CN106450553B - A kind of production technology that lithium ion battery ternary material production thin powder recovery recycles - Google Patents
A kind of production technology that lithium ion battery ternary material production thin powder recovery recycles Download PDFInfo
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- CN106450553B CN106450553B CN201610975705.4A CN201610975705A CN106450553B CN 106450553 B CN106450553 B CN 106450553B CN 201610975705 A CN201610975705 A CN 201610975705A CN 106450553 B CN106450553 B CN 106450553B
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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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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses the production technologies that a kind of lithium ion battery ternary material production thin powder recovery recycles.1) lithium ion battery ternary material production fine powder, fluxing agent and solvent the following steps are included: be mixed into slurry by it；2) slurry it is spray-dried after, be made powder；3) obtaining ternary material after powder sintering.Present invention process is simple, low for equipment requirements, high production efficiency, can direct large-scale production；The compacted density that material can be significantly improved reduces the pH of material, improves the processing performance of material；The side reaction that material and electrolyte can be reduced improves the cycle performance and high-temperature behavior of material；The manufacturing cost of enterprise can be reduced, and avoids environmental pollution.
Description
Technical field
The present invention relates to the production technologies that a kind of lithium ion battery ternary material production thin powder recovery recycles.
Background technique
Ternary material is the anode material of lithium battery newly risen in recent years, and such material combines three kinds of nickel, cobalt, manganese elements
The characteristics of, there is stable chemical property, high-energy density, high discharge-rate, thermal stability are good, safety is good, price
Cheap, occupation rate of market is high, and future probably occupies main status in power market.However due to its own production technology
Characteristic inevitably generates fine powder in process of production, and fine powder seriously affects the electrical property and processing performance of material, enterprise
In order to guarantee that product is with good performance, common practices is to separate fine powder, then using fine powder as waste disposal, is increased
The manufacturing cost for having added enterprise causes certain environmental pollution.
Summary of the invention
The purpose of the present invention is to provide the production works that a kind of lithium ion battery ternary material production thin powder recovery recycles
Skill makes primary particle grow up again, improves its electrical property and processing performance, thin powder recovery is utilized, and reduces enterprise's manufacturing cost,
Avoid environmental pollution.
Technical scheme is as follows:
A kind of production technology that lithium ion battery ternary material production thin powder recovery recycles, comprising the following steps:
1) lithium ion battery ternary material production fine powder, fluxing agent and solvent are mixed into slurry；
2) slurry it is spray-dried after, be made powder；
3) obtaining ternary material after powder sintering.
The lithium ion battery ternary material production fine powder is consisting of LiNixCoyMnzO2, wherein 0 < x < 1,0 < y < 1,
0 < z < 1, and x+y+z=1.
In step 1), the ternary material production fine powder partial size is 400 ~ 600nm.
In step 1), the fluxing agent is at least one of lithium compound, boron compound, silicon compound.
In step 1), the solvent is polar solvent.
In step 1), the mass ratio of fluxing agent and ternary material production fine powder is (0.5 ~ 5): 100.
In step 1), the mass ratio of solvent and ternary material production fine powder is 1:(1 ~ 4).
In step 3), the sintering atmosphere is oxygen；Its concentration of oxygen atmosphere is 30 ~ 90%.
In step 3), the sintering temperature is 900 ~ 1000 DEG C, and sintering time is 4 ~ 16h.
In step 3), the ternary material partial size is 2 ~ 5 μm.
Beneficial effects of the present invention are as follows:
(1) the method for the present invention simple process, low for equipment requirements, high production efficiency can direct large-scale production；(2)
The compacted density that material can be significantly improved reduces the pH of material, improves the processing performance of material；(3) can reduce material with
The side reaction of electrolyte improves the cycle performance and high-temperature behavior of material；(4) manufacturing cost of enterprise can be reduced, and is avoided
Environmental pollution.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph that embodiment 1 produces fine powder；
Fig. 2 is that embodiment 1 produces thin powder recovery treated scanning electron microscope (SEM) photograph；
Fig. 3 is the room temperature 1C circulation figure that embodiment 1 produces that battery is made in fine powder；
Fig. 4 is that embodiment 1 produces the room temperature 1C circulation figure that battery is made after thin powder recovery is handled.
