CN103151518A - Coating technology of lithium cobalt oxide - Google Patents
Coating technology of lithium cobalt oxide Download PDFInfo
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- CN103151518A CN103151518A CN2013100239376A CN201310023937A CN103151518A CN 103151518 A CN103151518 A CN 103151518A CN 2013100239376 A CN2013100239376 A CN 2013100239376A CN 201310023937 A CN201310023937 A CN 201310023937A CN 103151518 A CN103151518 A CN 103151518A
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Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a coating technology of lithium cobalt oxide. The coating technology of the lithium cobalt oxide includes the following steps of weighting out a certain amount of lithium cobalt oxide, measuring metal ionic compounds and water-solubility organics based on the molar weight of the lithium cobalt oxide according to ratios that the total molar weight of the metal ionic compounds is 0.5%-2% of the molar weight of the lithium cobalt oxide and the total molar weight of the water-solubility organics is 50%-70% of the molar weight of the lithium cobalt oxide, adding water to the metal ionic compounds and the water-solubility organics, conducting ball-milling to obtain primary slurry, adding the lithium cobalt oxide and water to the primary slurry, conducting the ball-milling to obtain secondary slurry, drying the secondary slurry, roasting the secondary slurry, and obtaining coated lithium cobalt oxide materials. The coating technology of the lithium cobalt oxide is simple in technology process, low in cost, appropriate for industrialization large batch production, and capable of effectively avoiding the phenomenon that metallic elements generate segregation in the high-temperature process. In addition, the lithium cobalt oxide obtained through the coating technology is even in particle, less in agglomeration, good in electrochemical performance, and high in stability in charge-discharge processes.
Description
Technical field
The present invention relates to technical field of lithium ion, especially relate to a kind of cladding process of cobalt acid lithium.
Background technology
In present commercial anode material for lithium-ion batteries, cobalt acid lithium (LiCoO
2) because chemical property is comparatively stable, good cycle, voltage platform is higher, and good with the compatibility of electrolyte, the compacted density of the anodal diaphragm of its composition can reach 4.1g/cm
3, and do not affect battery performance, be most widely used general, the most ripe positive electrode.
But the cobalt in lithium ion battery acid lithium, charging voltage when 4.3V is above, Li
xThe CoO structure begins distortion, and the thermal stability variation causes the cycle performance variation, and cobalt acid lithium takes off the product C oO of lithium fully
2Structural stability is very poor, easily cave in to cause safety problem, so cobalt acid lithium ion battery is in actual applications generally take charge protection voltage 4.2V as the upper limit, prevent from overcharging causing structural deterioration, but cobalt acid lithium can only be emitted 0.5 Li in discharging and recharging like this
+, make cobalt acid lithium can only bring into play its half theoretical capacity.
Therefore, how to obtain the high LiCoO of structural stability
2Material becomes LiCoO with capacity and the cycle performance that improves battery
2A developing direction.
To LiCoO
2Carrying out that the surface coats is one of effective method that improves cobalt acid lithium battery capacity and cycle performance, and different cladding process are to LiCoO
2Structure direct impact is arranged, resulting LiCoO
2Performance also be not quite similar.
China Patent Publication No. CN1556551A, open day on December 22nd, 2004, a kind of surface cladding tech of anode material for lithium-ion batteries is disclosed, this process using metallic compound and lithium compound are for coating raw material and initial positive electrode, join in solvent, in water or their mixture, metallic compound be hydrolyzed and be adsorbed on positive electrode by regulating the pH value, forming class colloidal sol; Then with after the oven dry of class colloidal sol, at high temperature roasting forms by LiMeO
2Clad anode material, in formula, Me is a kind of in Al, Sn, Zn.adopt metallic compound and lithium compound common as coating raw material in this technique, cost is higher, need to regulate pH value to alkalescence in this technique and just can make metallic compound be hydrolyzed and be adsorbed on formation class colloidal sol on positive electrode, regulating pH has increased operating procedure to a certain extent, in addition, positive active material mixes with the coating raw material and adds solvent, after in water or their mixture, owing to not regulating pH this moment, coat raw material and can not be coated on the positive active material surface fully, produce precipitation thereby can occur reunites, after regulating pH, these precipitations can be hydrolyzed and be adsorbed on positive active material surface formation class colloidal sol, oven dry, the positive electrode surface coating that obtains after roasting is inhomogeneous, reunite serious, cause cycle performance poor, and directly positive electrode is carried out roasting, can make each component produce segregation, even can cause separating out of Li element, the electrical property of the positive electrode after thereby impact coats greatly, the roasting process of the method is the bakes to burn the article process simultaneously, namely directly carry out roasting under steady temperature, thereby particle can burst due to violent dry causing in roasting process, cause particle inhomogeneous, thereby also can greatly affect electrical property and the cycle performance of the positive electrode after coating.
