CN103474623A - Preparation method of negative electrode piece and electrochemical device - Google Patents
Preparation method of negative electrode piece and electrochemical device Download PDFInfo
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- CN103474623A CN103474623A CN2013104197404A CN201310419740A CN103474623A CN 103474623 A CN103474623 A CN 103474623A CN 2013104197404 A CN2013104197404 A CN 2013104197404A CN 201310419740 A CN201310419740 A CN 201310419740A CN 103474623 A CN103474623 A CN 103474623A
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Abstract
The invention discloses a preparation method of a negative electrode piece and an electrochemical device. The method comprises the following steps: a negative electrode active substance, a thickener and a water-based organic binding agent are uniformly mixed in deionized water so as to prepare a negative electrode sizing agent, the negative electrode sizing agent is coated on a current collector; the drying treatment is carried out to obtain a pre-treated negative electrode piece; the pre-treated negative electrode piece is put into an oxygen-enriched atmosphere or an air-enriched atmosphere, and is subjected to UV (ultraviolet) light irradiation; the pre-treated negative electrode piece which is subjected to the UV light irradiation in the oxygen-enriched atmosphere or air-enriched atmosphere is subjected to the surface cleaning treatment in a drying room, so as to obtain the negative electrode piece. The electrochemical device comprises the negative electrode piece prepared by using the method disclosed by the invention; the negative electrode piece is subjected to the UV light irradiation in the oxygen-enriched atmosphere or air-enriched atmosphere; by using the electrochemical device disclosed by the invention, a compact organic matter binding agent layer on the surface of the negative electrode piece can be effectively removed, so that the poriness of the surface of the negative electrode piece is increased, the infiltration capacity of the negative electrode piece can be greatly improved, and the electrochemical performances of the electrochemical device are improved.
Description
Technical field
The present invention relates to field of electrochemical devices, relate in particular to a kind of preparation method and electrochemical appliance of cathode pole piece.
Background technology
For example, in the manufacture craft of the electrode slice of electrochemical appliance (lithium ion battery), can adopt the oiliness organic binder bond, also can adopt the water-based organic binder bond.Yet with respect to the oiliness organic binder bond, the more environmental protection of water-based organic binder bond, thereby be more suitable in large-scale application.But when adopting the water-based organic binder bond and in the process of baking electrode slice, the water-based organic binder bond is easy to float, thereby can form on the surface of electrode slice fine and close organic matter layer, and then cause the porosity of electrode slice to descend, electrode slice is inner is difficult for, ion transmission performance reduction in electrode slice slow by electrolyte complete wetting or wetting velocity etc.For example the cathode pole piece of lithium ion battery can adopt water-based organic binder bond sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) usually.In the manufacturing process of electrode slice, SBR is easy to floating, thereby usually can obtain the cathode pole piece that surface has fine and close SBR layer; The porosity of this cathode pole piece is lower, the electrolyte wettability is poor, chemical property is also poor.
Therefore need to take measures to remove the organic matter binding agent layer that the electrode slice surface forms.Order first two method can be removed the organic matter binding agent layer on electrode slice surface, (1) Physical: for example the sticking object of tool of green adhesive tape and so on is attached on electrode slice, then tear, but the compacted zone on remove portion electrode slice surface, yet the method is difficult to guarantee uniformity, often cause the electrode slice surface irregularity, be difficult to guarantee product quality; (2) laser method: the sintering that can put one by one by laser, to remove surperficial organic matter layer, yet the energy comparison of laser is high, therefore has the possibility reacted with active material, and treatment effeciency is very low and lack of homogeneity, be difficult to promote on producing.
