CN101355161B - Method for preparing lithium ion battery anode material nickel cobalt lithium manganate - Google Patents
Method for preparing lithium ion battery anode material nickel cobalt lithium manganate Download PDFInfo
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Abstract
The invention discloses a method for preparing nickel cobalt lithium manganate serving as a lithium ion battery anode material, and belongs to the technical field of preparation of lithium ion battery anode materials. The method comprises the steps of taking a manganese compound, a nickel compound, lithium cobaltate and lithium hydroxide as raw materials, obtaining a precursor with good combination of lithium, manganese, cobalt and nickel through hydrothermal reaction, supplementing a lithium source to the precursor, and grinding to obtain a precursor; the precursor is roasted for one time to obtain the nickel cobalt lithium manganate with excellent performance. The process provided by the invention is simple and easy to control, and the prepared product has low production cost and stable and excellent product performance and can be used for industrial production.
Description
Technical field
The present invention relates to the preparation method of anode material for lithium-ion batteries, especially the preparation method of anode material lithium nickle cobalt manganic acid of lithium ion battery.
Background technology
One of critical material of lithium ion battery is a positive electrode.The positive electrode that is most widely used at present is LiCoO
2(cobalt acid lithium).But, make LiCoO because cobalt resource is deficient and cost an arm and a leg, and exists certain potential safety hazard when overcharging
2Application in high capacity cell has been subjected to restriction.
Nickel-cobalt lithium manganate material is a kind of novel anode material for lithium-ion batteries, and its typical case's representative is a kind of with Ni, the Co that waits amount of substance, the ternary transition metal oxide positive electrode that Mn combines, and its typical molecular formula is LiNi
1/3Co
1/3Mn
1/3O
2Because of having replaced the cobalt of 2/3rds (or more) in the cobalt acid lithium with relatively inexpensive nickel and manganese, thereby the advantage of its cost aspect is very obvious.Simultaneously, its reversible capacity is big, Stability Analysis of Structures, and security performance is good, has higher conductivity and thermal stability.With other anode material for lithium-ion batteries, to compare as LiMn2O4, LiFePO 4 etc., nickel-cobalt lithium manganate material and cobalt acid lithium are very approaching aspect chemical property and processing characteristics, are a kind of materials that most possibly replaces cobalt acid lithium.
At present, the preparation method of nickle cobalt lithium manganate mainly adopts high temperature solid phase synthesis, coprecipitation.Wherein high temperature solid phase synthesis is about to lithium source, nickel source, cobalt source, manganese source ground and mixed, and calcining is synthesized under 1000 ℃ of left and right sides high temperature, forms through fine grinding at last.This method deficiency is: the one, and slow because of solid-state diffusion speed, batch mixing is difficult to evenly, and there is bigger difference in product at aspects such as structure, compositions, thereby causes its chemical property wayward; The 2nd, the powder body material bulk density of synthesizing is low, and general tap density only is 1.6～1.8g/cm
3, the volume and capacity ratio that makes nickle cobalt lithium manganate is affected practical application than low of the sour lithium of cobalt more.Coprecipitation prepares the preparation that the nickle cobalt lithium manganate technical process mainly is a presoma, mixes lithium and sintering.The co-precipitation from the soluble metal salting liquid of general elder generation goes out the presoma of hydroxide, carbonate or the oxide of nickeliferous manganese cobalt, presoma filter, wash, after dry back adopts the solid phase mixing mode to mix with lithium salts, sintering at high temperature, preparation nickle cobalt lithium manganate (seeing Yanko Marinov Todorov, Koichi Numata.Effects of the Li:(Mn+Co+Ni) molar ratio on the electrochemical properties of Li[Ni
1/3Co
1/3Mn
1/3] O
2Cathodematerial[J] .Electrochimica Acta, 2004,50:495-499).But this method is owing to be solid phase mixing, thereby can not fully guarantee the lithium in the nickle cobalt lithium manganate product and the uniformity of each composition of nickel cobalt manganese, influences the stable of its chemical property.
