CN108199040A - LiNi0.8Co0.2O2The preparation method and applications of material - Google Patents
LiNi0.8Co0.2O2The preparation method and applications of material Download PDFInfo
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- CN108199040A CN108199040A CN201711462158.0A CN201711462158A CN108199040A CN 108199040 A CN108199040 A CN 108199040A CN 201711462158 A CN201711462158 A CN 201711462158A CN 108199040 A CN108199040 A CN 108199040A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to a kind of LiNi0.8Co0.2O2The preparation method of material, includes the following steps：(1) it is lithium salts, nickel salt, cobalt salt and urea is soluble in water, hydro-thermal reaction is then carried out at 160 DEG C, obtains precursor solution；Wherein, the molar ratio of lithium salts, nickel salt and cobalt salt is 1:0.8:0.2；(2) the dry precursor solution, to remove water therein, is then calcined at 750 DEG C 850 DEG C under oxygen atmosphere, obtains LiNi0.8Co0.2O2Material.The method of the present invention is by controlling the structure and morphology of precursor product, effectively alleviate " cationic mixing " phenomenon in material synthesis processes, improve the structurally ordered degree of material, structure collapses of the material in cyclic process can be reduced, effectively improve the stability and high rate performance of circulating battery.
Description
Technical field
Preparing technical field more particularly to a kind of LiNi the present invention relates to material0.8Co0.2O2The preparation method of material and
It is applied.
Background technology
One of key technology for developing high-performance lithium ion battery is the exploitation of positive electrode.In recent years, negative material and
Electrolysis Quality Research all makes great progress, and in contrast, the development of positive electrode is more slow, commercialization lithium-ion electric
The specific capacity of positive electrode is far smaller than negative material in pond, becomes and restricts the weight that lithium ion battery overall performance further improves
Want factor.Therefore, the research of positive electrode is more and more paid attention to.
LiNi0.8Co0.2O2Material and widely applied LiCoO now2Material is the same, has α-NaFeO2Type layer structure
(R-3m space groups), theoretical capacity 275mAh/g have LiNiO concurrently as anode material for lithium-ion batteries2And LiCoO2It is excellent
Point, specific capacity is high, and good cycle is cheap, and pollution is small, prepares simple etc..Therefore, this series material becomes lithium in recent years
One hot spot of ion battery positive electrode research field.
However, LiNi0.8Co0.2O2The preparation condition of material is more harsh, because of Ni2+It is difficult to aoxidize, according to preparation
LiCoO2The LiNi that synthesizes of technique0.8Co0.2O2Hardly has electro-chemical activity, it is necessary to contain O2Atmosphere in into
Row reaction.And in the product of synthesis, part Ni2+Occupy Li+Position generates the cation distribution of partial order, drop in lithium position
The low structural order of material, in order to maintain Ni2+The electroneutral of system balances after into Li-O layers, also necessarily has in Ni-O layers
The Ni of equivalent2+In the presence of here it is " cationic mixing " phenomenons.This " cationic mixing " phenomenon has its chemical property larger
Influence.LiNi0.8Co0.2O2In occupy the Ni of lithium position2+It is smaller to be oxidized to radius at initial charge (de- lithium) for ion
Ni3+Ion even Ni4+Ion makes the irreversible reduction of interlamellar spacing, and causing the ion, nearby structure collapses, subsequent embedding
During lithium, Li+Ion is difficult to return to the position collapsed, so as to cause electric discharge (embedding lithium) when capacity irreversible loss,
This irreversible loss and the Ni for occupying lithium position2+The amount of ion has direct relation.This is also up till now series material to face most
Main problem.
Invention content
In order to solve the above technical problems, the object of the present invention is to provide a kind of LiNi0.8Co0.2O2The preparation method of material and
It is applied, and by controlling the structure and morphology of precursor product, is effectively alleviated " cationic mixing " in material synthesis processes
Phenomenon improves the structurally ordered degree of material, it is possible to reduce structure collapses of the material in cyclic process effectively improve battery and follow
The stability and high rate performance of ring.