Summary of the invention
Problem in view of the background technology existence, a kind of preparation method and electrochemical appliance of cathode pole piece have been the object of the present invention is to provide, it can be effectively and processes equably the organic matter binding agent layer on cathode pole piece surface, improve the porosity of cathode pole piece, improve the wetting capacity of cathode pole piece, and then improve the chemical property of electrochemical appliance.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of preparation method of cathode pole piece, comprise step: negative electrode active material, thickener and water-based organic binder bond are evenly mixed to be prepared into cathode size in deionized water, and described cathode size is coated on collector, carry out the drying processing and obtain pretreated cathode pole piece; Pretreated cathode pole piece is sent in oxygen-enriched atmosphere or air atmosphere, used the UV irradiation; To carry out the surface cleaning processing in drying shed at the pretreated cathode pole piece after the UV irradiation in oxygen-enriched atmosphere or air atmosphere, obtain cathode pole piece.
In a second aspect of the present invention, the invention provides a kind of electrochemical appliance, it comprises cathode pole piece prepared by the preparation method according to the described cathode pole piece of first aspect present invention.
Beneficial effect of the present invention is as follows:
By use UV irradiation cathode pole piece in oxygen-enriched atmosphere or air atmosphere, the present invention can remove the organic matter binding agent layer of cathode pole piece surface compact effectively, increase the porosity on cathode pole piece surface, increase substantially the wetting capacity of cathode pole piece, improve the chemical property of electrochemical appliance.
The accompanying drawing explanation
The cathode pole piece imbibition time that Fig. 1 is embodiments of the invention and Comparative Examples;
The high rate performance of the lithium ion battery that Fig. 2 is embodiments of the invention and Comparative Examples.
Embodiment
Below describe in detail according to the preparation method of cathode pole piece of the present invention and the embodiment of electrochemical appliance.
At first preparation method according to the cathode pole piece of first aspect present invention is described.
Comprise step according to the preparation method of the cathode pole piece of first aspect present invention: negative electrode active material, thickener and water-based organic binder bond are evenly mixed to be prepared into cathode size in deionized water, and described cathode size is coated on collector, carry out the drying processing and obtain pretreated cathode pole piece; Pretreated cathode pole piece is sent in oxygen-enriched atmosphere or air atmosphere, used the UV irradiation; To carry out the surface cleaning processing in drying shed at the pretreated cathode pole piece after the UV irradiation in oxygen-enriched atmosphere or air atmosphere, obtain cathode pole piece.
By use UV irradiation cathode pole piece in oxygen-enriched atmosphere or air atmosphere, by adopting ultraviolet-By Ozone to process the surface of cathode pole piece, can make the chemical bond rupture of the macromolecular compound (being the material in water-based organic binder bond layer) on cathode pole piece surface, thereby be that gas molecules is overflowed by its oxidation Decomposition, effectively and equably the organic matter binding agent layer on cathode pole piece surface is removed in oxidation, therefore greatly improve the porosity on cathode pole piece surface, contribute to improve the wetting capacity of cathode pole piece, and then improve the chemical property of electrochemical appliance.
In the preparation method of the cathode pole piece according to first aspect present invention, also can comprise the compaction treatment step, described compaction treatment step can carry out or carry out in drying shed carrying out after the surface cleaning processing before pretreated cathode pole piece is sent into to oxygen-enriched atmosphere or air atmosphere.Preferably, described compaction treatment is cold pressing treatment.
In the preparation method of the cathode pole piece according to first aspect present invention, also can comprise itemize, soldering polar ear and slicing step, described itemize, soldering polar ear and slicing step can carry out or carry out afterwards before pretreated cathode pole piece is sent into to oxygen-enriched atmosphere or air atmosphere.
Described negative electrode active material can be the negative active core-shell materials such as inorganic salts, metal simple-substance, non-metal simple-substance or metal oxide.Particularly, negative electrode active material can be one or more in graphite, soft carbon, hard carbon, lithium titanate, Si, Sn, V, Ti or their oxide.
In the preparation method of the cathode pole piece according to first aspect present invention, described thickener can be sodium carboxymethylcellulose (CMC).
In the preparation method of the cathode pole piece according to first aspect present invention, described water-based organic binder bond can be one or more in rubber latex class, aqueous polyvinylidene fluoride (PVDF) emulsion, polyacrylonitrile-esters of acrylic acid, polyacrylate, Polystyrene-acrylate, polyethylene-ethyl acetate class binding agent.