Summary of the invention
The object of the present invention is to provide a kind of technical process simple and easy to control, lithium and each composition of nickel cobalt manganese evenly mix, the preparation method of the nickle cobalt lithium manganate that can be used for suitability for industrialized production of tap density height, chemical property good stable.
Technical scheme of the present invention is: elder generation carries out hydro-thermal reaction with manganese compound, nickel compound and cobalt acid lithium and lithium hydroxide aqueous solution, obtains lithium, manganese, cobalt, nickel in conjunction with good precursor, again precursor is replenished to allocate the lithium source into and grind to obtain presoma; Presoma is through obtaining the nickle cobalt lithium manganate of function admirable behind the bakes to burn the article; Concrete steps are as follows:
(1) hydro-thermal reaction
A preparation mol ratio is manganese compound, nickel compound and the cobalt acid lithium of Ni:Co:Mn=0.2～0.5:0.2～0.5:0.3～0.5;
B preparation lithium concentration is the lithium hydroxide solution of 15～30g/l;
C joins the manganese compound of above-mentioned metering ratio, nickel compound and cobalt acid lithium simultaneously and carries out hydro-thermal reaction in the hydrothermal reaction kettle that lithium hydroxide solution is housed, the temperature of hydro-thermal reaction is 120～300 ℃, in 2～30 hours reaction time, obtain lithium, manganese, cobalt, nickel in conjunction with good precursor slurry.In the precursor, the molar ratio LI:M (Ni+Mn+Go) of lithium and transition metal nickel, manganese, cobalt〉0.9.
(2) presoma preparation
Precursor slurry is filtered, washs, dried, add the lithium source, make Li/M=1.0～1.20, obtain presoma after the grinding.
(3) roasting
Presoma is carried out bakes to burn the article, and the roasting system is: 1～10 ℃/min of programming rate, 600～1100 ℃ of holding temperatures, temperature retention time 1～20 hour, 1～10 ℃/min of cooling rate.Obtain the nickle cobalt lithium manganate of function admirable.
Manganese compound is one or more in mangano-manganic oxide, manganese dioxide, manganous hydroxide, manganese carbonate or the manganese acetate in the said method; Nickel compound is one or more in nickel oxide, nickel hydroxide, nickelous carbonate or the nickel acetate; The lithium in small amounts source that adds in the precursor is one or both in lithium hydroxide or the lithium carbonate.
Characteristics of the present invention are:
1, adopts manganese compound, nickel compound and cobalt acid lithium to carry out hydro-thermal reaction, utilize the embedding lithium reaction realization lithium of manganese and nickel compound and the even mixing of transition metal as raw material and lithium hydroxide solution;
2, through in the product after the hydro-thermal reaction, the molar ratio of lithium and transition metal (nickel, manganese, cobalt) only needs small amount of supplemental lithium source can obtain well behaved presoma more than 0.9;
Though 3, the product after the process hydro-thermal reaction is near layer structure, crystallization is also imperfect, and this has fully guaranteed the activity of presoma in roasting process.
4, presoma only need can obtain the product that chemical property is good and tap density is high through bakes to burn the article.
Description of drawings
Fig. 1 is that hydro-thermal reaction product and nickle cobalt lithium manganate product compare XRD figure (a product, b hydrothermal product)
The nickle cobalt lithium manganate shape appearance figure of Fig. 2 the present invention preparation.
As can be seen from Figure 1: through after the hydro-thermal reaction, product has tentatively possessed the feature of layer structure, and dephasign is not obvious, but crystallization imperfection (referring to b among Fig. 1); Through after the roasting, product presents complete layer structure, no dephasign peak, and degree of crystallinity is good (referring to Fig. 1 a).
The typical chemical composition analysis of hydrothermal product the results are shown in Table 1.By table 1 data as seen, through after the hydro-thermal reaction, lithium in the product of washes clean and transition metal (total amount of nickel manganese cobalt) mol ratio has reached 0.92, this means that degree that the reaction of embedding lithium carries out is than higher.
