CN109950549A - A kind of lithium ion battery collector and preparation method thereof - Google Patents
A kind of lithium ion battery collector and preparation method thereof Download PDFInfo
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- CN109950549A CN109950549A CN201910304907.XA CN201910304907A CN109950549A CN 109950549 A CN109950549 A CN 109950549A CN 201910304907 A CN201910304907 A CN 201910304907A CN 109950549 A CN109950549 A CN 109950549A
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- carbon material
- lithium ion
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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 invention discloses a kind of lithium ion battery collectors and preparation method thereof, the collector includes metal foil and the carbon material layer with good electric conductivity coated in metal foil surface, the metal foil is one kind of plane copper foil, plane aluminium foil, porous aluminium foil, porous copper foil, and the carbon material layer is one of super-P, Ketjen black, acetylene black, carbon nanotube, redox graphene (RGO), nanocrystal graphene (GNC) or two kinds or more mixtures.The carbon material coating can be with the Interface Construction between modified electrode collector and active material.Using the lithium battery of this collector, have the characteristics that low with electrode material contacts resistance, bond strength is high.Afflux preparation simple process of the invention is efficient, can effectively improve cycle performance of the battery under high magnification, while reducing the internal resistance of lithium battery, improve the charge-discharge performance of lithium battery.
Description
Technical field
The present invention relates to a kind of preparation methods of affluxion body in lithium ion batteries, belong to technical field of lithium ion.
Background technique
The electronic product to make rapid progress with the modern times and the industry of the energy automobile of rapid development, additional traditional fossil energy
The problems such as consuming excessively with severe environmental pollution, urgent need develop low internal resistance, high-energy density, high rate performance Zhuo
More, the high-performance serondary lithium battery of stable cycle performance.Affluxion body in lithium ion batteries not only acts as support inside battery structure
Effect, and be the first step channel that extraneous electronics enters lithium battery.Self-evident, it is to the high rate performance of lithium battery and long-term
Cyclical stability all plays extremely important influence.
In conventional lithium secondary battery manufacturing process, active material slurry is directly coated at plane or porous current collector
The fixation of active material and collection liquid surface is realized on surface by binder after dry.Can there are collector and active material in this way
The defects of material contact area is small, bad adhesion, interface resistance is big.In order to promote the power density and cycle life of lithium battery, apply
Carbon metal foil becomes research hotspot in recent years.
Chinese invention patent application CN 108950570A discloses a kind of negative electrode of lithium ion battery collector porous copper foil
Preparation method, however, the copper foil of acidizing corrosion is not coated with the conductive carbon material bed of material, contact resistance between electrode material and
Bond strength needs to be considered.Chinese invention patent application CN 108950570A discloses a kind of lithium battery collector conductive coating,
However, conductive coating is applied directly on smooth surface collector using scraper, this method conductive coating is thicker, lithium battery energy
Density is low.
Summary of the invention
The purpose of the present invention is small, bad adhesion, electrodes for current lithium battery collector and active material contact area
The defects of material is easy to fall off, and interface resistance is big is directly coated one layer thin on metal foil using a kind of simple and easy method
And the stable conductive carbon material bed of material, a kind of preparation method of affluxion body in lithium ion batteries is provided.
To achieve the above object, the invention adopts the following technical scheme.
The invention discloses a kind of preparation method of affluxion body in lithium ion batteries, the collector is metal foil and coating
In the forming with a thickness of 0.2 μm -5 μm of carbon material layer with good electric conductivity of metal foil surface, the carbon material is
One of super-P, Ketjen black, acetylene black, carbon nanotube, graphene oxide (RGO), nanocrystal graphene (GNC) or
Two kinds or more mixtures, between the partial size 5nm-100nm of the carbon material, and at least 90% particle diameter distribution 5nm-50nm it
Between.
Further, the metal foil is plane aluminium foil, plane copper foil, porous aluminium foil, one kind of porous copper foil.
Further, the metal foil with a thickness of 4 μm -30 μm.
Further, the lithium battery afflux preparation includes the following steps:
(1) by weight, the ratio of conductive carbon material, dispersed component, NMP or alcohol is (0.2~10): (0~5): (85~
99) abundant ultrasonic mixing obtains conductive carbon material bed of material slurry.
(2) conductive carbon pastes for obtaining step (1) are coated in the metal by Langmuir-Blodget scooping method
The surface of foil.
(3) the lithium battery collector for preparing step (2) is in convection oven controlled at 3-5 hour of 60 to 100 DEG C of bakings.
Further, the Langmuir-Blodget scooping method includes the following steps,
(1) metal foil surface is subjected to surface preparation with aqueous isopropanol.
(2) conductive carbon pastes are added dropwise in support phase, conductive carbon phase is in support phase surface spreading.
(3) preferably, the support phase is deionized water.
(4) pretreated metal foil is lifted, conductive carbon phase is deposited in metal foil.
(5) after being dried in vacuo, the metal foil for being attached with thin and stable conductive carbon layer is obtained.