In the preparation method of the cathode pole piece according to first aspect present invention, in described oxygen-enriched atmosphere or air atmosphere, the volume fraction of oxygen is 21%～100%.Contribute to like this oxygen to generate O under the UV irradiation
3thereby, the organic matter binding agent layer on oxidation cathode pole piece surface effectively.
In the preparation method of the cathode pole piece according to first aspect present invention, described UV light wavelength is 120nm～254nm, is preferably 120nm～186nm.When wavelength is less than 120nm, the excessive cathode pole piece that easily causes of energy is out of shape; When wavelength is greater than 254nm, energy is too little to be not enough to the organic matter binding agent layer oxidation Decomposition on cathode pole piece surface.Preferably, wave-length coverage is 120nm～186nm, because when wavelength is less than 186nm, more is conducive to O
3generation, thereby treatment effect is better.
In the preparation method of the cathode pole piece according to first aspect present invention, the irradiation time of described UV light is 0.5min～120min.When irradiation time is less than 0.5min, treatment effect is obvious not, and irradiation time is greater than 120min, loses time, and reduces production efficiency.
In the preparation method of the cathode pole piece according to first aspect present invention, the time that described surface cleaning is processed is 0.5min～5min.
In the preparation method of the cathode pole piece according to first aspect present invention, described surface cleaning is processed and is adopted the brush dust mode to carry out.Can effectively clean the dust on cathode pole piece surface like this, the mode that certainly also can adopt surface to purge.
Secondly explanation is according to the electrochemical appliance of second aspect present invention.
According to the electrochemical appliance of second aspect present invention, it comprises cathode pole piece prepared by the preparation method according to the described cathode pole piece of first aspect present invention.
In the electrochemical appliance according to second aspect present invention, described electrochemical appliance can be selected from one of them in lithium rechargeable battery, lithium ion battery, lithium ion super capacitor.
Finally illustrate according to the preparation method of cathode pole piece of the present invention and embodiment, Comparative Examples and the test result of electrochemical appliance (take lithium ion battery as example).
Embodiment 1
Prepare cathode pole piece: graphite, sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR, rubber latex class water-based organic binder bond) are evenly mixed in deionized water with mass ratio 97:1.5:1.5, make cathode size; Cathode size is stirred and be coated on copper foil of affluxion body, the drying operation makes pretreated cathode pole piece; Then it is colded pressing, then this cathode pole piece is sent in oxygen-enriched atmosphere by conveyer belt, wherein the volume fraction of oxygen is 80%, and irradiate 1min under the UV lamp that is 186nm at wavelength, obtain the cathode pole piece after UV processes, through itemize, soldering polar ear, section, then in drying shed, brush dust carries out after surface cleaning is processed 3min obtaining cathode pole piece again.
Prepare anode pole piece: cobalt acid lithium, conductive black, polyvinylidene fluoride (PVDF) are evenly mixed in 1-METHYLPYRROLIDONE (NMP) with mass ratio 95:2:3, make anode sizing agent; By anode sizing agent according to stirring, be coated on the collector aluminium foil, dry, cold pressing, the operations such as itemize, soldering polar ear, section make anode pole piece.
Prepare lithium ion battery: both positive and negative polarity pole piece and three layers of composite microporous barrier film of polypropylene, polyethylene/polypropylene are made to battery core by winding method; Then the battery case of battery core being packed into, through baking except desolventizing; Then inject electrolyte (EC:PC:DEC=1:1:1(mass ratio), 1mol/L LiPF
6); Welded seal, then through changing into, aging technique makes lithium ion battery.
Embodiment 2
Prepare cathode pole piece: graphite, CMC, SBR are evenly mixed in deionized water with mass ratio 97:1.5:1.5, make cathode size; Cathode size is stirred and be coated on copper foil of affluxion body, the drying operation makes pretreated cathode pole piece; Then by conveyer belt, be sent in oxygen-enriched atmosphere, wherein the volume fraction of oxygen is 100%, and irradiates 0.5min under the UV lamp that is 186nm at wavelength, obtains the cathode pole piece after UV processes; In drying shed, brush dust carries out after surface cleaning is processed 5min obtaining cathode pole piece again.The cathode pole piece obtained is carried out to cold pressing treatment, then carry out itemize, soldering polar ear, section, obtain cathode pole piece to be assembled.