In addition, China Patent Publication No. CN1697212A, open day on November 16th, 2005, a kind of processing method of lithium ion cell anode material lithium cobaltate is disclosed, the method needs positive electrode is dissolved in to obtain dispersion liquid in solvent, or else stirring and adjusting pH breaks, then the salt compounds solution of one or more clad metals M is put in described dispersion liquid and be hydrolyzed, hydrolysate M(OH) n is adsorbed on the active material surface, finally by the positive electrode that obtains after oven dry, roasting being covered by metal oxide.its weak point is, the uniformity of the method for guaranteeing that positive electrode coats need make positive electrode dissolve fully, and the solvent use amount is large, and cost is higher, the method also needs the pH of dispersion liquid is controlled at 11 left and right, and operation easier is larger in suitability for industrialized production, is not suitable for large batch of production, in the method, when hydrolysate M(OH) n is adsorbed on the active material surface, easily cause the excessive grain growth of active material, cause obtaining at last the active material particle size inhomogeneous, affect its performance, and be directly positive electrode to be carried out roasting equally in the method, can make equally each component produce segregation, even can cause separating out of Li element, same, the roasting process of the method is the bakes to burn the article process, thereby particle can burst due to violent dry causing in roasting process, cause particle inhomogeneous, electrical property and the cycle performance of the positive electrode after thereby impact coats greatly.
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Summary of the invention
The present invention is in order to overcome the existing above-mentioned deficiency of existing cobalt acid lithium cladding process, a kind of cladding process of cobalt acid lithium is provided, this cladding process step is simple, cost is low, be fit to industrialized mass, cobalt acid lithium after the coating that obtains coats evenly, reunites few, has good chemical property.
To achieve these goals, the present invention is by the following technical solutions:
A kind of cladding process of cobalt acid lithium comprises the following steps:
(1) take a certain amount of cobalt acid lithium, take cobalt acid lithium mole as benchmark, be 0.5 ~ 2% of cobalt acid lithium mole by metal ionic compound integral molar quantity, the water soluble organic substance integral molar quantity is 50 ~ 70% ratio metering metal ion compound and water soluble organic substance of cobalt acid lithium mole.Cobalt acid lithium, metal ion compound and water soluble organic substance adopt said ratio, and the cobalt acid lithium electrical property after the coating that obtains is good, and metal ion compound integral molar quantity and water soluble organic substance integral molar quantity are the wherein mole sum of each material.
(2) metal ion compound and water soluble organic substance are mixed after, be incorporated as the water of water soluble organic substance gross mass 10 ~ 20%, the rotating speed ball milling 2 ~ 5h with 100 ~ 300rpm gets slurry one time.the present invention first with metal ion compound with add water for ball milling after water soluble organic substance mixes, can make metal ion compound and the water soluble organic substance can Uniform Dispersion, and granularity attenuates, be conducive to improve the uniformity of coating, in the present invention, the metal ion compound that adds does not need dissolving, can greatly reduce production costs, processing step is also more simple, the most important thing is, the energy that first utilizes ball milling to produce in the present invention makes metal ion compound and water soluble organic substance complexing together, in the follow-up drying of cobalt acid lithium, can keep each component homogeneous in roasting process, stable, avoid metal ion compound to produce the phenomenon of segregation in pyroprocess, prevent that element from separating out, the electrical property of the cobalt acid lithium after guaranteeing to coat, efficiently solve the affected problem of cobalt acid lithium electrical property after high-temperature roasting.
