CN105470460B - A kind of anode plate for lithium ionic cell and preparation method thereof - Google Patents
A kind of anode plate for lithium ionic cell and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of anode plate for lithium ionic cell and preparation method thereof.The anode plate for lithium ionic cell includes: negative current collector, coated on the negative electrode material layer on collector and coated on the soft carbon layer on negative electrode material layer.The production method of the anode plate for lithium ionic cell the following steps are included: negative electrode slurry preparation；Negative electrode slurry coating；The preparation of soft carbon slurry；The coating of soft carbon slurry；Negative electrode tab rolls.Soft carbon slurry is uniformly coated on negative electrode material layer the compatibility that can not only increase negative electrode tab and electrolyte by the present invention, reduce the generation of cathode and electrolyte side reaction, the expansion of cathode can also be reduced to a certain extent, to improve the cycle performance of battery, while it can also improve the cryogenic property of battery.
Description
Technical field
The present invention relates to field of lithium ion battery, and more particularly to a kind of good cycle, cycle life is high, while also can
Improve the anode plate for lithium ionic cell of cryogenic property and preparation method thereof of battery.
Background technique
With the fast development of electric vehicle and hybrid-power electric vehicle, for having higher power density and energy density,
It is suitable for the power-type lithium ion battery of fast charging and discharging and the energy type lithium ion battery with more permanent cruising ability
Demand it is very urgent.
With the development of lithium ion battery industry, lithium ion battery applications are more and more wider, and market is to lithium ion battery
It is required that it is also higher and higher, it is especially higher and higher to the energy density requirement of lithium ion battery, especially in electric vehicle engineering
Improved day by day today, lithium-ion-power cell not only require in the continuation of the journey for having higher energy density to guarantee electric car
Journey, while it being also required to the cycle life for having excellent, and core one of of the negative electrode material as lithium ion battery, guarantee negative
Improving its cycle life while the material high capacity of pole is also one of the effective way to solve the above problems.
101807725 A of Chinese patent publication No. CN, date of publication on August 18th, 2010, entitled lithium ion battery should
Application case discloses a kind of lithium ion battery, and cathode sheets, anode strip and the isolation of electrode group are wound into including battery case and stacking
Film, cathode sheets include cathode current collector and the cathode diaphragm that is attached on cathode current collector, anode strip include anode collector and
The anode diaphragm being attached in anode collector, between isolation film interval and adjacent anode and cathode slice, cathode current collector is by graphite
Material is made, and cathode sheets and anode strip are respectively in the width direction equipped with the exposed division of uncoated Yin/Yang pole diaphragm, exposed division
It is electrically connected as tab on the cathode and anode of battery case.Disadvantage is that cycle life is short, specific capacity is low.
Summary of the invention
It is an object of the invention in order to solve existing lithium ion battery negative material using natural graphite battery be followed
The defect of ring performance difference and provide good cycle, cycle life is high, at the same can also improve battery cryogenic property lithium from
Sub- battery cathode sheet.
Another object of the present invention is to provide a kind of production methods of anode plate for lithium ionic cell.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of anode plate for lithium ionic cell, including negative current collector coat negative electrode material layer on the negative current collector, bear
Soft carbon layer is coated in the material layer of pole, the soft carbon layer is made of soft carbon, conductive agent and binder.In the technical scheme, soft
The interplanar distance of carbon material is big compared with graphite material, and material deformation is relatively small during lithium ion is embedded in, especially in height
In the case where rate charge-discharge, negative electrode material peeling and dusting are not easily caused, can effectively inhibit the decaying of battery capacity.It is another
Aspect, soft carbon material is good with compatibility of electrolyte, and the SEI membrane structure formed on the surface thereof is form compact and stable, while can be effectively
The total insertion for preventing solvent molecule, effectively improves cycle performance of battery.
Preferably, negative electrode material composition and weight percentage of each component are respectively as follows: negative electrode active material 88-96%, conduction
Agent 0.5-6%, sodium carboxymethylcellulose 1-2.5%, butadiene-styrene rubber 1.5-3.5%.
Preferably, the negative electrode active material is the mixing of one or both of electrographite, natural graphite, conductive agent
For the mixing of one or more of conductive black, superconduction carbon, electrically conductive graphite, carbon nano-fiber or carbon nanotube, butadiene-styrene rubber is
Emulsion form, solid content 50%.
Preferably, the component and its weight percent of soft carbon layer are respectively soft carbon 80-96%, conductive agent 2-10%, bonding
Agent 2-10%.
Preferably, conductive agent is one in conductive black, superconduction carbon, electrically conductive graphite, carbon nano-fiber and carbon nanotube
Kind is several, and binder is Kynoar.
Preferably, the copper foil that collector is 5-15 μm of thickness.
