CN103178257A - Method for preparing precursor of positive material of nickel manganese cobalt multi-element lithium ion battery - Google Patents
Method for preparing precursor of positive material of nickel manganese cobalt multi-element lithium ion battery Download PDFInfo
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- CN103178257A CN103178257A CN2012105256231A CN201210525623A CN103178257A CN 103178257 A CN103178257 A CN 103178257A CN 2012105256231 A CN2012105256231 A CN 2012105256231A CN 201210525623 A CN201210525623 A CN 201210525623A CN 103178257 A CN103178257 A CN 103178257A
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Abstract
The invention discloses a method for preparing a precursor of a positive material of a nickel manganese cobalt multi-element lithium ion battery. The method comprises the following steps of: firstly, dissolving nickel, cobalt and manganese with deionized water, and preparing a multi-element metal salt solution with the total metal ionic molar concentration between 0.8 and 2.5mol/L, wherein the molar ratio of nickel to cobalt to manganese elements in the multi-element metal salt solution is (0-1):(0-1):(0-1); secondly, preparing alkali solution with concentration between 2 and 4mol/L; thirdly, reacting the salt solution with the alkali solution, wherein the temperature is controlled to be between 40 and 70 DEG C and the stirring speed is controlled to be between 100 and 600 revolutions/min, and the adding speed of salt and alkali solutions is controlled, so that the pH value of the reaction system is controlled to be between 8 and 11; and continuously stirring for 30 minutes to 2 hours after the reaction is completed, standing for 2 to 4 hours, filtering to obtain solid matters, and washing with deionized water until the content of Na<+> is lower than 0.03 percent, and drying to obtain the required precursor of the positive material of the nickel manganese cobalt multi-element lithium ion battery. According to the invention, an ammonia complexing agent is not used, and the method has the advantages of no ammonia or nitrogen pollution risk, good product sphericity, uniform granules, narrow granularity distribution and the like.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries manufacturing technology field, relate in particular to the preparation method of lithium ion battery nickel-cobalt-manganese ternary material presoma.
Background technology
Prepare first LiNi from calendar year 2001 Ohzuku etc.
1/3Mn
1/3Co
1/3O
2Since, this material is just with height ratio capacity, stable cycle performance, the characteristics such as cost is relatively low, security performance is good and be subject to researcher's extensive concern.At LiNi
1/3Mn
1/3Co
1/3O
2Middle nickel, cobalt, manganese belong to the cycle adjacent element, can reach individual material properties by regulating Ni, Co, Mn mol ratio composition, have developed in recent years the nickel-cobalt-manganese multi positive electrode of different component, and its general formula can be written as: LiNi
xMn
yCo
1-x-yO
2Take off in the embedding process at lithium ion, LiMn is compared in its structural change
2O
4, LiNO
3, LiCoO
2Compare much smaller.This material is considered to replace LiCoO
2One of best positive electrode, also be considered to for pure electromotive power source (EV) and mixed type electrical source of power (HEV) ideal chose.
Present LiNi
xMn
yCo
1-x-yO
2Common preparation method solid phase mixing high-temperature sintering process, sol-gel process, spray drying process, coprecipitation etc. are arranged.The high temperature solid-state mixed-sintering method is with LiOH.HO
2Or Li
2CO
3With Co
3O
4, NiO and MnO
2Form by the high temperature solid state reaction sintering after mixing, the shortcoming of these class methods is: powder body material needs long ground and mixed, and mixing uniformity is limited, the inhomogeneous distribution that directly has influence on nickel cobalt manganese in positive electrode that mixes due to raw material in high temperature solid state reaction, therefore, product exists than big difference aspect composition, structure and particle size distribution, and the material electrochemical performance reappearance is bad.All there are the shortcomings such as flow process is complicated, cost is high, material pattern that produce is not good in sol-gel process, spray drying process.Hydroxide coprecipitation step is to realize at present the most frequently used method of suitability for industrialized production nickel-cobalt-manganese multi material, and it can make nickel, cobalt, manganese reach on atomic level evenly to mix, and synthetic material spherical degree is good, and tap density is high, even particle size distribution, the advantage such as controlled.But add a large amount of ammoniacal liquor complexing agents during coprecipitation reaction, can cause the damage ratio of environment more seriously, during the sewage disposal ammonia nitrogen, engineering is complicated, and input cost is higher." 12 " energy-saving and emission-reduction planning of country's proposition has in the recent period been carried out strict requirement to the ammonia nitrogen discharge capacity, and various places environmental administration can be more and more tighter to the ammonia nitrogen emission request from now on.