(3) add cobalt acid lithium and be the water of water soluble organic substance gross mass 30 ~ 50% in a slurry, the rotating speed ball milling 6 ~ 12h with 50 ~ 80rpm gets secondary slurry.secondary ball milling not only can be opened the agglomerated particle of cobalt acid lithium material, and metal ion compound is dispersed in around cobalt acid lithium particle, improve the uniformity that coats, simultaneously, secondary ball milling makes again water soluble organic substance and cobalt acid lithium set up and contacts, make water soluble organic substance can play sterically hindered effect in heat treatment process, not only can effectively prevent separating out of elemental lithium, and can also suppress the excessive grain growth of product, reduce the generation of product agglomeration, make the cobalt acid lithium good crystallinity after coating, coat evenly, reunite and reach less the electrical property excellence, in addition, ball milling speed when preparing a slurry in the present invention is 100 ~ 300rpm, Ball-milling Time is 2 ~ 5h, and the ball milling speed of preparation during secondary slurry is 50 ~ 80rpm, Ball-milling Time is 6 ~ 12h, preparation during a slurry owing to not adding cobalt acid lithium, but so high speed short time ball milling, in order to make metal ion compound and water soluble organic substance rapid mixing, and preparation has added cobalt acid lithium during secondary slurry, easily reunite, the long-time ball milling of low speed, not only can fully open the particle of reunion, prevent from again reuniting, can also make metal ion compound, water soluble organic substance and the full and uniform mixing of cobalt acid lithium, and the granularity of particle is also thinner more even, rotational speed of ball-mill turns low by height, Ball-milling Time turns long by short, can guarantee metal ion compound, water soluble organic substance and the full and uniform mixing of cobalt acid lithium, and the granularity of particle is also thinner more even, be conducive to improve the uniformity of coating.
(4) secondary slurry is dried.
(5) the cobalt acid lithium after the secondary slurry after drying must coat after roasting under air atmosphere.
As preferably, described metal ion compound is one or more of aluminium oxide, magnesium oxide, zinc oxide, zirconia, cerium oxide and alum.Metal ion compound is selected one or more of aluminium oxide, magnesium oxide, zinc oxide, zirconia, cerium oxide and alum, and aluminium oxide, magnesium oxide, zinc oxide, zirconia, cerium oxide and alum are easy to obtain, and cost is low, and covered effect is good.
As preferably, described water soluble organic substance is one or more in citric acid, glucose, sucrose, acrylic acid, oxalic acid and ascorbic acid.Water soluble organic substance is one or more in citric acid, glucose, sucrose, acrylic acid, oxalic acid and ascorbic acid, and citric acid, glucose, sucrose, acrylic acid, oxalic acid and ascorbic acid are easy to obtain, and cost is low, and complexing and space resistance position effect is good.
As preferably, in step (4), the condition of oven dry is: 100 ~ 300 ℃ of temperature, time 3 ~ 8h.
As preferably, in step (5), the concrete steps of roasting are:
(a) low-temperature bake: the secondary slurry after drying is under air atmosphere, with the temperature calcining 3 ~ 8h of 400 ~ 600 ℃.First roasting under the lower temperature of 400 ~ 600 ℃, thus to avoid directly causing at the beginning violent dry the causing of particle to burst because sintering temperature is higher, affect covered effect, and bakes to burn the article plays the effect of buffering.
(b) high-temperature roasting: sintering temperature is increased to 700 ~ 800 ℃ continues roasting 3 ~ 8h.Sintering temperature is too high, and metal component is more easily separated out, and makes simultaneously material have lamination, causes the product structure that obtains inconsistent, affects electrical property, and the after baking temperature is controlled at 700 ~ 800 ℃, the product good crystallinity that obtains, and the product component is even, stable.
As preferably, in step (b), heating rate is 50 ~ 100 ℃/h.Heating rate is 50 ~ 100 ℃/h, and increasing extent of temperature is comparatively mild, can avoid particle acutely dry.