A kind of production method of anode plate for lithium ionic cell, the preparation method include the following steps:
A) preparation of negative electrode slurry: sodium carboxymethylcellulose CMC is dissolved in deionized water, after agitated dispersion 3-5h
Then conductive agent is added in CMC glue and carries out being dispersed with stirring for 1-2h, then by the CMC glue for being 1.6-1.8% to solid content
Divide n times that negative electrode active material is added, the interval time that each negative electrode material is added is 0.5h, and each additional amount is negative electrode active
The 1/n of substance gross mass adds styrene butadiene rubber sbr, deionized water is added after uniform stirring 2-4h after high-speed stirred 5-6h
Slurry viscosity adjusting is carried out, slurry viscosity is controlled in 2000-8000cps；
B) negative electrode slurry for obtaining step a) is uniformly coated on negative current collector copper foil, through 80-110 DEG C, 10-
Coated negative electrode material layer is obtained after 12h baking is dry；
C) preparation of soft carbon slurry: first Kynoar is dissolved in organic solvent N-Methyl pyrrolidone, is stirred through 4-12h
The glue for obtaining solid content in a solvent as 4-10% is made it completely dissolved after mixing, then conductive agent is dispersed in above-mentioned glue, is passed through
The high speed dispersion that soft carbon powder carries out 2-4h is added after the high-speed stirred dispersion of 1-2h, slurry viscosity is controlled in 6000-
10000cps；
D) the soft carbon slurry that step c) obtains is uniformly coated on the negative electrode material layer of step b) completion, through 90-
105 DEG C, semi-finished product negative electrode tab is obtained after 12-16h baking is dry.
Preferably, the thickness of negative electrode material layer and soft carbon layer is than range in 5:1-25:1, the thickness control of negative electrode material layer
System is at 100-200 μm, and the thickness control of soft carbon layer is at 4-40 μm.
Preferably, compacted density when negative electrode tab rolls is 1.2-1.5g/cm3。
The beneficial effects of the present invention are:
1) lithium ion battery negative material raw material sources provided by the invention are wide, and preparation method is simple, lithium obtained
Ion battery cathode material has high capacity, high rate capability, and stable structure, is not easy to react with electrolyte, not occur
Reunite, so that lithium ion battery durability with higher and cyclical stability；
2) interplanar distance of soft carbon material is big compared with graphite material, lithium ion be embedded in deviate from during material deformation relatively
It is small, especially in the case where high power charging-discharging, negative electrode material peeling and dusting are not easily caused, can effectively inhibit battery capacity
Decaying.On the other hand, soft carbon material is good with compatibility of electrolyte, and the SEI membrane structure formed on the surface thereof is form compact and stable, together
When can be effectively prevented the total insertion of solvent molecule, effectively improve cycle performance of battery；
3) soft carbon slurry is uniformly coated on negative electrode material layer by the present invention can not only increase negative electrode tab and electrolyte
Compatibility reduces the generation of cathode and electrolyte side reaction, can also reduce to a certain extent the expansion of cathode, to improve electricity
The cycle performance in pond, while can also improve the cryogenic property of battery.
Detailed description of the invention
Fig. 1 is that the embodiment of the present invention 1 and comparative example 1 recycle contrast curve chart.
Specific embodiment
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art.
Embodiment 1
A kind of production method of anode plate for lithium ionic cell, the production method include the following steps: a) negative electrode slurry
Preparation: 20g sodium carboxymethylcellulose CMC is dissolved in 1230g deionized water, obtaining solid content after agitated dispersion 5h is about
Then 10g VGCF and 10g SP are added in CMC glue and carry out being dispersed with stirring for 1h, then by 935g by 1.6% CMC glue
Natural graphite average mark 2 times additions, the interval time that 2 negative electrode materials are added are that 0.5h is added after high-speed stirred 3h
The styrene butadiene rubber sbr lotion that 25g solid content is 50%, detection slurry viscosity is 2600cps after uniform stirring 2h, and slurry is solid at this time
Content is 36%；
B) negative electrode slurry prepared is uniformly coated on a thickness of on 10 μm of negative current collector copper foils, coats surface density
For 200g/m2, through 100 DEG C, coated negative electrode material layer is obtained after 10h baking is dry.
40g Kynoar: being first dissolved in 460g organic solvent N-Methyl pyrrolidone by the c) preparation of soft carbon slurry, warp
It is made it completely dissolved after 6h stirring and obtains solid content in a solvent and be 8% glue, then 60g conductive agent VGCF is dispersed to above-mentioned
In glue, the high speed dispersion that 900g soft carbon powder carries out 3h is added after the dispersion of the high-speed stirred of 1h, 300gN- first is added later
Base pyrrolidones carries out viscosity-adjusting agent, and final slurry viscosity is 8400cps, solid content 56.7%；
D) the soft carbon slurry prepared is uniformly coated on the negative electrode material layer that above-mentioned preparation is completed, coats surface density
For 25g/m2, through 105 DEG C, semi-finished product negative electrode tab is obtained after 14h baking is dry.At this time negative electrode material layer with a thickness of 186 μm, it is soft
Carbon-coating with a thickness of 29 μm.