The present invention's provides a kind of LiNi0.8Co0.2O2The preparation method of material, includes the following steps：
(1) it is lithium salts, nickel salt, cobalt salt and urea is soluble in water, then at 155 DEG C -165 DEG C carry out hydro-thermal reaction (or
Claim solvent thermal reaction), obtain precursor solution；Wherein, the molar ratio of lithium salts, nickel salt and cobalt salt is 1:0.8:0.2；
(2) the dry precursor solution, to remove water therein, then under oxygen atmosphere at 750 DEG C -850 DEG C
It is calcined, obtains LiNi0.8Co0.2O2Material.
Further, in step (1), lithium salts is lithium acetate, and nickel salt is nickel acetate, and cobalt salt is cobalt acetate.
Further, in step (1), water is deionized water.
Further, in step (1), ultrasonic agitation method is used during dissolving.Further, in step (1), metal from
The molar ratio of son and urea is 2:1, metal ion is lithium salts, nickel salt and cobalt salt.It is heavy that urea plays in hydrothermal reaction process
The effect of shallow lake agent promotes the generation of target presoma.
Further, in step (1), the hydro-thermal reaction time 8h-12h.
Preferably, in step (1), 10h is reacted at 160 DEG C.
Further, after step (1), the step of further including natural cooling precursor solution, it is cooled to room temperature
It is dried again afterwards.Further, in step (2), include the following steps when dry：First precursor solution is added at 80 DEG C
Then thermal agitation is dried in vacuo to no liquid at 120 DEG C.
The present invention is by the modification of precipitating reagent, by controlling the synthesis items such as temperature, reaction time during hydrothermal synthesis
Part has prepared the persursor material for having special appearance structure, and the flower that diameter is about 5 μm can be formed in hydrothermal reaction process
Piece shape structure, flower shape structure are made of a large amount of linear structures, and the flower shape structure in presoma is largely reunited together and
Even distribution.
Further, in step (2), calcination time 4-6h.
Preferably, in step (2), 5h is calcined at 800 DEG C.Further, it in step (2), is also wrapped before and after calcining
The step of including the product grind into powder by dried product or after calcining.
For presoma made above by the calcining in oxygen, the lava that can be efficiently reduced in final product is mutually miscellaneous
Matter improves the material structure degree of order, the bulky grain material being made of little particle of uniform size reunion is obtained, so as to obtain Gao Rong
The excellent anode LiNi of amount, cyclical stability0.8Co0.2O2Material.
The invention also discloses using the LiNi prepared by above-mentioned preparation method0.8Co0.2O2Material is as lithium-ion electric
Application in the positive electrode of pond.
According to the above aspect of the present invention, the present invention has at least the following advantages：
1st, there is good structural integrity by presoma prepared by solvent thermal reaction, is that a large amount of threads are reunited
Flower shape structure together, while also ensure various elements being uniformly distributed in presoma, and such open structure has
Conducive to the entrance of oxygen in calcination process so that material various pieces can fully be reacted；
2nd, obtained LiNi is calcined0.8Co0.2O2Material has good structurally ordered degree, and " cationic mixing " phenomenon obtains
Effective inhibition so that material generated irreversible structural phase transition in cyclic process is more slow；
3rd, the LiNi prepared0.8Co0.2O2Material also greatly improves while lithium ion battery charge/discharge capacity is improved
Cyclical stability and high rate performance are relative to LiNi made of conventional sol-gel method0.8Co0.2O2Material, chemical property
Have and significantly promoted.
Above description is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be implemented in accordance with the contents of the specification, below with presently preferred embodiments of the present invention and after attached drawing is coordinated to be described in detail such as.
Description of the drawings
Fig. 1 is LiNi prepared by the embodiment of the present invention 10.8Co0.2O2The SEM figures of presoma；
Fig. 2 is LiNi prepared by the embodiment of the present invention 10.8Co0.2O2The SEM figures of material.
Specific embodiment
With reference to the accompanying drawings and examples, the specific embodiment of the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but be not limited to the scope of the present invention.