Table 1 hydrothermal product chemical composition
| Ni(wt％) | Mn(wt％) | Co(wt％) | Li(wt％) | Li/M |
| 18.35 | 16.6 | 18.42 | 5.93 | 0.92 |
Embodiment
Embodiment 1 gets nickel hydroxide, electrolytic manganese dioxide, each 5mol of cobalt acid lithium, adds in 10 liters of water heating kettles.Place 8 liters of lithium hydroxide solutions in the water heating kettle in advance, lithium concentration 25g/l.Be heated to 250 ℃ of insulations after 5 hours, be cooled to normal temperature, the filtration washing slurry.Behind the oven dry slurry, analyzing its Li/M (lithium and transition metal mol ratio) is 0.92.Replenish and allocate lithium carbonate into, making Li/M is 1.10, adds grinding in ball grinder after 2 hours, carries out roasting.The roasting system is: be warming up to 1020 ℃ of insulations 10 hours with 3 ℃/min speed, with 3 ℃/min of cooling rate cooling, obtain the nickle cobalt lithium manganate product.Products obtained therefrom shows that through X-ray diffraction analysis its thing is layer structure mutually; Tap density is 2.55g/cm
3Product is made the R2016 button cell and is detected, and 0.5C discharges and recharges, and its initial discharge capacity is 151.3mAh/g; After 10 circulations, capacity attenuation 0.5%.
Embodiment 3 gets nickel hydroxide, mangano-manganic oxide, each 5mol of cobalt acid lithium, adds in 10 liters of water heating kettles.Place 8 liters of lithium hydroxide solutions in the water heating kettle in advance, lithium concentration 30g/1.Be heated to 130 ℃ of insulations after 18 hours, be cooled to normal temperature, the filtration washing slurry.Behind the oven dry slurry, analyzing its Li/M is 0.91.Replenish and allocate lithium carbonate into, making Li/M is 1.06, adds grinding in ball grinder after 2 hours, carries out roasting.The roasting system is: be warming up to 1050 ℃ of insulations 15 hours with 5 ℃/min speed, with stove cooling material, obtain the nickle cobalt lithium manganate product.Products obtained therefrom shows that through X-ray diffraction analysis its thing is layer structure mutually; Tap density is 2.58g/cm
3Product is made the R2016 button cell and is detected, and 0.5C discharges and recharges, and its initial discharge capacity is 150.6mAh/g; After 10 circulations, capacity attenuation 0.3%.
Embodiment 4 gets nickelous carbonate, manganese carbonate, each 5mol of cobalt acid lithium, adds in 10 liters of water heating kettles.Place 8 liters of lithium hydroxide solutions in the water heating kettle in advance, lithium concentration 28g/l.Be heated to 280 ℃ of insulations after 20 hours, be cooled to normal temperature, the filtration washing slurry.Behind the oven dry slurry, analyzing its Li/M is 0.92.Replenish and allocate lithium carbonate into, making Li/M is 1.10, adds grinding in ball grinder after 2 hours, carries out roasting.The roasting system is: be warming up to 1000 ℃ of insulations 20 hours with 5 ℃/min speed, with stove cooling material, obtain the nickle cobalt lithium manganate product.The products obtained therefrom thing shows that through X-ray diffraction analysis its thing is layer structure mutually; Tap density is 2.59g/cm
3Product is made the R2016 button cell and is detected, and 0.5C discharges and recharges, and its initial discharge capacity is 152.1mAh/g; After 10 circulations, capacity attenuation 0.5%.
