CN200710178196A CN101445278B CN 101445278 B CN101445278 B CN 101445278B CN 2007101781963 A CN2007101781963 A CN 2007101781963A CN 200710178196 A CN200710178196 A CN 200710178196A CN 101445278 B CN101445278 B CN 101445278B
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Abstract
The invention provides a method for preparing anode material lithium cobalt oxide used by a lithium ion battery, belonging to the technical field of the preparation of anode materials of lithium ion batteries. The method is characterized in that metal cobalt powder is substituted for conventional cobalt compound as a raw material, lithium compound is added according to a certain proportion, and the cobalt powder and the lithium compound undergo ball grinding, then are uniformly mixed, undergo low temperature sintering reaction respectively at a temperature of 400 DEG C to 600 DEG C and a temperature of 650 DEG C to 750 DEG C and then undergo high temperature crystallization at a temperature of 850 DEG C to 950 DEG C so as to obtain a lithium cobalt oxide product which has good electrochemical performance, wherein, the specific capacity of the lithium cobalt oxide product is greater than 145 mAh/g and the tap density of the lithium cobalt oxide product is greater than 2.8 g/cm<3>. The method has the advantage that due to the adoption of the metal cobalt powder to replace the conventional cobalt compound and the adoption of a segment sintering method, the obtained lithium cobalt oxide has greater specific capacity and tap density and better circulation stability; in addition, the method simplifies the process, does not need the step of crushing and directly obtains secondary particles which are completely crystallized, and the particles are near-spherical. Compared with the conventional preparation process, the process of the method is simpler and more energy-conserving and is a preparation technique with wide prospect.
Description
Technical field
The invention belongs to the technical field of anode material for lithium-ion batteries preparation.
Background technology
Since Sony in 1992 develops the commercialization lithium ion battery, distinguishing features such as lithium ion battery is big, in light weight with its specific energy, memory-less effect, develop rapidly, be used widely in fields such as mobile telephone, portable electronics, military equipment power supply, electric car power supplies.Cobalt acid lithium has higher specific storage and cycle performance, has been leading positive electrode material since the lithium ion battery commercialization always.Its preparation method generally has liquid phase synthesizing methods such as high temperature solid-state method and co-precipitation etc., and wherein high temperature solid-state method technology is fairly simple, is fit to scale operation, is adopted by numerous production firms.Its technology generally is that to adopt lithium salts such as cobalt salt, Quilonum Retard such as tricobalt tetroxide be raw material, proportioning according to a certain percentage, behind the thorough mixing, in 800 ℃～1000 ℃ synthetic down, synthetic product is through obtaining required cobalt acid lithium product behind the crushing and classification.This method shortcoming is that synthesis temperature is higher, and synthetic cobalt acid lithium particle is bigger, need reach required particle diameter by pulverization process, pulverizes back cobalt acid lithium primary particle and is destroyed, and is difficult to prepare class spheric cobalt acid lithium.Liquid phase method is to be raw material with Lithium Acetate, Cobaltous diacetate such as oxalic acid coprecipitation, under the effect of acetic acid, stirs in the solution and generates precipitation, and regulate suitable pH value with ammoniacal liquor, after the cryodrying, sintering obtains positive pole material of lithium cobalt acid under high temperature, and this method can generate primary particle, uniform particles, can obtain the particle of class ball-type by the control reaction process, chemical property is better, and liquid phase method synthetic shortcoming is that technology is complicated, the liquid waste disposal amount is big, the bad control of scale operation etc.
Summary of the invention
The objective of the invention is to adopt metal cobalt powder to replace traditional cobalt salts such as tricobalt tetroxide is raw material, by the multistage sintering process, utilize metal cobalt powder active big, low temperature is reaction down, the high temperature crystallization, directly obtain the spherical offspring of class, do not need to pulverize, simplified the solid phase method production technique, and institute's synthetic cobalt acid lithium specific storage height, tap density is higher, improved the battery energy density per unit volume greatly, cyclical stability is better, and this invention provides a kind of strong operability, technology is simple, and product performance are better than the preparation method of conventional high-temperature solid phase method.
To achieve these goals, the present invention is by the following technical solutions:
A kind of manufacture method of anode material lithium cobalt oxide used by lithium ion battery, the compound of metal cobalt powder, lithium is prepared burden than 0.98～1.1 ratio according to the lithium cobalt atom, thorough mixing is 2～48 hours in ball mill, at 400 ℃～600 ℃, sintering 5～24 hours is warmed up to 650 ℃～750 ℃ continuously then, 5～12 hours heat preservation sintering time, be warmed up to 850 ℃～950 ℃ more continuously, heat preservation sintering 2～10 hours obtains required lithium cobaltate cathode material.