Obtained semi-finished product negative electrode tab is first rolled, compacted density 1.4g/cm3, then it is washed into our institutes
The negative electrode tab of the shape needed.
Negative electrode tab made from above procedure is assembled into flexible-packed battery.Positive electrode is using LiNi1/3Co1/3Mn1/ 3O2Positive electrode.
Embodiment 2
A kind of production method of anode plate for lithium ionic cell, the production method include the following steps: a) negative electrode slurry
Preparation: 10g sodium carboxymethylcellulose CMC is dissolved in 545.55g deionized water, obtaining solid content after agitated dispersion 4h is about
Then 2.5g electrically conductive graphite and 2.5g SP are added in CMC glue and carry out being dispersed with stirring for 1.5h, then by 1.8% CMC glue
960g natural graphite average mark 4 times are added, the interval time that each negative electrode material is added is 0.5h, through high-speed stirred 5.5h
Afterwards, the styrene butadiene rubber sbr lotion that 15g solid content is 50% is added, detection slurry viscosity is 5600cps after uniform stirring 3h, this
When slurry solid content be 46%；
B) negative electrode slurry prepared is uniformly coated on a thickness of on 15 μm of negative current collector copper foils, coats surface density
For 200g/m2, through 80 DEG C, coated negative electrode material layer is obtained after 12h baking is dry.
20g Kynoar: being first dissolved in 480g organic solvent N-Methyl pyrrolidone by the c) preparation of soft carbon slurry, warp
It is made it completely dissolved after 4h stirring and obtains solid content in a solvent as 4% glue, then 20g conductive agent carbon nanotube is dispersed to
In above-mentioned glue, the high speed dispersion that 960g soft carbon powder carries out 2h is added after the dispersion of the high-speed stirred of 1.5h, is added later
300gN- methyl pyrrolidone carries out viscosity-adjusting agent, and final slurry viscosity is 8400cps, solid content 56.7%；
D) the soft carbon slurry prepared is uniformly coated on the negative electrode material layer that above-mentioned preparation is completed, coats surface density
For 25g/m2, through 90 DEG C, semi-finished product negative electrode tab is obtained after 16h baking is dry.At this time negative electrode material layer with a thickness of 100 μm, it is soft
Carbon-coating with a thickness of 4 μm.
Obtained semi-finished product negative electrode tab is first rolled, compacted density 1.2g/cm3, then it is washed into our institutes
The negative electrode tab of the shape needed.
Negative electrode tab made from above procedure is assembled into flexible-packed battery.Positive electrode is using LiNi1/3Co1/3Mn1/ 3O2Positive electrode.
Embodiment 3
A kind of production method of anode plate for lithium ionic cell, the production method include the following steps: a) negative electrode slurry
Preparation: 25g sodium carboxymethylcellulose CMC is dissolved in 1641.67g deionized water, obtains solid content about after agitated dispersion 5h
For 1.5% CMC glue, then 60g superconduction carbon is added in CMC glue and carries out being dispersed with stirring for 2h, then by 880g natural stone
Ink is averagely added three times, and the interval time that each negative electrode material is added is that 0.5h adds 35g and contain admittedly after high-speed stirred 6h
The styrene butadiene rubber sbr lotion for being 50% is measured, detection slurry viscosity is 8000cps after uniform stirring 4h, and slurry solid content is at this time
36%；
B) negative electrode slurry prepared is uniformly coated on a thickness of on 5 μm of negative current collector copper foils, coats surface density
For 200g/m2, through 110 DEG C, coated negative electrode material layer is obtained after 11h baking is dry；
100g Kynoar: being first dissolved in 900g organic solvent N-Methyl pyrrolidone by the c) preparation of soft carbon slurry,
It is made it completely dissolved after 12h is stirred and obtains solid content in a solvent as 10% glue, then 50g conductive agent VGCF and 50g is surpassed
It leads carbon to be dispersed in above-mentioned glue, the high speed dispersion that 800g soft carbon powder carries out 4h is added after the dispersion of the high-speed stirred of 2h, it
300gN- methyl pyrrolidone is added afterwards and carries out viscosity-adjusting agent, final slurry viscosity is 10000cps, solid content 56.7%；
D) the soft carbon slurry prepared is uniformly coated on the negative electrode material layer that above-mentioned preparation is completed, coats surface density
For 25g/m2, through 100 DEG C, semi-finished product negative electrode tab is obtained after 16h baking is dry.At this time negative electrode material layer with a thickness of 200 μm, it is soft
Carbon-coating with a thickness of 40 μm.
