CN107565100A - A kind of method for improving anode material for lithium-ion batteries cycle performance - Google Patents
A kind of method for improving anode material for lithium-ion batteries cycle performance Download PDFInfo
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- CN107565100A CN107565100A CN201610509304.XA CN201610509304A CN107565100A CN 107565100 A CN107565100 A CN 107565100A CN 201610509304 A CN201610509304 A CN 201610509304A CN 107565100 A CN107565100 A CN 107565100A
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- lithium
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to a kind of method for improving anode material for lithium-ion batteries cycle performance, anode material for lithium-ion batteries is dispersed in water by (1), and it is 10~70% to make solid content, is sufficiently stirred to ensure that material dispersion is uniform；(2) according to YPO4With anode material for lithium-ion batteries mass ratio 0.05~3%, the soluble yttrium salt of respective quality is weighed, and is configured to the aqueous solution, is added in (1), stirs；(3) according to mol ratio Y3+：PO4 3‑=1：1, weigh (the NH of respective quality4)2HPO4, and add in (2), stir, fully reaction；(4) material in (3) is filtered, washed, after 80~150 DEG C are dried, is put into high temperature furnace, 400~800 DEG C of 2~8h of heat treatment；(5) the material ultrasonic wave after heat treatment is sieved, that is, obtains being coated with YPO4Anode material for lithium-ion batteries.The present invention is simple to operate, and technique is easily controllable, and production cost is low, short preparation period, it is easy to accomplish scale industrial production.
Description
Technical field
The present invention relates to a kind of root lithium ion battery material, and in particular to one kind improves lithium-ion electric
The method of pond positive electrode cycle performance.
Background technology
In recent years, haze, which has become many cities in the whole nation including Beijing, needs the moment to face
The problem of.The region of haze constantly extends, and number of days continues to increase, and this shows that the environment of China is controlled
Reason has arrived very urgent stage.While environmental pollution is increasingly severe, fuel oil supplies
Contradiction is asked also to become increasingly conspicuous.To tackle above mentioned problem, it is all that development is new that Global Auto manufactures big state
Energy automobile lifting increases holding power one after another to the height of national strategy in policy and fund aspect
Degree.Chinese in May, 2015 issue《Made in China 2025》" energy-conservation and new energy vapour
Car " is classified as country 10 and gives priority to one of field greatly, is China's new-energy automobile industry development
Specify direction.With the fast development of New-energy electric vehicle, China is to dynamic lithium battery
Energy density steps up requirement, to more than 300Wh/kg from 180Wh/kg to 200Wh/kg,
And the energy density of cobalt acid lithium, LiMn2O4, LiFePO4 can not meet demand, then lithium from
Sub- battery multielement positive electrode (LiaNixCoyMn1-x-yO2) application on electric automobile is big
Scale increases.
With the raising that country is required New-energy electric vehicle, lithium ion battery multielement positive pole
The cycle life of material also turns into an index paid close attention to.It is more in order to improve lithium ion battery
The cycle life of element positive electrode, patent CN200710035746.6 is on positive electrode surface
AlF is coated, patent CN201080047968.X is in positive electrode Surface coating ZrO2, patent
CN201010162890.8 is in positive electrode Surface coating Al2O3Or TiO2Or ZrO2, patent
CN201210530292.0 is in positive electrode Surface coating AlPO4.At present, in positive electrode
Surface coating YPO4Research it is seldom, the present invention provide one kind by coating YPO4To improve
The method of anode material for lithium-ion batteries cycle performance.
The content of the invention
It is an object of the invention to provide a kind of raising anode material for lithium-ion batteries cycle performance
Method, simple to operate, technique is easily controllable, and production cost is low, short preparation period, is easy to real
Existing scale industrial production；It can make lithium ion battery that there is preferable cycle performance；Cladding
Yttrium salt is yttrium nitrate, yttrium chloride, yttrium acetate or yttrium sulfate, and raw material are readily obtained.