Embodiment 1
Present embodiments provide a kind of lithium ion cell positive LiNi0.8Co0.2O2The preparation method of material, including as follows
Step：
1) 0.2551g lithium acetates, 0.4977g nickel acetates, 0.1246g cobalt acetates and 0.3003g urea are weighed and is placed in 50mL
In beaker, 40g deionized waters are added in, obtain mixed liquor；
2) mixed liquor is stirred by ultrasonic, all materials is made to be completely dissolved to obtain yellow solution；
3) solution is poured into 50mL hydrothermal reaction kettles, solvent thermal reaction is carried out in 160 DEG C of air dry oven, reacted
Cooled to room temperature after 10h；
4) precursor solution that hydro-thermal reaction obtains is transferred in beaker, beaker is placed on 80 DEG C of perseverances of progress in water-bath
Warm heating stirring, to remove the water in solution；
5) beaker equipped with dried product exhibited is put into 120 DEG C of vacuum drying chambers, be further dried；
6) by the presoma being completely dried in beaker take out, be ground into uniform powder, in tube furnace at 800 DEG C
5h is calcined under oxygen atmosphere, calcined product grind into powder is obtained into LiNi0.8Co0.2O2Material.
Fig. 1 is LiNi under different enlargement ratios0.8Co0.2O2The SEM figures of presoma, Fig. 2 is under different enlargement ratios
LiNi0.8Co0.2O2The SEM figures of material.It can be seen from figure 1 that presoma is about diametrically 5 μm of flower shape structure, flower shape
Structure is made of a large amount of linear structures, and the flower shape structure in presoma is largely reunited together and is uniformly distributed.It can from Fig. 2
Find out, last LiNi obtained0.8Co0.2O2Positive electrode is made of together little particle reunion of many diameters less than 1 μm
Secondary bulky grain, this phenomenon have generality.
Table 1 is the LiNi obtained by the present invention0.8Co0.2O2Made from positive electrode and common sol-gel method
LiNi0.8Co0.2O2Chemical property comparison of the material under different circulating ratios after multiple charge and discharge cycles, it can be seen that
Material obtained by the present invention is compared to material made from common sol-gel method in charge/discharge capacity, cyclical stability and high magnification
Very big improvement and raising are suffered from terms of cycle performance.
LiNi prepared by 1 distinct methods of table0.8Co0.2O2The chemical property comparison of positive electrode
(note：Data are the specific discharge capacity in circle cycle in table.)
Embodiment 2
Present embodiments provide a kind of lithium ion cell positive LiNi0.8Co0.2O2The preparation method of material, including as follows
Step：
1) 0.2551g lithium acetates, 0.4977g nickel acetates, 0.1246g cobalt acetates and 0.3003g urea are weighed and is placed in 50mL
In beaker, 40g deionized waters are added in, obtain mixed liquor；
2) mixed liquor is stirred by ultrasonic, all materials is made to be completely dissolved to obtain yellow solution；
3) solution is poured into 50mL hydrothermal reaction kettles, solvent thermal reaction is carried out in 155 DEG C of air dry oven, reacted
Cooled to room temperature after 12h；
4) precursor solution that hydro-thermal reaction obtains is transferred in beaker, beaker is placed on 80 DEG C of perseverances of progress in water-bath
Warm heating stirring, to remove the water in solution；
5) beaker equipped with dried product exhibited is put into 120 DEG C of vacuum drying chambers, be further dried；
6) by the presoma being completely dried in beaker take out, be ground into uniform powder, in tube furnace at 750 DEG C
6h is calcined under oxygen atmosphere, calcined product grind into powder is obtained into LiNi0.8Co0.2O2Material.
Embodiment 3
Present embodiments provide a kind of lithium ion cell positive LiNi0.8Co0.2O2The preparation method of material, including as follows
Step：
1) 0.2551g lithium acetates, 0.4977g nickel acetates, 0.1246g cobalt acetates and 0.3003g urea are weighed and is placed in 50mL
In beaker, 40g deionized waters are added in, obtain mixed liquor；
2) mixed liquor is stirred by ultrasonic, all materials is made to be completely dissolved to obtain yellow solution；
3) solution is poured into 50mL hydrothermal reaction kettles, solvent thermal reaction is carried out in 165 DEG C of air dry oven, reacted
Cooled to room temperature after 8h；
4) precursor solution that hydro-thermal reaction obtains is transferred in beaker, beaker is placed on 80 DEG C of perseverances of progress in water-bath
Warm heating stirring, to remove the water in solution；
5) beaker equipped with dried product exhibited is put into 120 DEG C of vacuum drying chambers, be further dried；
6) by the presoma being completely dried in beaker take out, be ground into uniform powder, in tube furnace at 850 DEG C
4h is calcined under oxygen atmosphere, calcined product grind into powder is obtained into LiNi0.8Co0.2O2Material.