Prepare anode pole piece: with embodiment 1
Prepare lithium ion battery: with embodiment 1
Embodiment 3
Prepare cathode pole piece: graphite, CMC, SBR are evenly mixed in deionized water with mass ratio 97:1.5:1.5, make cathode size; Cathode size is stirred and be coated on copper foil of affluxion body, the drying operation makes pretreated cathode pole piece; Then it is carried out to the hot pressing compaction treatment, then itemize, soldering polar ear, section; Then by conveyer belt, be sent in air atmosphere, wherein the volume fraction of oxygen is 21%, and irradiates 120min under the UV lamp that is 254nm at wavelength, obtains the cathode pole piece after UV processes; In drying shed, brush dust carries out after surface cleaning is processed 0.5min obtaining cathode pole piece.
Prepare anode pole piece: with embodiment 1
Prepare lithium ion battery: with embodiment 1
Embodiment 4
Prepare cathode pole piece: graphite, CMC, SBR are evenly mixed in deionized water with mass ratio 97:1.5:1.5, make cathode size; Cathode size is stirred and is coated on copper foil of affluxion body, drying, cold pressing, the operation such as itemize, soldering polar ear, itemize makes pretreated cathode pole piece; Then by conveyer belt, be sent in oxygen-enriched atmosphere, wherein the volume fraction of oxygen is 40%, and irradiates 2min under the UV lamp that is 120nm at wavelength, obtains the cathode pole piece after UV processes; In drying shed, brush dust carries out after surface cleaning is processed 3min obtaining cathode pole piece again.
Prepare anode pole piece: with embodiment 1
Prepare lithium ion battery: with embodiment 1
Embodiment 5
Prepare cathode pole piece: by graphite, CMC, LA132(polyacrylonitrile-esters of acrylic acid water-based organic binder bond) with mass ratio 97:1.5:1.5, in deionized water, evenly mix, make cathode size; By cathode size according to stirring, be coated on copper foil of affluxion body, dry, cold pressing, the operations such as itemize, soldering polar ear, section make pretreated cathode pole piece; Then by conveyer belt, be sent in oxygen-enriched atmosphere, wherein the volume fraction of oxygen is 60%, and irradiates 1.5min under the UV lamp that is 150nm at wavelength, obtains the cathode pole piece that UV processes; In drying shed, brush dust carries out after surface cleaning is processed 3min obtaining cathode pole piece again.
Prepare anode pole piece: with embodiment 1
Prepare lithium ion battery: with embodiment 1
Comparative Examples 1
Prepare cathode pole piece: except the anticathode pole piece does not carry out UV irradiation and clean, all the other are with embodiment 1.
Prepare anode pole piece: with embodiment 1
Prepare lithium ion battery: with embodiment 1
Comparative Examples 2
Prepare cathode pole piece: except the anticathode pole piece does not carry out UV irradiation and clean, all the other are with embodiment 5.
Prepare anode pole piece: with embodiment 1
Prepare lithium ion battery: with embodiment 1
Finally provide the performance of lithium ion battery test result of embodiment 1-5 and Comparative Examples 1-2.
(1) the imbibition time test of the cathode pole piece that prepared by embodiment 1-5 and Comparative Examples 1-2:
Adopt dropper to drip upper 6 electrolyte the cathode pole piece of embodiment 1-5 and Comparative Examples 1-2, record electrolyte with stopwatch and absorbed by cathode pole piece the time needed fully.