In order to achieve the above object, the present invention has following technical scheme：
A kind of method of raising anode material for lithium-ion batteries cycle performance of the present invention, including with
Lower step：
(1) anode material for lithium-ion batteries is dispersed in water, it is 10~70% to make solid content,
It is sufficiently stirred to ensure that material dispersion is uniform；
(2) according to YPO4With anode material for lithium-ion batteries mass ratio 0.05~3%, phase is weighed
The soluble yttrium salt of quality is answered, and is configured to the aqueous solution, is added in step (1), is stirred
Uniformly；
(3) according to mol ratio Y3+：PO4 3-=1：1, weigh (the NH of respective quality4)2HPO4,
And add in step (2), stir, fully reaction；
(4) material in step (3) is filtered, washed, after 80~150 DEG C are dried,
It is put into high temperature furnace, 400~800 DEG C of 2~8h of heat treatment；
(5) the material ultrasonic wave after heat treatment is sieved, that is, obtains being coated with YPO4Lithium from
Sub- cell positive material.
Wherein, the anode material for lithium-ion batteries is LiaNixCoyMn1-x-yO2, wherein 0.9
The ＜ y ＜ 1 of 1.2,0 ＜ x ＜ of ＜ a ＜ 1,0, and 0 ＜ x+y ＜ 1.
Wherein, described soluble yttrium salt is in yttrium nitrate, yttrium chloride, yttrium acetate, yttrium sulfate
One kind.
Due to taking above technical scheme, the advantage of the invention is that：
(1) yttrium salt of cladding is yttrium nitrate, yttrium chloride, yttrium acetate or yttrium sulfate, former material
Material is readily obtained.
(2) present invention is coated using chemical precipitation-high-temperature calcination, this method for coating behaviour
Make simply, technique is easily controllable, and production cost is low, short preparation period, it is easy to accomplish scale
Industrial production.
(3) positive electrode prepared in the process of the present invention, can have lithium ion battery preferable
Cycle performance.
Brief description of the drawings
Fig. 1 is YPO4Positive electrode LiNi before and after cladding0.5Co0.2Mn0.3O2X ray spread out
Penetrate figure.
Fig. 2 is YPO4Positive electrode LiNi before and after cladding0.5Co0.2Mn0.3O2Scanning electron show
Micro mirror figure.
Fig. 3 is YPO4Positive electrode LiNi before and after cladding0.5Co0.2Mn0.3O2Circulation figure.
In figure：1st, uncoated matrix material battery X-ray diffraction curve；2nd, the X of embodiment 1
Ray diffraction graph；3rd, the X-ray diffraction curve of embodiment 2；4th, the X ray of embodiment 3
Diffraction curve；1-1, uncoated matrix material cell performance curve；2-1, embodiment 1 are followed
Ring performance curve；3-1, embodiment 2 cycle performance curve；4-1, embodiment 3 cyclicity
Can curve；A, uncoated matrix material battery scanning electron microscope diagram shadow；B, embodiment 1
Scanning electron microscope diagram shadow；C, the scanning electron microscope diagram shadow of embodiment 2；D, reality
Apply the scanning electron microscope diagram shadow of example 3.
Embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
It is as follows the step of method of the invention referring to accompanying drawing 1- Fig. 3：
(1) anode material for lithium-ion batteries is dispersed in water, it is 10~70% to make solid content,
It is sufficiently stirred to ensure that material dispersion is uniform；
(2) according to YPO4With anode material for lithium-ion batteries mass ratio 0.05~3%, phase is weighed
The soluble yttrium salt of quality is answered, and is configured to the aqueous solution, is added in step (1), is stirred
Uniformly；
(3) according to mol ratio Y3+：PO4 3-=1：1, weigh (the NH of respective quality4)2HPO4,
And add in step (2), stir, fully reaction；
(4) material in step (3) is filtered, washed, after 80~150 DEG C are dried,
It is put into high temperature furnace, 400~800 DEG C of 2~8h of heat treatment；
(5) the material ultrasonic wave after heat treatment is sieved, that is, obtains being coated with YPO4Lithium from
Sub- cell positive material.