Specific embodiment
A kind of production technology that lithium ion battery ternary material production thin powder recovery recycles, comprising the following steps:
1) lithium ion battery ternary material production fine powder, fluxing agent and solvent are mixed into slurry；
2) slurry it is spray-dried after, be made powder；
3) obtaining ternary material after powder sintering.
Preferably, lithium ion battery ternary material production fine powder is consisting of LiNixCoyMnzO2, wherein 0 < x <
1,0 < y < 1,0 < z < 1, and x+y+z=1；It is further preferred that the described lithium ion battery ternary material production fine powder consisting of
LiNi0.5Co0.2Mn0.3、LiNi1/3Co1/3Mn1/3、LiNi0.4Co0.3Mn0.3、LiNi0.6Co0.2Mn0.2、LiNi0.8Co0.1Mn0.1In
At least one；Still further preferably, the described lithium ion battery ternary material production fine powder consisting of
LiNi0.5Co0.2Mn0.3。
Preferably, in step 1), the ternary material production fine powder partial size is 400 ~ 600nm；It is further preferred that step
It is rapid 1) in, the described ternary material production fine powder partial size is 450 ~ 550nm.
Preferably, in step 1), the fluxing agent is at least one of lithium compound, boron compound, silicon compound；
It is further preferred that the fluxing agent is lithium fluoride, lithium chloride, lithia, lithium carbonate, lithium phosphate, hydroxide in step 1)
At least one of lithium, diboron trioxide, boric acid, borax, silica, silicic acid；Still further preferably, in step 1), institute
The fluxing agent stated is at least one of lithium fluoride, lithium carbonate, lithium hydroxide, diboron trioxide.
Preferably, in step 1), the solvent is polar solvent；It is further preferred that in step 1), the solvent
For at least one of water, alcohol, ketone；Still further preferably, in step 1), the solvent be water, methanol, ethyl alcohol, propyl alcohol,
At least one of isopropanol, acetone, espeleton, methylisobutylketone, n-formyl sarcolysine yl pyridines alkanone；Still further preferably, it walks
It is rapid 1) in, the solvent be at least one of water, methanol, ethyl alcohol, propyl alcohol, n-formyl sarcolysine yl pyridines alkanone；Still further preferably
, in step 1), the solvent is at least one of methanol, ethyl alcohol, n-formyl sarcolysine yl pyridines alkanone.
Preferably, in step 1), the mass ratio of fluxing agent and ternary material production fine powder is (0.5 ~ 5): 100；Further
Preferably, in step 1), the mass ratio of fluxing agent and ternary material production fine powder is (1 ~ 4): 100.
Preferably, in step 1), the mass ratio of solvent and ternary material production fine powder is 1:(1 ~ 4)；It is further preferred that
In step 1), the mass ratio of solvent and ternary material production fine powder is 1:(2 ~ 3).
Preferably, in step 1), the mixing machine revolving speed is 800 ~ 1200rp, and incorporation time is 10 ~ 50min；Into one
Step is preferred, and in step 1), the mixing machine revolving speed is 800 ~ 1200rpm, and incorporation time is 20 ~ 40min.
Preferably, in step 3), the sintering atmosphere is oxygen；Its concentration of oxygen atmosphere is 30 ~ 90%.
Preferably, in step 3), the sintering temperature is 900 ~ 1000 DEG C, and sintering time is 4 ~ 16h；Further preferably
, in step 3), the sintering temperature is 900 ~ 1000 DEG C, and sintering time is 8 ~ 12h；Still further preferably, step 3)
In, the sintering temperature is 920 ~ 980 DEG C, and sintering time is 8 ~ 12h.
Preferably, in step 3), the ternary material partial size is 2 ~ 5 μm；It is further preferred that in step 3), it is described
Ternary material partial size be 2.5 ~ 3.5 μm.
Preferably, in step 3), the ternary material is ball-type or class ball-type.