The compound of said lithium is a kind of or two several mixtures in lithium hydroxide and the Quilonum Retard;
Said metal cobalt powder granularity D
50It is 1～10 micron.Here said granularity is meant mean particle size.
Advantage of the present invention is: it is raw material that the present invention adopts metal cobalt powder to replace the compound of traditional cobalt, utilize metal cobalt powder chemically reactive height, make its 400 ℃ at a lower temperature～600 ℃ chemical reaction takes place, obtain the less primary particle of granularity, make reaction more complete at 650 ℃～750 ℃ then, carry out the cobalt acid lithium material that the high temperature crystallization obtains desired particle size at 850 ℃～950 ℃ at last.This method technology is simple, by the control synthesis technique, directly obtains class spheric offspring, and material has higher specific storage, does not need traditional disintegrating process, has simplified technology.
Positive effect of the present invention is that the employing metal cobalt powder is that raw material does not need through pulverizing, directly obtain the offspring of desired particle size, particle has pattern preferably, realized better electrochemical performance, improved the material volume specific storage, and simplified technology greatly, this method technology is simple, workable, easy realization of large-scale production.
Description of drawings
Fig. 1 embodiment 1 obtains the granule-morphology of cobalt acid lithium
Fig. 2 comparative example obtains cobalt acid lithium granule-morphology
Fig. 3 embodiment 1 obtains the first charge-discharge curve of cobalt acid lithium
Fig. 4 comparative example obtains cobalt acid lithium first charge-discharge curve
Fig. 5 embodiment 1 obtains cobalt acid lithium cyclic curve
Fig. 6 comparative example obtains cobalt acid lithium cyclic curve
Embodiment
Method of the present invention is synthesized according to following steps:
(1) be the cobalt source with the metal cobalt powder, Quilonum Retard or lithium hydroxide etc. is the lithium source, prepares burden uniform mixing in ball mill than 0.98～1.1 molar ratio according to the lithium cobalt;
(2) with the starting material that mix 400 ℃～600 ℃ low-temperature sinterings 5～24 hours, be warmed up to 650 ℃～750 ℃ continuously, heat preservation sintering 5-12 hour, be warmed up to 850 ℃～950 ℃ more continuously, heat preservation sintering 2～10 hours obtains cobalt acid lithium material.
The lithium source of selecting for use of the present invention is one or both mixtures in lithium hydroxide and the Quilonum Retard; The metal cobalt powder granularity D that selects for use
50Be 1～10 micron, said here granularity is meant mean particle size.
In order to detect physics and the chemical property of lithium ion battery of the present invention, carry out structured testing with Dutch X ' Pert PROMPD type XRD diffractometer with cobalt acid lithium; The method of all knowing with the those of ordinary skill under this area, it is assembled into flat test cell carries out electrochemical property test, with lithium ion battery of the present invention lithium cobaltate cathode material 85～92% (weight percentage), conductive agent (graphite or carbon black) 4～8%, binding agent PVDF (polyvinylidene difluoride (PVDF)) 4～8% mixes the furnishing pulpous state, is coated on the two sides of aluminium foil, at air drying, make electrode.Counter electrode is formed test cell for the lithium tinsel.Electrolytic solution is 1M (mol/L) LiPF
6/ EC+DMC etc., EC are NSC 11801, and DMC is a methylcarbonate.Charging and discharging currents density 0.2C, discharging and recharging upper and lower limit voltage is 3.0～4.25V, specific storage method of calculation C=mA * h/g, wherein C: specific storage, temperature is 25 ± 2 ℃, the continuous current tester that computerizeds control carries out electrochemistry capacitance and loop test.
Embodiment 1
Take by weighing purity 99.9% granularity (said granularity is meant mean particle size) D here according to lithium cobalt mol ratio 0.98
50Be 1 micron metal cobalt powder 50g, put into the ball milling mixing machine with the Quilonum Retard 31.28g of purity 98%, add agate ball, ratio of grinding media to material 1: 3, thorough mixing 5 hours, put into alumina crucible then, 500 ℃ of sintering are 10 hours in the retort furnace, are warmed up to 750 ℃ continuously, heat preservation sintering 5 hours, be warmed up to 900 ℃ more continuously, heat preservation sintering obtained cobalt acid lithium in 2 hours.0.1C test specific storage 149mAh/g, first charge-discharge efficiency is 96.4%, tap density 2.8g/cm
3The granule-morphology of cobalt that embodiment 1 obtains acid lithium as shown in Figure 1, the pattern of the cobalt acid lithium that obtains with Fig. 2 comparative example is compared, particle of the present invention is near-spherical, particle is tiny, even; The first charge-discharge curve of the cobalt acid lithium that embodiment 1 obtains is compared with the cobalt acid lithium first charge-discharge curve that comparative example shown in Figure 4 obtains as shown in Figure 3, and specific storage of the present invention has obtained bigger raising; The cycle performance of the cobalt acid lithium that embodiment 1 obtains is (1C) as shown in Figure 5, compares with the cobalt acid lithium cyclic curve that comparative example shown in Figure 6 obtains, and cycle performance of the present invention has obtained bigger improvement.