The preparation method of material of the present invention is illustrated with reference to specific embodiment.
Embodiment 1
Weigh 100g matrix materials LiNi0.5Co0.2Mn0.3O2, add in 500ml beakers, then
100g pure water is added, opens stirring；After stirring 5min, 0.10g Y (NO are weighed3)3·6H2O,
It is added in 10ml pure water and is configured to solution, yttrium salt solution is slowly added in material；Stir again
After mixing 5min, 0.036g (NH are added4)2HPO4, it is sufficiently stirred 30min；Then filter,
Washing, in an oven after 120 DEG C of dry 4h, it is put into high temperature furnace, 400 DEG C of heat treatment 5h；From
So it is cold go after, ultrasonic wave crosses 325 mesh sieves, that is, obtains being coated with 0.05%YPO4Positive pole material
Expect LiNi0.5Co0.2Mn0.3O2。
Embodiment 2
Weigh 100g matrix materials LiNi0.5Co0.2Mn0.3O2, add in 500ml beakers, then
100g pure water is added, opens stirring；After stirring 5min, 2.0g Y (NO are weighed3)3·6H2O,
It is added in 10ml pure water and is configured to solution, yttrium salt solution is slowly added in material；Stir again
After mixing 5min, 0.72g (NH are added4)2HPO4, it is sufficiently stirred 30min.Then filter,
Washing, in an oven after 120 DEG C of dry 4h, it is put into high temperature furnace, 400 DEG C of heat treatment 5h；From
So it is cold go after, ultrasonic wave crosses 325 mesh sieves, that is, obtains being coated with 1%YPO4Positive electrode
LiNi0.5Co0.2Mn0.3O2。
Embodiment 3
Weigh 100g matrix materials LiNi0.5Co0.2Mn0.3O2, add in 500ml beakers, then
100g pure water is added, opens stirring.After stirring 5min, 6.0g Y (NO are weighed3)3·6H2O,
It is added in 10ml pure water and is configured to solution, yttrium salt solution is slowly added in material.Stir again
After mixing 5min, 2.16g (NH are added4)2HPO4, it is sufficiently stirred 30min.Then filter,
Washing, in an oven after 120 DEG C of dry 4h, it is put into high temperature furnace, 400 DEG C of heat treatment 5h.From
So it is cold go after, ultrasonic wave crosses 325 mesh sieves, that is, obtains being coated with 3%YPO4Positive electrode
LiNi0.5Co0.2Mn0.3O2。
By embodiment 1,2,3 and uncoated matrix material, CR2016 type buttons are prepared into respectively
Battery, under room temperature condition, charging/discharging voltage scope 2.75-4.25V, 0.5C charge and discharge circulation 100
Week.From figure 3, it can be seen that cladding YPO4Afterwards, the cycle performance of embodiment 1,2,3 is not more
The battery of cladding matrix material is obviously improved；Especially embodiment 2, coat 1%YPO4
Afterwards, 0.5C charge and discharges circulate 100 weeks conservation rates and bring up to 96% or so, and uncoated matrix material
Battery conservation rate there was only 88% or so.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate the act that the present invention is made
Example, and it is not the restriction to embodiments of the present invention.For the ordinary skill of art
For personnel, other various forms of changes or change can also be made on the basis of the above description
It is dynamic.Here all embodiments can not be exhaustive.Every technical side for belonging to the present invention
Row of the obvious changes or variations that case is extended out still in protection scope of the present invention.