The contents of the present invention are described in further detail below by way of specific embodiment.
Embodiment 1
(1) ternary material (LiNi is weighed0.5Co0.2Mn0.3) production fine powder 1000g, lithium hydroxide 10g, lithium fluoride 5g, nothing
Water-ethanol 500g, while being added in high-speed mixer, 30min is mixed at revolving speed 1000rpm, obtains uniformly mixed slurry；
(2) revolving speed is adjusted to 300rpm, guarantees that slurry is uniform, by metering pump slurry be pumped into spray dryer into
Row drying obtains uniformly mixed powder；
(3) powder 500g obtained in above-mentioned (2) is taken, is placed in and is connected with 50% oxygen concentration, the atmosphere of Ventilation Rate 1L/min
In furnace, in 950 DEG C of sintering 10h, temperature rate control obtains the ternary material that primary particle is 3um or so in 2 DEG C/min.
The pattern that fine powder is produced in the present embodiment is as shown in Fig. 1, the ternary material fine powder pattern attached drawing 2 after recovery processing
It is shown.It is compared by two figures as it can be seen that producing one of primary particle of the fine powder before recovery processing after 500nm or so, recovery processing
Secondary particle obviously becomes larger in 3um or so, primary particle.The ternary material particle obtained after recovery processing is in class ball-type.
It is anode with ternary material production fine powder, using lithium piece as cathode, 2032 button cells is made, in 0.2C, 1C multiplying power
Under, it is tested under 4.3-3.0V voltage ranges, 0.2C discharges gram volume 171.1mAh/g for the first time, and electric discharge gram is held under 1C multiplying power
162.0mAh/g is measured, 1C recycles 100 capacity retention ratios 89.6%, and battery room temperature 1C circulation figure is as shown in Fig. 3.
To produce the ternary material after thin powder recovery utilizes as anode, using lithium piece as cathode, 2032 button cells are made,
Under 0.2C, 1C multiplying power, being tested under 4.3-3.0V voltage ranges, 0.2C discharges gram volume 171.53mAh/g for the first time, and 1C times
Discharge gram volume 161.5mAh/g under rate, and 1C recycles 100 capacity retention ratios 98.8%, and battery room temperature 1C circulation figure is such as 4 institute of attached drawing
Show.As it can be seen that the cycle performance of battery obviously improves after ternary material is produced the recovered processing of fine powder.
Embodiment 2
(1) ternary material (LiNi is weighed0.5Co0.2Mn0.3) production fine powder 1000g, lithium carbonate 10g, diboron trioxide 5g,
Dehydrated alcohol 400g, n-formyl sarcolysine yl pyridines alkanone 100g, while being added in high-speed mixer, it is mixed at revolving speed 1000rpm
30min obtains uniformly mixed slurry；
(2) revolving speed is adjusted to 300rpm, guarantees that slurry is uniform, by metering pump slurry be pumped into spray dryer into
Row drying obtains uniformly mixed powder；
(3) powder 500g obtained in above-mentioned (2) is taken, is placed in and is connected with 90% oxygen concentration, the atmosphere of Ventilation Rate 1L/min
In furnace, in 940 DEG C of sintering 10h, temperature rate control obtains the ternary material that primary particle is 3um or so in 2 DEG C/min.
Embodiment 3
(1) ternary material (LiNi is weighed0.5Co0.2Mn0.3) production fine powder 1000g, lithium carbonate 15g, lithium fluoride 25g, methanol
400g, while being added in high-speed mixer, 20min is mixed at revolving speed 1200rpm, obtains uniformly mixed slurry；
(2) revolving speed is adjusted to 300rpm, guarantees that slurry is uniform, by metering pump slurry be pumped into spray dryer into
Row drying obtains uniformly mixed powder；
(3) powder 500g obtained in above-mentioned (2) is taken, is placed in and is connected with 70% oxygen concentration, the atmosphere of Ventilation Rate 1L/min
In furnace, in 980 DEG C of sintering 8h, temperature rate control obtains the ternary material that primary particle is 3um or so in 2 DEG C/min.