Claims (5)
1. the method for preparing anode material lithium nickle cobalt manganic acid of lithium ion battery, it is characterized in that: earlier manganese compound, nickel compound and cobalt acid lithium and lithium hydroxide aqueous solution are carried out hydro-thermal reaction, obtain lithium, manganese, cobalt, nickel in conjunction with good precursor, again precursor is replenished to allocate the lithium source into and to grind and obtain presoma; Presoma obtains nickle cobalt lithium manganate through behind the bakes to burn the article; Concrete steps are as follows:
(1) hydro-thermal reaction
A preparation mol ratio is manganese compound, nickel compound and the cobalt acid lithium of Ni: Co: Mn=0.2～0.5: 0.2～0.5: 0.3～0.5;
B preparation lithium concentration is the lithium hydroxide solution of 15～30g/l;
C joins manganese compound, nickel compound and cobalt acid lithium simultaneously and carries out hydro-thermal reaction in the hydrothermal reaction kettle that lithium hydroxide solution is housed, the temperature of hydro-thermal reaction is 120～300 ℃, 2～30 hours reaction time, obtain lithium, manganese, cobalt, nickel in conjunction with good precursor slurry, in the precursor that hydro-thermal reaction obtains, mol ratio Li/ (Ni+Mn+Co) is more than 0.9;
(2) presoma preparation
Precursor slurry is filtered, washs, dried, add the lithium source, make mol ratio Li/ (Ni+Mn+Co)=1.0～1.20, obtain presoma after the grinding;
(3) roasting
Presoma is carried out bakes to burn the article, obtain nickle cobalt lithium manganate.
2. the method for preparing anode material lithium nickle cobalt manganic acid of lithium ion battery according to claim 1 is characterized in that: manganese compound is one or more in mangano-manganic oxide, manganese dioxide, manganous hydroxide, manganese carbonate or the manganese acetate.
3. the method for preparing anode material lithium nickle cobalt manganic acid of lithium ion battery according to claim 1 is characterized in that: nickel compound is one or more in nickel oxide, nickel hydroxide, nickelous carbonate or the nickel acetate.
4. the described method for preparing anode material lithium nickle cobalt manganic acid of lithium ion battery of claim 1, it is characterized in that: the lithium source is one or both in lithium hydroxide or the lithium carbonate.
5. the described method for preparing anode material lithium nickle cobalt manganic acid of lithium ion battery of claim 1, it is characterized in that: the roasting system is: 1～10 ℃/min of programming rate, 600～1100 ℃ of holding temperatures, temperature retention time 1～20 hour, 1～10 ℃/min of cooling rate.
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| CN102336441B (en) * | 2011-06-29 | 2013-07-03 | 金瑞新材料科技股份有限公司 | Method for preparing lithium manganate used as lithium ion battery anode material by using trimanganese tetroxide |
| CN102328961A (en) * | 2011-09-07 | 2012-01-25 | 先进储能材料国家工程研究中心有限责任公司 | Precursor of nickel cobalt lithium manganate positive material for lithium ion battery and production method thereof |
| CN102517448B (en) * | 2012-01-04 | 2013-09-25 | 北京理工大学 | Method for recycling metal ion from waste lithium-ion battery |
| CN103094555A (en) * | 2013-01-31 | 2013-05-08 | 中国科学院上海技术物理研究所 | Method for preparing manganese, cobalt, nickel, oxygen and lithium quinary lithium ion battery anode material with nanometer structure |
| CN104118913B (en) * | 2014-08-06 | 2015-12-30 | 哈尔滨工程大学 | For the hydrothermal synthesis method of the iron sodium manganate of water system positively charged ion battery electrode material and the preparation method of water system battery |
| CN105692703B (en) * | 2014-11-24 | 2017-09-08 | 苏州世名科技股份有限公司 | Lithium-rich manganese-based anode material and preparation method thereof and lithium ion battery |
| CN106784783B (en) * | 2015-11-19 | 2019-07-05 | 荆门市格林美新材料有限公司 | The method of synthesizing lithium ion battery nickel cobalt manganese anode material |
| CN114068898A (en) * | 2016-03-14 | 2022-02-18 | 苹果公司 | Cathode active material for lithium ion 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 |
| CN106904668B (en) * | 2017-04-14 | 2018-03-20 | 郑州科技学院 | A kind of preparation method of cell positive material tetrakaidecahedron shape nanometer nickel-cobalt LiMn2O4 |
| CN108172822B (en) * | 2017-12-29 | 2020-10-09 | 昶联金属材料应用制品(广州)有限公司 | Nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| US11757096B2 (en) | 2019-08-21 | 2023-09-12 | Apple Inc. | Aluminum-doped lithium cobalt manganese oxide batteries |
| US12074321B2 (en) | 2019-08-21 | 2024-08-27 | Apple Inc. | Cathode active materials for lithium ion batteries |
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