Therefore, the present invention has following beneficial effect:
(1) add water soluble organic substance in the coating process, can keep each component homogeneous, stable in the follow-up drying of cobalt acid lithium, roasting process, avoid metal ion compound to produce the phenomenon of segregation in pyroprocess, prevent that element from separating out, the electrical property of the cobalt acid lithium after guaranteeing to coat efficiently solves the affected problem of cobalt acid lithium electrical property after high-temperature roasting;
(2) water soluble organic substance can play sterically hindered effect in heat treatment process, not only can effectively prevent separating out of elemental lithium, and can also suppress the excessive grain growth of product, reduce the generation of product agglomeration, make cobalt acid lithium good crystallinity after coating, coat evenly, reuniting reaches the electrical property excellence less;
(3) slurry high speed short time ball millings, the long-time ball milling of secondary slurry low speed, guarantee metal ion compound, water soluble organic substance and the full and uniform mixing of cobalt acid lithium, and the granularity of particle is also thinner more even, is conducive to improve the uniformity of coating and the electrical property of product;
(4) the ladder roasting by high temperature after first low temperature, thus avoid particle to burst because of violent dry causing;
(5) adopt the standby cobalt acid lithium that coats of solid-phase ball milling legal system, the metal ion compound of interpolation does not need dissolving, and processing step is simple, and production cost is low, is fit to produce in enormous quantities.
Description of drawings
Fig. 1 is the Electronic Speculum figure of cobalt acid lithium after coating in embodiment 1.
Fig. 2 is the XRD figure of cobalt acid lithium after coating in embodiment 1.
Fig. 3 is the first charge-discharge curve chart of half-cell under 1C that after coating in embodiment 1, cobalt acid lithium is made.
Fig. 4 be by the capacity that cobalt acid lithium after coating in embodiment 1 makes be the lithium ion battery of 1600mAh at 20 ± 5 ℃, the loop test figure with the 1C/1C charge-discharge magnification in the voltage range of 3.0 ~ 4.35V.
Fig. 5 be by the capacity that cobalt acid lithium after coating in embodiment 1 makes be the lithium ion battery of 1600mAh at 20 ± 5 ℃, the loop test figure with the 1C/1C charge-discharge magnification in the voltage range of 3.0 ~ 4.4V.
Embodiment
The present invention will be further described below in conjunction with the drawings and specific embodiments.
In the present invention, if not refer in particular to, all devices and raw material all can be buied from market or the industry is commonly used, and the method in following embodiment if no special instructions, is this area conventional method.
(1) take 98g cobalt acid lithium (M
Cobalt acid lithium: 98 g/mol), take cobalt acid lithium mole (1mol) as benchmark, be 0.5% of cobalt acid lithium mole by metal ionic compound integral molar quantity, the water soluble organic substance integral molar quantity is 50% ratio metering metal ion compound and water soluble organic substance of cobalt acid lithium mole, wherein, metal ion compound is magnesium oxide (M
Magnesium oxide: 40 g/mol), water soluble organic substance is glucose (M
Glucose: 180 g/mol), claim to get magnesium oxide 0.2 g, glucose 90 g.
(2) magnesium oxide and glucose are mixed after, be incorporated as glucose quality 10%(9 g) water, the rotating speed ball milling 5h with 100rpm gets slurry one time.
(3) add in a slurry cobalt acid lithium and be glucose quality 30%(27 g) water, with the rotating speed ball milling 12h of 50rpm, get secondary slurry.
(4) with the secondary slurry oven dry, drying condition is: 100 ℃ of temperature, time 8h.
(5) the cobalt acid lithium after the secondary slurry after drying must coat after roasting under air atmosphere, the concrete steps of roasting are:
(a) low-temperature bake: the secondary slurry after drying is under air atmosphere, with the temperature calcining 8h of 400 ℃.
(b) high-temperature roasting: sintering temperature is increased to 700 ℃ continues roasting 8h, heating rate is 100 ℃/h.
One, Micro-Structure Analysis
Utilize the cobalt acid lithium after electron microscope observation coats, the microscopic pattern that obtains as shown in Figure 1.
Cobalt acid lithium after coating is carried out X-ray diffraction, and the spectrogram that obtains as shown in Figure 2.
Two, electrochemical property test
Take the cobalt that obtains acid lithium as anodal, pure lithium is that negative pole is made half-cell, and at 20 ± 5 ℃, 1C carries out the half-cell test under the condition of 3.0 ~ 4.3 V, and the first charge-discharge curve that obtains as shown in Figure 3.