In view of above shortcoming, and national " 12 " energy-saving and emission-reduction planning requirement of response, the invention provides a kind of complexing agents such as ammoniacal liquor that do not add, the coprecipitation reaction that reduces process costs, environmental contamination reduction prepares the method for the presoma that the nickel-cobalt-manganese multi positive electrode uses, use this invention, can obtain the product sphericity better, grain graininess is homogeneous more, particle size distribution is narrower, and jolt ramming can reach 1.6g/cm
3After above nickel-cobalt-manganese multi positive electrode presoma, presoma were processed through lithiumation mixing, sintering, gas powder, the gained positive electrode can reach the chemical property of equivalent material equally.
Summary of the invention
The technical problem to be solved in the present invention is to overcome when in prior art, coprecipitation prepares anode material for lithium-ion batteries need add the shortcoming that ammoniacal liquor easily causes environmental pollution, and provide a kind of method that the complexing agents such as ammoniacal liquor prepare nickel-cobalt-manganese multi precursor of lithium ionic cell positive material material of need not adding, gained persursor material particle good sphericity, grain graininess homogeneous, narrowly distributing, average grain diameter exists
The left and right.
To achieve the above object of the invention, the technical scheme taked of the present invention is as follows:
A kind of preparation method of nickel-cobalt-manganese multi precursor of lithium ionic cell positive material comprises the following steps:
(1) with deionized water with nickel, cobalt, the dissolving of manganese salt, the multi-element metal salting liquid that to be configured to total metal ion molar concentration be 0.8-2.5mol/L, in this multi-element metal salting liquid, the mol ratio of nickel, cobalt, manganese element is (0-1): (0-1): (0-1);
(2) with deionized water, alkali is mixed with the aqueous slkali of 2-4mol/L;
(3) described multi-element metal salting liquid and aqueous slkali are added in reactor react, control reaction temperature at 40 ℃-70 ℃, the reaction mixing speed is that 100-600 turns/min, controls the speed that adds of salt, aqueous slkali, makes reacting system PH value be controlled at 8-11;
(4) 30min-2h is stirred in the complete rear continuation of reaction, and standing 2-4h filters, and gets solid content, washs to Na with deionized water
+Content is below 0.03%, and is then dry at the temperature of 90 ℃-150 ℃, namely obtains required nickel-cobalt-manganese multi precursor of lithium ionic cell positive material.
Described nickel, cobalt, manganese salt are selected one or more in sulfate, nitrate or the chlorate of nickel, cobalt, manganese, and alkali is one or more in NaOH, lithium hydroxide, potassium hydroxide.
Described reacting system PH value is preferably 9-11 in an embodiment, and mixing speed is 300 to turn/min.
Compared with prior art, the present invention has following substantial advantage: do not use the ammoniacal liquor complexing agent in the precipitation reaction process that (1) the present invention relates to, without the ammonia and nitrogen pollution risk; (2) product is spherical good, and particle is even all, narrow particle size distribution.
Brief Description Of Drawings:
Fig. 1: be nickel-cobalt-manganese multi precursor of lithium ionic cell positive material particle size distribution figure of the present invention;
Fig. 2 and Fig. 3: be nickel-cobalt-manganese multi precursor of lithium ionic cell positive material SEM figure of the present invention;
Fig. 4 and Fig. 5: be nickel-cobalt-manganese multi anode material for lithium-ion batteries finished product SEM figure of the present invention.