(2) high rate performance of the lithium ion battery of embodiment 1-5 and Comparative Examples 1-2 test:
Standing 5min; 0.5C constant current charge is to 4.2V, constant voltage charge is to 0.05C; Standing 5min; 0.2C constant-current discharge is to 3.0V; Standing 5min; 0.5C constant current charge is to 4.2V, constant voltage charge is to 0.05C, standing 5min;
0.5C constant-current discharge is to 3.0V; After standing 5min, with the 0.5C constant current charge, to 4.2V, constant voltage charge is to 0.05C, standing 3min;
1C is discharged to 3.0V, and the 0.5C constant current charge is to 4.2V, and constant voltage charge is to 0.05C, standing 5min;
1.5C constant-current discharge is to 3.0V; 0.5C constant current charge is to 4.2V, constant voltage charge is to 0.05C, standing 5min;
The 2C constant-current discharge is to 3.0V; Record respectively the discharge capacity (mAh) under each multiplying power.
As can be seen from Figure 1, adopt UV/O
3cathode pole piece after method is processed, the electrolyte infiltrating time of the lithium ion battery that it prepares obviously reduces, after this processes mainly due to cathode pole piece, its surface porosity factor increases, and then specific area increases, therefore greatly improved the rate of liquid aspiration of cathode pole piece, reduce infiltrating time.As can be seen from Figure 2, high rate performance has also obtained significantly and has improved.
In sum, the present invention can remove the organic matter binding agent layer of electrode slice surface compact effectively, increase the porosity on electrode slice surface, increase substantially the wetting capacity of electrode slice, improve the chemical property (such as high rate performance and cryogenic property etc.) of electrochemical appliance.
Claims (10)
1. the preparation method of a cathode pole piece comprises step:
Negative electrode active material, thickener and water-based organic binder bond are evenly mixed to be prepared into cathode size in deionized water, and described cathode size is coated on collector, carry out the drying processing and obtain pretreated cathode pole piece;
Pretreated cathode pole piece is sent in oxygen-enriched atmosphere or air atmosphere, used the UV irradiation;
To carry out the surface cleaning processing in drying shed at the pretreated cathode pole piece after the UV irradiation in oxygen-enriched atmosphere or air atmosphere, obtain cathode pole piece.
2. the preparation method of cathode pole piece according to claim 1, it is characterized in that, also comprise the compaction treatment step, described compaction treatment step carried out or carries out in drying shed carrying out after the surface cleaning processing before pretreated cathode pole piece is sent into to oxygen-enriched atmosphere or air atmosphere, and described compaction treatment is preferably cold pressing treatment.
3. the preparation method of cathode pole piece according to claim 1, is characterized in that, also comprises itemize, soldering polar ear and slicing step, and this step was carried out or carried out afterwards before pretreated cathode pole piece is sent into to oxygen-enriched atmosphere or air atmosphere.
4. the preparation method of cathode pole piece according to claim 1, is characterized in that, described negative electrode active material is one or more in graphite, soft carbon, hard carbon, lithium titanate, Si, Sn, V, Ti or their oxide; Described thickener is sodium carboxymethylcellulose.
5. the preparation method of cathode pole piece according to claim 1, it is characterized in that, described water-based organic binder bond is at least one in rubber latex class, aqueous polyvinylidene fluoride (PVDF) emulsion, polyacrylonitrile-esters of acrylic acid, polyacrylate, Polystyrene-acrylate, polyethylene-ethyl acetate class binding agent.
6. the preparation method of cathode pole piece according to claim 1, is characterized in that, in described oxygen-enriched atmosphere or air atmosphere, the volume fraction of oxygen is 21%～100%.
7. the preparation method of cathode pole piece according to claim 1, is characterized in that, described UV light wavelength is 120nm～254nm, and the irradiation time of described UV light is 0.5min～120min, and described UV light wavelength is preferably 120nm～186nm.
8. the preparation method of cathode pole piece according to claim 1, is characterized in that, the time that described surface cleaning is processed is 0.5min～5min.
9. an electrochemical appliance, is characterized in that, described electrochemical appliance comprises cathode pole piece prepared by the preparation method according to the described cathode pole piece of any one in claim 1-8.