With the cobalt after the coating that obtains acid lithium as positive electrode, making model is 495148, and nominal capacity is the lithium ion battery of 1600mAh, at 20 ± 5 ℃, carry out loop test in the voltage range of 3.0 ~ 4.35V with the 1C/1C charge-discharge magnification, the loop test figure that obtains as shown in Figure 4.
With the cobalt after the coating that obtains acid lithium as positive electrode, making model is 495148, and nominal capacity is the lithium ion battery of 1600mAh, at 20 ± 5 ℃, carry out loop test in the voltage range of 3.0 ~ 4.4V with the 1C/1C charge-discharge magnification, the loop test figure that obtains as shown in Figure 5.
Embodiment 2
(1) take 98g cobalt acid lithium (M
Cobalt acid lithium: 98 g/mol), take cobalt acid lithium mole (1mol) as benchmark, be 1% of cobalt acid lithium mole by metal ionic compound integral molar quantity, the water soluble organic substance integral molar quantity is 60% ratio metering metal ion compound and water soluble organic substance of cobalt acid lithium mole, wherein, metal ion compound is aluminium oxide and magnesium oxide (M
Aluminium oxide: 102 g/mol, M
Magnesium oxide: 40 g/mol), aluminium oxide and magnesium oxide are respectively 0.005mol, and water soluble organic substance is oxalic acid and citric acid (M
Oxalic acid: 90 g/mol, M
Citric acid: 192 g/mol), oxalic acid and citric acid are respectively 0.3mol, claim to get aluminium oxide 0.51 g, magnesium oxide 0.2 g, oxalic acid 27 g, citric acid 57.6 g.
(2) aluminium oxide, magnesium oxide and oxalic acid, citric acid are mixed after, be incorporated as oxalic acid and citric acid gross mass 15%(12.69 g) water, the rotating speed ball milling 3h with 200rpm gets slurry one time.
(3) add in a slurry cobalt acid lithium and be oxalic acid and citric acid gross mass 40%(33.84 g) water, with the rotating speed ball milling 10h of 60rpm, get secondary slurry.
(4) with the secondary slurry oven dry, drying condition is: 200 ℃ of temperature, time 5h.
(5) the cobalt acid lithium after the secondary slurry after drying must coat after roasting under air atmosphere, the concrete steps of roasting are:
(a) low-temperature bake: the secondary slurry after drying is under air atmosphere, with the temperature calcining 6h of 450 ℃.
(b) high-temperature roasting: sintering temperature is increased to 750 ℃ continues roasting 6h, heating rate is 60 ℃/h.
The Micro-Structure Analysis of the cobalt acid lithium after coating in the present embodiment is identical with embodiment 1 with the method for electrochemical property test, and the result that obtains is similar, therefore do not give unnecessary details and enumerate at this.
Embodiment 3
(1) take 98g cobalt acid lithium (M
Cobalt acid lithium: 98 g/mol), take cobalt acid lithium mole (1mol) as benchmark, be 2% of cobalt acid lithium mole by metal ionic compound integral molar quantity, the water soluble organic substance integral molar quantity is 70% ratio metering metal ion compound and water soluble organic substance of cobalt acid lithium mole, wherein, metal ion compound is aluminium oxide, magnesium oxide and alum (M
Aluminium oxide: 102 g/mol, M
Magnesium oxide: 40 g/mol, M
Alum: 474 g/mol), aluminium oxide and magnesium oxide are respectively 0.005mol, and alum 0.01mol, water soluble organic substance are oxalic acid, glucose and acrylic acid (M
Oxalic acid: 90 g/mol, M
Glucose: 180 g/mol, M
Acrylic acid: 72 g/mol), oxalic acid and glucose are respectively 0.3mol, and acrylic acid is 0.1mol, claim to get aluminium oxide 0.51 g, magnesium oxide 0.2 g, alum 4.74 g, oxalic acid 27 g, glucose 54 g, acrylic acid 7.2 g.
(2) aluminium oxide, magnesium oxide, alum and oxalic acid, glucose, acrylic acid are mixed after, be incorporated as oxalic acid, glucose and acrylic acid gross mass 20%(17.64g) water, the rotating speed ball milling 2h with 300rpm gets slurry one time.