Embodiment
In order to understand more in detail technical solution of the present invention, elaborate below in conjunction with the accompanying drawings and the specific embodiments:
Fig. 1 has showed nickel-cobalt-manganese multi lithium ion anode material presoma particle size distribution figure of the present invention, and this figure shows, positive electrode granular precursor of the present invention evenly, narrow particle size distribution.
Fig. 2 and Fig. 3 have showed nickel-cobalt-manganese multi precursor of lithium ionic cell positive material SEM figure of the present invention, and this figure shows, spherical good, the epigranular of nickel-cobalt-manganese multi lithium ion anode material presoma product of the present invention.
Fig. 4 and Fig. 5 have showed nickel-cobalt-manganese multi lithium ion anode material finished product SEM figure of the present invention.
Embodiment 1:
(1) with deionized water as solvent, nickelous sulfate, cobaltous sulfate, manganese sulfate are pressed Ni
2+: Co
2+: Mn
2+The dissolving of the ratio of mol ratio=0.5:0.2:0.3, the complex salt solution that to be configured to total metal molar concentration be 2mol/L;
(2) with deionized water, NaOH is mixed with the NaOH aqueous slkali of 4mol/L;
(3) the complex salt solution that (1) is prepared joins in reaction vessel with the aqueous slkali that prepare (2) jointly, control reaction temperature at 50 ℃, the reaction mixing speed is 300 to turn/min, controls salt, aqueous slkali rate of addition, makes reacting system PH value be controlled at 9-11.
(4) reaction continues to stir 2h after 60 hours, and standing 4h filters, and washs to Na with deionized water
+Content is below 0.03%, and is then dry at the temperature of 120 ℃, namely obtains required nickel-cobalt-manganese multi anode material for lithium-ion batteries presoma.
Above-mentioned gained nickel cobalt manganese presoma and lithium salts mol ratio are pressed: Li/(Ni+Co+Mn)=1.1 grind, mix; Through calcining, pulverize again, sieve, namely obtain finished product nickel cobalt manganese anode material for lithium-ion batteries.
Table 1 is the actual measurement index of preparation-obtained nickel-cobalt-manganese multi precursor of lithium ionic cell positive material and finished product:
Table 1: precursor and finished product achievement data
Utilize product that such presoma is done to reach commercial index from top index.
Embodiment 2:
With deionized water as solvent, nickel nitrate, cobalt nitrate, manganese nitrate are pressed Ni
2+: Co
2+: Mn
2+The dissolving of the ratio of mol ratio=0.8:0.1:0.1, the complex salt solution that to be configured to total metal molar concentration be 0.8mol/L;
(2) with deionized water, NaOH is mixed with the NaOH aqueous slkali of 2mol/L;
(3) the complex salt solution that (1) is prepared joins in reaction vessel with the aqueous slkali that prepare (2) jointly, control reaction temperature at 50 ℃, the reaction mixing speed is 300 to turn/min, controls salt, aqueous slkali rate of addition, makes reacting system PH value be controlled at 9-10.
(4) reaction continues to stir 2h after 60 hours, and standing 2h filters, and washs to Na with deionized water
+Content is below 0.03%, and is then dry at the temperature of 115 ℃, namely obtains nickel-cobalt-manganese multi anode material for lithium-ion batteries presoma.
Above-mentioned gained nickel cobalt manganese presoma and lithium salts mol ratio are pressed: Li/(Ni+Co+Mn)=1.2 grind, mix; Through calcining, pulverize again, sieve, namely obtain finished product nickel cobalt manganese anode material for lithium-ion batteries.