The above is only the preferred embodiment of the present invention, is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of LiNi0.8Co0.2O2The preparation method of material, which is characterized in that include the following steps：
(1) it is lithium salts, nickel salt, cobalt salt and urea is soluble in water, hydro-thermal reaction then is carried out at 155 DEG C -165 DEG C, before obtaining
Drive liquid solution；Wherein, the molar ratio of the lithium salts, nickel salt and cobalt salt is 1:0.8:0.2；
(2) the dry precursor solution, to remove water therein, then carries out under oxygen atmosphere at 750 DEG C -850 DEG C
Calcining, obtains the LiNi0.8Co0.2O2Material.
2. LiNi according to claim 10.8Co0.2O2The preparation method of material, it is characterised in that：In step (1), institute
Lithium salts is stated as lithium acetate, the nickel salt is nickel acetate, and the cobalt salt is cobalt acetate.
3. LiNi according to claim 10.8Co0.2O2The preparation method of material, it is characterised in that：In step (1), gold
The molar ratio for belonging to ion and urea is 2:1, the metal ion is lithium salts, nickel salt and cobalt salt.
4. LiNi according to claim 10.8Co0.2O2The preparation method of material, it is characterised in that：In step (1), water
The thermal response time is 8h-12h.
5. LiNi according to claim 10.8Co0.2O2The preparation method of material, it is characterised in that：After step (1),
The step of further including precursor solution described in natural cooling.
6. LiNi according to claim 10.8Co0.2O2The preparation method of material, which is characterized in that in step (2), do
Include the following steps when dry：
First by the precursor solution, heating stirring to no liquid, is then dried in vacuo at 120 DEG C at 80 DEG C.
7. LiNi according to claim 10.8Co0.2O2The preparation method of material, it is characterised in that：In step (2), forge
The burning time is 4h-6h.
8. LiNi according to claim 10.8Co0.2O2The preparation method of material, it is characterised in that：In step (2), forge
The step of product grind into powder by dried product or after calcining is further included before and after burning.
9. the LiNi prepared by preparation method according to any one of claim 1-80.8Co0.2O2Material as lithium from
Application in sub- cell positive material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112054182A (en) * | 2019-06-06 | 2020-12-08 | 惠州比亚迪实业有限公司 | Nickel cobalt lithium manganate ternary precursor and preparation method thereof, and nickel cobalt lithium manganate positive electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1567620A (en) * | 2003-06-25 | 2005-01-19 | 南都瑞宝能源科技（上海）有限公司 | Anode material--lithium nickelate cobalt for lithium ion battery and preparation method thereof |
| CN101867039A (en) * | 2010-06-22 | 2010-10-20 | 彩虹集团公司 | Method for preparing nano-scale lithium ion battery anode material |
| CN105390666A (en) * | 2015-12-24 | 2016-03-09 | 哈尔滨工业大学 | Lithium mixing method for lithium ion positive electrode material synthetic process |
-
2017
- 2017-12-28 CN CN201711462158.0A patent/CN108199040A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1567620A (en) * | 2003-06-25 | 2005-01-19 | 南都瑞宝能源科技（上海）有限公司 | Anode material--lithium nickelate cobalt for lithium ion battery and preparation method thereof |
| CN101867039A (en) * | 2010-06-22 | 2010-10-20 | 彩虹集团公司 | Method for preparing nano-scale lithium ion battery anode material |
| CN105390666A (en) * | 2015-12-24 | 2016-03-09 | 哈尔滨工业大学 | Lithium mixing method for lithium ion positive electrode material synthetic process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112054182A (en) * | 2019-06-06 | 2020-12-08 | 惠州比亚迪实业有限公司 | Nickel cobalt lithium manganate ternary precursor and preparation method thereof, and nickel cobalt lithium manganate positive electrode material |
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