Embodiment 4
(1) ternary material (LiNi is weighed0.5Co0.2Mn0.3) production fine powder 1000g, lithium hydroxide 5g, diboron trioxide 5g,
Methanol 300g, n-formyl sarcolysine yl pyridines alkanone 50g, while being added in high-speed mixer, 40min is mixed at revolving speed 800rpm, is obtained
Uniformly mixed slurry；
(2) revolving speed is adjusted to 300rpm, guarantees that slurry is uniform, by metering pump slurry be pumped into spray dryer into
Row drying obtains uniformly mixed powder；
(3) powder 500g obtained in above-mentioned (2) is taken, is placed in and is connected with 30% oxygen concentration, the atmosphere of Ventilation Rate 1L/min
In furnace, in 920 DEG C of sintering 12h, temperature rate control obtains the ternary material that primary particle is 3um or so in 2 DEG C/min.
Claims (1)
1. a kind of production technology that lithium ion battery ternary material production thin powder recovery recycles, it is characterised in that: including following
Step:
1) lithium ion battery ternary material production fine powder, fluxing agent and solvent are mixed into slurry；
2) slurry it is spray-dried after, be made powder；
3) obtaining ternary material after powder sintering；
The lithium ion battery ternary material production fine powder is consisting of LiNi0.5Co0.2Mn0.3O2；
In step 1), the ternary material production fine powder partial size is 450~550nm；
In step 1), the fluxing agent is at least one of lithium fluoride, lithium carbonate, lithium hydroxide, diboron trioxide；
In step 1), the solvent is at least one of methanol, ethyl alcohol, n-formyl sarcolysine yl pyridines alkanone；
In step 1), the mass ratio of fluxing agent and ternary material production fine powder is (1~4): 100；
In step 1), the mass ratio of solvent and ternary material production fine powder is 1:(2~3)；
In step 3), the sintering atmosphere is oxygen；Its concentration of oxygen atmosphere is 30~90%；
In step 3), the sintering temperature is 920~980 DEG C, and sintering time is 8~12h；
In step 3), the ternary material partial size is 2.5~3.5 μm.
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| CN109494364A (en) * | 2018-11-09 | 2019-03-19 | 浙江德升新能源科技有限公司 | A kind of preparation method of spherical nickel cobalt manganese ternary material |
| CN110137488B (en) * | 2019-05-28 | 2021-07-02 | 郑州中科新兴产业技术研究院 | High-nickel positive electrode material for lithium secondary battery and preparation method thereof |
| CN111943283A (en) * | 2020-08-13 | 2020-11-17 | 松山湖材料实验室 | Positive electrode active material, preparation method thereof, secondary battery positive electrode and lithium battery |
| CN114988488A (en) * | 2022-06-24 | 2022-09-02 | 合肥融捷能源材料有限公司 | Application of lithium cobaltate fine powder in preparation of lithium cobaltate positive electrode material |
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| CN101369651A (en) * | 2008-09-27 | 2009-02-18 | 浙江华友钴业股份有限公司 | Novel method for preparing lithium ion battery anode ternary material LiCoxNiyMn2O2 |
| CN102751549A (en) * | 2012-07-04 | 2012-10-24 | 中国科学院过程工程研究所 | Full-component resource reclamation method for waste positive electrode materials of lithium ion batteries |
| CN105990617A (en) * | 2015-02-28 | 2016-10-05 | 微宏动力***（湖州）有限公司 | Method for recycling and regenerating waste lithium ion battery electrode materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101369651A (en) * | 2008-09-27 | 2009-02-18 | 浙江华友钴业股份有限公司 | Novel method for preparing lithium ion battery anode ternary material LiCoxNiyMn2O2 |
| CN102751549A (en) * | 2012-07-04 | 2012-10-24 | 中国科学院过程工程研究所 | Full-component resource reclamation method for waste positive electrode materials of lithium ion batteries |
| CN105990617A (en) * | 2015-02-28 | 2016-10-05 | 微宏动力***（湖州）有限公司 | Method for recycling and regenerating waste lithium ion battery electrode materials |
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