Claims (3)
1. the preparation method of a nickel-cobalt-manganese multi precursor of lithium ionic cell positive material is characterized in that comprising the following steps:
(1) with deionized water with nickel, cobalt, the dissolving of manganese salt, the multi-element metal salting liquid that to be configured to total metal ion molar concentration be 0.8-2.5mol/L, in this multi-element metal salting liquid, the mol ratio of nickel, cobalt, manganese element is (0-1): (0-1): (0-1);
(2) with deionized water, alkali is mixed with the aqueous slkali of 2-4mol/L;
(3) described multi-element metal salting liquid and aqueous slkali are added in reactor react, control reaction temperature at 40 ℃-70 ℃, the reaction mixing speed is that 100-600 turns/min, controls the speed that adds of salt, aqueous slkali, makes reacting system PH value be controlled at 8-11;
(4) 30min-2h is stirred in the complete rear continuation of reaction, and standing 2-4h filters, and gets solid content, washs to Na with deionized water
+Content is below 0.03%, and is then dry at the temperature of 90 ℃-150 ℃, namely obtains required nickel-cobalt-manganese multi precursor of lithium ionic cell positive material.
2. the preparation method of nickel-cobalt-manganese multi precursor of lithium ionic cell positive material according to claim 1, it is characterized in that described nickel, cobalt, manganese salt selects one or more in sulfate, nitrate or the chlorate of nickel, cobalt, manganese, alkali is one or more in NaOH, lithium hydroxide, potassium hydroxide.
3. the preparation method of nickel-cobalt-manganese multi precursor of lithium ionic cell positive material according to claim 1, is characterized in that described reacting system PH value is 9-11, and mixing speed is 500 to turn/min.
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Cited By (4)
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|---|---|---|---|---|
| WO2016013674A1 (en) * | 2014-07-25 | 2016-01-28 | 住友金属鉱山株式会社 | Nickel manganese compound hydroxide particles and method for producing same |
| CN106887585A (en) * | 2017-03-13 | 2017-06-23 | 成都育芽科技有限公司 | A kind of preparation method of new energy battery nickel-cobalt lithium manganate cathode material |
| US10903516B2 (en) | 2016-12-19 | 2021-01-26 | Grst International Limited | Method of preparing cathode material for secondary battery |
| CN113690419A (en) * | 2021-08-25 | 2021-11-23 | 蜂巢能源科技有限公司 | Ternary positive electrode composite material, preparation method thereof and lithium ion battery |
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| CN102347483A (en) * | 2011-10-11 | 2012-02-08 | 上海中兴派能能源科技有限公司 | Multilayer composite ternary material and precursor thereof as well as preparation method of multilayer composite ternary material and precursor |
| CN102368548A (en) * | 2011-10-31 | 2012-03-07 | 上海中兴派能能源科技有限公司 | Modified ternary material and precursor thereof and preparation methods of modified ternary material and precursor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016013674A1 (en) * | 2014-07-25 | 2016-01-28 | 住友金属鉱山株式会社 | Nickel manganese compound hydroxide particles and method for producing same |
| JPWO2016013674A1 (en) * | 2014-07-25 | 2017-04-27 | 住友金属鉱山株式会社 | Nickel-manganese composite hydroxide particles and method for producing the same |
| US10903516B2 (en) | 2016-12-19 | 2021-01-26 | Grst International Limited | Method of preparing cathode material for secondary battery |
| CN106887585A (en) * | 2017-03-13 | 2017-06-23 | 成都育芽科技有限公司 | A kind of preparation method of new energy battery nickel-cobalt lithium manganate cathode material |
| CN113690419A (en) * | 2021-08-25 | 2021-11-23 | 蜂巢能源科技有限公司 | Ternary positive electrode composite material, preparation method thereof and lithium ion battery |
| CN113690419B (en) * | 2021-08-25 | 2023-04-14 | 蜂巢能源科技有限公司 | Ternary positive electrode composite material, preparation method thereof and lithium ion battery |
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Application publication date: 20130626 |