Take by weighing purity 99.9% granularity (said granularity is meant mean particle size) D here according to lithium cobalt mol ratio 1.1
50Be 1 micron metal cobalt powder 50g, put into the ball milling mixing machine with the lithium hydroxide 41.19g of purity 95%, add agate ball, ratio of grinding media to material 1: 3, thorough mixing 5 hours, put into alumina crucible then, 480 ℃ of sintering are 7 hours in the retort furnace, are warmed up to 750 ℃ continuously, heat preservation sintering 6 hours, be warmed up to 900 ℃ more continuously, heat preservation sintering obtained cobalt acid lithium in 2 hours.0.1C test specific storage 147mAh/g, first charge-discharge efficiency is 95%, tap density 2.9g/cm
3Obtain cobalt acid lithium tap density with comparative example and compare, tap density of the present invention obtains bigger raising.
Comparative example
Take by weighing purity 99% tricobalt tetroxide 68.72g according to lithium cobalt mol ratio 0.98, put into the ball milling mixing machine with the Quilonum Retard 31.28g of purity 98%, add agate ball, ratio of grinding media to material 1: 3, thorough mixing 5 hours, put into alumina crucible then, 900 ℃ of sintering are 15 hours in the retort furnace, obtain cobalt acid lithium after the pulverizing.0.1C test specific storage 141mAh/g, first charge-discharge efficiency is 94.2%, tap density 2.3g/cm
3The granule-morphology of cobalt that comparative example obtains acid lithium as shown in Figure 2, it is irregularly shaped that particle is, granular size is inhomogeneous; The first charge-discharge curve of cobalt that comparative example obtains acid lithium as shown in Figure 4, the cobalt acid lithium cyclic curve that comparative example obtains is as shown in Figure 6.
Claims (3)
1. the preparation method of a lithium ion cell anode material lithium cobaltate, it is characterized in that, the compound of metal cobalt powder, lithium is prepared burden ball milling than 0.98～1.1 ratio according to the lithium cobalt atom, uniform mixing 2～48 hours, at 400 ℃～600 ℃, sintering 5～24 hours is warmed up to 650 ℃～750 ℃ continuously then, heat preservation sintering 5～12 hours, be warmed up to 850 ℃～950 ℃ more continuously, heat preservation sintering 2～10 hours obtains required lithium cobaltate cathode material.
2. according to the preparation method of a kind of lithium ion cell anode material lithium cobaltate of claim 1, it is characterized in that the compound of said lithium is one or both mixtures of lithium hydroxide and Quilonum Retard.
3. according to the preparation method of a kind of lithium ion cell anode material lithium cobaltate of claim 1 or 2, it is characterized in that said metal cobalt powder granularity is D
501-10 μ m.
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| CN101445278B true CN101445278B (en) | 2010-09-01 |
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| CN105655578A (en) * | 2015-12-17 | 2016-06-08 | 贵州梅岭电源有限公司 | Lithium ion secondary battery made from small-particle-size lithium cobalt oxide anode material |
| CN110085835B (en) * | 2019-04-30 | 2021-09-21 | 河南固锂电技术有限公司 | Preparation method of positive electrode composite material for high-energy-density all-solid-state lithium ion battery |
| CN115490272B (en) * | 2022-11-04 | 2023-12-15 | 江西潮实新能源科技有限公司 | Lithium cobaltate material and preparation process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4764300A (en) * | 1985-05-23 | 1988-08-16 | Basf Aktiengesellschaft | Preparation of finely divided and acicular hexagonal ferrites and their use for the production of magnetic recording media and plastoferrites |
| CN1610153A (en) * | 2003-10-23 | 2005-04-27 | 广东风华高新科技集团有限公司 | Lithium ion cell positive pole material and producing method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4764300A (en) * | 1985-05-23 | 1988-08-16 | Basf Aktiengesellschaft | Preparation of finely divided and acicular hexagonal ferrites and their use for the production of magnetic recording media and plastoferrites |
| CN1610153A (en) * | 2003-10-23 | 2005-04-27 | 广东风华高新科技集团有限公司 | Lithium ion cell positive pole material and producing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2002-173325A 2002.06.21 |
| JP特开2003-100510A 2003.04.04 |
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Effective date of registration: 20160318 Address after: 101407 Beijing Yanqi Yanqi Economic Development Zone Huairou District Road No. 3 Patentee after: GUOLIAN AUTOMOBILE POWER CELL INSTITUTE CO., LTD. Address before: 100088, 2, Xinjie street, Beijing Patentee before: General Research Institute for Nonferrous Metals |