(3) add in a slurry cobalt acid lithium and be oxalic acid, glucose and acrylic acid gross mass 50%(44.1 g) water, with the rotating speed ball milling 6h of 80rpm, get secondary slurry.
(4) with the secondary slurry oven dry, drying condition is: 300 ℃ of temperature, time 3h.
(5) the cobalt acid lithium after the secondary slurry after drying must coat after roasting under air atmosphere, the concrete steps of roasting are:
(a) low-temperature bake: the secondary slurry after drying is under air atmosphere, with the temperature calcining 3h of 650 ℃.
(b) high-temperature roasting: sintering temperature is increased to 800 ℃ continues roasting 3h, heating rate is 100 ℃/h.
The Micro-Structure Analysis of the cobalt acid lithium after coating in the present embodiment is identical with embodiment 1 with the method for electrochemical property test, and the result that obtains is similar, therefore do not give unnecessary details and enumerate at this.
Can obviously find out from Fig. 1, the particle diameter of the cobalt acid lithium after the present invention coats is even, without obviously reuniting.
As can be seen from Figure 2, the XRD spectra of the cobalt acid lithium after the present invention coats can be corresponding one by one with the standard spectrogram of cobalt acid lithium, illustrates that the present invention separates out without elemental lithium or cobalt element in roasting process, the good crystallinity of cobalt acid lithium, crystal structure is good, and the cobalt acid lithium crystalline phase after coating is single, complete.
As can be seen from Figure 3, cobalt acid lithium after the present invention coats is when first charge-discharge, the initial charge specific capacity reaches 162 mAh/g, first discharge specific capacity reaches 160 mAh/g, but reverse efficiency reaches 98.8% first, compare with specific capacity 140 mAh/g of existing commercially available cobalt acid lithium and totally exceed 14%, illustrate that the sour lithium specific capacity of cobalt after the present invention coats is significantly improved, have good chemical property.
Can find out from Fig. 4, Fig. 5, battery is in the voltage range of 3.0 ~ 4.35V and 3.0 ~ 4.4V, all can remain on 94% left and right of initial capacity with the capability retention after 1C multiplying power circulation 300 times, after illustrating that charging upper limit voltage is increased to 4.35 ~ 4.4V, the cycle performance of battery is still good, namely positive electrode (the cobalt acid lithium after the coating that makes by the present invention) stability, good cycle.
Above-described embodiment is a kind of better scheme of the present invention, is not that the present invention is done any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim puts down in writing.
Claims (6)
1. the cladding process of a cobalt acid lithium, is characterized in that, comprises the following steps:
(1) take a certain amount of cobalt acid lithium, take cobalt acid lithium mole as benchmark, be 0.5 ~ 2% of cobalt acid lithium mole by metal ionic compound integral molar quantity, the water soluble organic substance integral molar quantity is 50 ~ 70% ratio metering metal ion compound and water soluble organic substance of cobalt acid lithium mole;
(2) metal ion compound and water soluble organic substance are mixed after, be incorporated as the water of water soluble organic substance gross mass 10 ~ 20%, the rotating speed ball milling 2 ~ 5h with 100 ~ 300rpm gets slurry one time;
(3) add cobalt acid lithium and be the water of water soluble organic substance gross mass 30 ~ 50% in a slurry, the rotating speed ball milling 6 ~ 12h with 50 ~ 80rpm gets secondary slurry;
(4) secondary slurry is dried;
(5) the cobalt acid lithium after the secondary slurry after drying must coat after roasting under air atmosphere.
2. the cladding process of a kind of cobalt acid lithium according to claim 1, is characterized in that, described metal ion compound is one or more in aluminium oxide, magnesium oxide, zinc oxide, zirconia, cerium oxide and alum.
3. the cladding process of a kind of cobalt acid lithium according to claim 1, is characterized in that, described water soluble organic substance is one or more in citric acid, glucose, sucrose, acrylic acid, oxalic acid and ascorbic acid.