Claims (3)
- A kind of 1. method for improving anode material for lithium-ion batteries cycle performance, it is characterised in that Comprise the following steps：(1) anode material for lithium-ion batteries is dispersed in water, it is 10~70% to make solid content, It is sufficiently stirred to ensure that material dispersion is uniform；(2) according to YPO4With anode material for lithium-ion batteries mass ratio 0.05~3%, phase is weighed The soluble yttrium salt of quality is answered, and is configured to the aqueous solution, is added in step (1), is stirred Uniformly；(3) according to mol ratio Y3+：PO4 3-=1：1, weigh (the NH of respective quality4)2HPO4, And add in step (2), stir, fully reaction；(4) material in step (3) is filtered, washed, after 80~150 DEG C are dried, It is put into high temperature furnace, 400~800 DEG C of 2~8h of heat treatment；(5) the material ultrasonic wave after heat treatment is sieved, that is, obtains being coated with YPO4Lithium from Sub- cell positive material.
- A kind of 2. raising anode material for lithium-ion batteries cyclicity according to claim 1 The method of energy, it is characterised in that：The anode material for lithium-ion batteries is LiaNixCoyMn1-x-yO2, wherein the ＜ y ＜ 1 of 0.9 ＜ a ＜, 1.2,0 ＜ x ＜ 1,0, and 0 ＜ x+y ＜ 1.
- A kind of 3. raising anode material for lithium-ion batteries cyclicity according to claim 1 The method of energy, it is characterised in that：Described soluble yttrium salt is yttrium nitrate, yttrium chloride, acetic acid One kind in yttrium, yttrium sulfate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790321A (en) * | 2019-11-06 | 2020-02-14 | 四川富骅新能源科技有限公司 | Doped high-voltage NCA positive electrode material of lithium ion battery and preparation method thereof |
| CN111785974A (en) * | 2020-08-25 | 2020-10-16 | 中南大学 | Positive electrode coating method for sulfide solid-state lithium ion battery, positive electrode and battery |
| CN113488620A (en) * | 2021-06-28 | 2021-10-08 | 恒大新能源技术(深圳)有限公司 | Ternary positive electrode precursor and preparation method thereof, ternary positive electrode material and preparation method thereof, and lithium ion battery |
| CN114899397A (en) * | 2022-03-24 | 2022-08-12 | 楚能新能源股份有限公司 | Preparation method of lithium ion battery anode material and secondary battery |
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| CN102969482A (en) * | 2012-12-10 | 2013-03-13 | 天津巴莫科技股份有限公司 | Method for improving stability of anode material of lithium ion battery |
| CN103515594A (en) * | 2012-06-26 | 2014-01-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon coated lithium manganese phosphate/lithium iron phosphate core-shell structure material as well as preparation method thereof |
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| CN103515594A (en) * | 2012-06-26 | 2014-01-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon coated lithium manganese phosphate/lithium iron phosphate core-shell structure material as well as preparation method thereof |
| CN102969482A (en) * | 2012-12-10 | 2013-03-13 | 天津巴莫科技股份有限公司 | Method for improving stability of anode material of lithium ion battery |
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| SEN ZHAO ET AL: "Enhanced cycling stability and thermal stability of YPO4-coated LiMn2O4 cathode materials for lithium ion batteries", 《SOLID STATE IONICS》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790321A (en) * | 2019-11-06 | 2020-02-14 | 四川富骅新能源科技有限公司 | Doped high-voltage NCA positive electrode material of lithium ion battery and preparation method thereof |
| CN111785974A (en) * | 2020-08-25 | 2020-10-16 | 中南大学 | Positive electrode coating method for sulfide solid-state lithium ion battery, positive electrode and battery |
| CN113488620A (en) * | 2021-06-28 | 2021-10-08 | 恒大新能源技术(深圳)有限公司 | Ternary positive electrode precursor and preparation method thereof, ternary positive electrode material and preparation method thereof, and lithium ion battery |
| CN114899397A (en) * | 2022-03-24 | 2022-08-12 | 楚能新能源股份有限公司 | Preparation method of lithium ion battery anode material and secondary battery |
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Application publication date: 20180109 |