Obtained semi-finished product negative electrode tab is first rolled, compacted density 1.5g/cm3, then it is washed into our institutes
The negative electrode tab of the shape needed.
Negative electrode tab made from above procedure is assembled into flexible-packed battery.Positive electrode is using LiNi1/3Co1/3Mn1/ 3O2Positive electrode.
Comparative example 1
Negative electrode material layer coated in above-described embodiment 1 directly roll punching as negative electrode tab, then by its group
Dress up the flexible-packed battery in same embodiment 1.
By in embodiment 1 battery and comparative example 1 in battery charge and discharge blanking voltage be 2.7-4.2V under the conditions of into
Row 1C/1C charge-discharge test, below table are the capacity of two kinds of batteries, weight, the information of energy density:
| Battery capacity (Ah) | Battery weight (g) | Battery energy density (Wh/kg) | |
| Embodiment 1 | 38.5 | 830 | 170 |
| Comparative example 1 | 38.5 | 810 | 173 |
By in embodiment 1 battery and comparative example 1 in battery charge and discharge blanking voltage be 2.7-4.2V under the conditions of into
The test of row 1C/1C charge-discharge performance, is shown in Fig. 1；
As seen from the above table, under same battery system, the energy density of 1 battery of embodiment is also slightly below 1 electricity of comparative example
Pond.But improve clearly from 1 battery of embodiment from the point of view of above circulation comparison diagram relative to the cycle performance of comparative example 1, warp
550 weeks charge and discharge cycles are crossed, the capacity retention ratio of 1 battery of embodiment is 87.79%, and the capacity retention ratio of 1 battery of comparative example
It is 83.98%.Result above is summarized it is found that the energy density of 1 battery of embodiment has reduction slightly compared with comparative example 1, but reduces width
Degree influences less, while cycle performance is but greatly improved.
Claims (1)
1. a kind of production method of anode plate for lithium ionic cell, which is characterized in that the production method includes the following steps:
A) preparation of negative electrode slurry: 20g sodium carboxymethylcellulose CMC is dissolved in 1230g deionized water, after agitated dispersion 5h
The CMC glue that solid content is 1.6% is obtained, then 10g VGCF and 10g SP are added in CMC glue to the stirring point for carrying out 1h
It dissipates, then 935g natural graphite average mark 2 times is added, the interval time that 2 negative electrode materials are added is 0.5h, through high-speed stirred
After 3h, the styrene butadiene rubber sbr lotion that 25g solid content is 50% is added, detection slurry viscosity is 2600cps after uniform stirring 2h,
Slurry solid content is 36% at this time；
B) negative electrode slurry prepared is uniformly coated on a thickness of on 10 μm of negative current collector copper foils, coating surface density is
200g/m2, through 100 DEG C, coated negative electrode material layer is obtained after 10h baking is dry；
C) preparation of soft carbon slurry: first 40g Kynoar is dissolved in 460g organic solvent N-Methyl pyrrolidone, is stirred through 6h
It is made it completely dissolved after mixing and obtains solid content in a solvent as 8% glue, then 60g conductive agent VGCF is dispersed to above-mentioned glue
In, the high speed dispersion that 900g soft carbon powder carries out 3h is added after the dispersion of the high-speed stirred of 1h, 300gN- methyl pyrrole is added later
Pyrrolidone carries out viscosity-adjusting agent, and final slurry viscosity is 8400cps, solid content 56.7%；
D) the soft carbon slurry prepared is uniformly coated on the negative electrode material layer that above-mentioned preparation is completed, coating surface density is
25g/m2, through 105 DEG C, semi-finished product negative electrode tab is obtained after 14h baking is dry；
Negative electrode material layer with a thickness of 186 μm, soft carbon layer with a thickness of 29 μm；
Obtained semi-finished product negative electrode tab is first rolled, compacted density 1.4g/cm3, then it is washed into required shape
Negative electrode tab.
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| PL3958353T3 (en) * | 2020-04-30 | 2023-10-23 | Contemporary Amperex Technology Co., Limited | Secondary battery, process for preparing the same and apparatus containing the secondary battery |
| CN115224238B (en) * | 2022-09-20 | 2022-11-29 | 河南锂动电源有限公司 | Lithium ion battery negative pole piece, manufacturing method thereof and laser carbonization device |
| CN116093267B (en) * | 2022-12-31 | 2024-06-25 | 安徽理士新能源发展有限公司 | Preparation method of negative electrode slurry, negative electrode plate and lithium battery |
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