10. electrochemical appliance according to claim 9, is characterized in that, described electrochemical appliance is selected from one of them in lithium rechargeable battery, lithium ion battery, lithium ion super capacitor.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104393303A (en) * | 2014-12-05 | 2015-03-04 | 上海空间电源研究所 | Lithium titanate battery using waterborne binder |
| CN105655592A (en) * | 2016-03-12 | 2016-06-08 | 浙江大学 | Silicon-based negative electrode of lithium ion battery and method for preparing silicon-based negative electrode of lithium ion battery |
| CN109155398A (en) * | 2016-11-21 | 2019-01-04 | 株式会社Lg化学 | Electrode and its manufacturing method for electrochemical appliance |
| CN110993884A (en) * | 2019-12-06 | 2020-04-10 | 联动天翼新能源有限公司 | Lithium ion battery negative electrode slurry, preparation method, negative electrode plate and battery |
| CN111525093A (en) * | 2019-02-01 | 2020-08-11 | 大众汽车有限公司 | Method for producing an electrode |
| CN111948542A (en) * | 2019-05-14 | 2020-11-17 | 宝山钢铁股份有限公司 | Method for rapidly evaluating electrochemical performance of silicon negative electrode material |
| CN112054164A (en) * | 2020-09-15 | 2020-12-08 | 天津市捷威动力工业有限公司 | Method and device for adding binder for lithium ion battery |
| CN112640166A (en) * | 2018-08-10 | 2021-04-09 | 株式会社丰田自动织机 | Negative electrode, method for producing negative electrode, and binder for electrode |
| CN114725370A (en) * | 2022-04-07 | 2022-07-08 | 珠海汉格能源科技有限公司 | Water-based positive electrode slurry and preparation method thereof |
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|---|---|---|---|---|
| CN104393303A (en) * | 2014-12-05 | 2015-03-04 | 上海空间电源研究所 | Lithium titanate battery using waterborne binder |
| CN105655592B (en) * | 2016-03-12 | 2019-02-05 | 浙江大学 | A kind of negative electrode of lithium ion battery and preparation method thereof based on silicon |
| CN105655592A (en) * | 2016-03-12 | 2016-06-08 | 浙江大学 | Silicon-based negative electrode of lithium ion battery and method for preparing silicon-based negative electrode of lithium ion battery |
| CN109155398B (en) * | 2016-11-21 | 2021-07-13 | 株式会社Lg化学 | Electrode for electrochemical device and method for manufacturing the same |
| CN109155398A (en) * | 2016-11-21 | 2019-01-04 | 株式会社Lg化学 | Electrode and its manufacturing method for electrochemical appliance |
| US11094921B2 (en) | 2016-11-21 | 2021-08-17 | Lg Chem, Ltd. | Electrode for electrochemical device and method for manufacturing the same |
| CN112640166A (en) * | 2018-08-10 | 2021-04-09 | 株式会社丰田自动织机 | Negative electrode, method for producing negative electrode, and binder for electrode |
| CN112640166B (en) * | 2018-08-10 | 2023-10-27 | 株式会社丰田自动织机 | Negative electrode, method for producing negative electrode, and binder for electrode |
| CN111525093A (en) * | 2019-02-01 | 2020-08-11 | 大众汽车有限公司 | Method for producing an electrode |
| CN111948542A (en) * | 2019-05-14 | 2020-11-17 | 宝山钢铁股份有限公司 | Method for rapidly evaluating electrochemical performance of silicon negative electrode material |
| CN110993884A (en) * | 2019-12-06 | 2020-04-10 | 联动天翼新能源有限公司 | Lithium ion battery negative electrode slurry, preparation method, negative electrode plate and battery |
| CN110993884B (en) * | 2019-12-06 | 2021-07-23 | 联动天翼新能源有限公司 | Lithium ion battery negative electrode slurry, preparation method, negative electrode plate and battery |
| CN112054164A (en) * | 2020-09-15 | 2020-12-08 | 天津市捷威动力工业有限公司 | Method and device for adding binder for lithium ion battery |
| CN114725370A (en) * | 2022-04-07 | 2022-07-08 | 珠海汉格能源科技有限公司 | Water-based positive electrode slurry and preparation method thereof |
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