4. the cladding process of according to claim 1 and 2 or 3 described a kind of cobalt acid lithiums, is characterized in that, in step (4), the condition of oven dry is: 100 ~ 300 ℃ of temperature, time 3 ~ 8h.
5. the cladding process of a kind of cobalt acid lithium according to claim 1, is characterized in that, in step (5), the concrete steps of roasting are:
(a) low-temperature bake: the secondary slurry after drying is under air atmosphere, with the temperature calcining 3 ~ 8h of 400 ~ 600 ℃;
(b) high-temperature roasting: sintering temperature is increased to 700 ~ 800 ℃ continues roasting 3 ~ 8h.
6. the cladding process of a kind of cobalt acid lithium according to claim 5, is characterized in that, in step (b), heating rate is 50 ~ 100 ℃/h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104393286A (en) * | 2014-11-26 | 2015-03-04 | 南通瑞翔新材料有限公司 | Aqueous coating method for high-voltage lithium cobalt oxide positive electrode material |
| WO2016155314A1 (en) * | 2015-03-31 | 2016-10-06 | 南通瑞翔新材料有限公司 | Aqueous coating method for high-voltage lithium cobaltate positive electrode material |
| CN106784739A (en) * | 2017-02-15 | 2017-05-31 | 湖南瑞翔新材料股份有限公司 | A kind of cobalt acid lithium material and preparation method thereof, positive electrode |
| CN109494370A (en) * | 2018-12-12 | 2019-03-19 | 北方奥钛纳米技术有限公司 | A kind of method for coating of electrode material of lithium battery and electrode material containing clad |
| CN113851617A (en) * | 2020-06-28 | 2021-12-28 | 天津国安盟固利新材料科技股份有限公司 | Double-metal-element co-coated lithium cobaltate material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050130042A1 (en) * | 2003-12-11 | 2005-06-16 | Byd America Corporation | Materials for positive electrodes of lithium ion batteries and their methods of fabrication |
| CN1986429A (en) * | 2006-12-14 | 2007-06-27 | 复旦大学 | Carbon coated nano LiCoO2 material and its preparing method and application |
| CN102237515A (en) * | 2010-04-20 | 2011-11-09 | 深圳市比克电池有限公司 | Lithium ion battery, active cathode material and preparation methods thereof |
-
2013
- 2013-01-23 CN CN201310023937.6A patent/CN103151518B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050130042A1 (en) * | 2003-12-11 | 2005-06-16 | Byd America Corporation | Materials for positive electrodes of lithium ion batteries and their methods of fabrication |
| CN1986429A (en) * | 2006-12-14 | 2007-06-27 | 复旦大学 | Carbon coated nano LiCoO2 material and its preparing method and application |
| CN102237515A (en) * | 2010-04-20 | 2011-11-09 | 深圳市比克电池有限公司 | Lithium ion battery, active cathode material and preparation methods thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104393286A (en) * | 2014-11-26 | 2015-03-04 | 南通瑞翔新材料有限公司 | Aqueous coating method for high-voltage lithium cobalt oxide positive electrode material |
| WO2016082672A1 (en) * | 2014-11-26 | 2016-06-02 | 南通瑞翔新材料有限公司 | Aqueous coating method of high-voltage lithium cobalt oxide positive electrode material |
| WO2016155314A1 (en) * | 2015-03-31 | 2016-10-06 | 南通瑞翔新材料有限公司 | Aqueous coating method for high-voltage lithium cobaltate positive electrode material |
| CN106784739A (en) * | 2017-02-15 | 2017-05-31 | 湖南瑞翔新材料股份有限公司 | A kind of cobalt acid lithium material and preparation method thereof, positive electrode |
| CN106784739B (en) * | 2017-02-15 | 2019-09-13 | 湖南瑞翔新材料股份有限公司 | A kind of cobalt acid lithium material and preparation method thereof, positive electrode |
| CN109494370A (en) * | 2018-12-12 | 2019-03-19 | 北方奥钛纳米技术有限公司 | A kind of method for coating of electrode material of lithium battery and electrode material containing clad |
| CN113851617A (en) * | 2020-06-28 | 2021-12-28 | 天津国安盟固利新材料科技股份有限公司 | Double-metal-element co-coated lithium cobaltate material and preparation method thereof |
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