Detailed description of the invention
Fig. 1 is the preparation method schematic diagram that affluxion body in lithium ion batteries is prepared by Langmuir-Blodget scooping method.
Fig. 2 is the circulation figure that lithium ion battery multiplying power is 0.5C.
Specific embodiment
The present invention is further described with case study on implementation below, but the present invention is not limited solely to following example.
The test mode that the present invention uses is assembled into silicon-carbon for CR2025 battery testing, using lithium battery collector of the present invention
Cathode is to lithium half-cell.
Embodiment 1
By the mixture of 0.4g carbon nanotube (CNTs) and nanocrystal graphene (GNC), 0.2g dispersing agent is dissolved in 9.4g NMP
In, ultrasonic disperse 2h is coated in a thickness of on 10 μm of plane copper foil with Langmuir-Blodget scooping method, is placed in
80 DEG C of convection oven, 2h dries NMP;
The preparation of cathode pole piece: by negative electrode material silicon-carbon 450, binder CMC, binder SBR and conductive agent super-P according to 8:
The mass ratio of 0.5:0.5:1 is weighed, and is dissolved in deionized water, and the slurry of appropriate viscosity is made in stirring.Slurry is coated on
On the copper foil of affluxion body prepared, then with 80~100 DEG C of drying, roll-in, cut-parts obtain diameter as the silicon-carbon cathode pole piece of 14mm,
Weigh, calculate and record the quality of active material, then it is vacuum dried after be put into it is stand-by in the glove box of argon gas protection atmosphere.
Electrolyte: ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) are electrolysis by 1:1:1 volume ratio
Liquid solvent, lithium salts LiPF6, molal volume concentration is 1mol/L.
Lithium ion half-cell: silicon-carbon 450 is assembled in argon gas glove box to lithium piece half-cell.
Embodiment 2
By the mixture of 0.02g carbon nanotube (CNTs) and nanocrystal graphene (GNC), 0.01g dispersing agent is dissolved in 9.97g
In NMP.
Other raw materials and production method are the same as embodiment 1.
Embodiment 3
By the mixture of 1g carbon nanotube (CNTs) and nanocrystal graphene (GNC), 0.5g dispersing agent is dissolved in 8.5g NMP.
Other raw materials and production method are the same as embodiment 1.
Embodiment 4
By 0.4g conductive black (super-P), 0.2g dispersing agent is dissolved in 9.4g alcohol.
Other raw materials and production method are the same as embodiment 1.
Embodiment 5
By 0.02g conductive black (super-P), 0.01g dispersing agent is dissolved in 9.97g alcohol.
Other raw materials and production method are the same as embodiment 1.
Embodiment 6
By 1g conductive black (super-P), 0.5g dispersing agent is dissolved in 8.5g alcohol.
Other raw materials and production method are the same as embodiment 1.
Comparative example 1
Difference is, lithium battery collector used is plane copper foil in comparative example 1, and planar metal foil surface is without conductive carbon material
Layer.
Other raw materials and production method are the same as embodiment 1.
Comparative example 2
Difference is, lithium battery collector used is porous copper foil in comparative example 2, and multicellular metal foil surface is without conductive carbon material
Layer.
Other raw materials and production method are the same as embodiment 1.
The lithium ion battery that embodiment 1-6 is prepared with comparative example 1-2 is tested for the property, test result is shown in Table 1:
Table 1.
As shown in Table 1, lithium ion battery prepared by the present invention has good cycle performance and high rate performance, by 1 He of embodiment
The comparison of comparative example 1-2 it is found that using the plane copper foil of conductive carbon coating modification as collector when, lithium ion battery it is straight
Stream internal resistance has apparent reduction, and can recycle steadily in the long term;No matter the comparison of embodiment 1-3 and embodiment 4-6 are it is found that adopt
Use carbon nanotube (CNTs) and nanocrystal graphene (GNC) mixture or individually using conductive black (super-P) as
Conductive carbon material, the overall performance of lithium ion battery have a degree of improvement.
Claims (9)
1. a kind of lithium ion battery collector, which is characterized in that the collector include metal foil and be coated in metal foil
The carbon material layer with good electric conductivity on surface.
2. lithium ion battery collector according to claim 1, which is characterized in that the metal foil be plane aluminium foil,
Plane copper foil, porous aluminium foil, one kind of porous copper foil.
3. lithium ion battery collector according to claim 1, which is characterized in that the metal foil with a thickness of 4 μm-
30 μm, porosity 0%-60%;
Preferably, the metal foil with a thickness of 8 μm -12 μm;
Preferably, the porosity of the metal foil should be less than 30%.
4. lithium ion battery collector according to claim 1, the carbon material is super-P, Ketjen black, carbon nanometer
One of pipe, redox graphene (RGO), nanocrystal graphene (GNC) or two kinds or more mixtures, the carbon material
Partial size between 5nm-100nm, and at least 90% particle diameter distribution between 5nm-50nm.
5. lithium ion battery collector according to claim 1, which is characterized in that the carbon material layer with a thickness of
0.2μm-5μm;
Preferably, the thickness of the carbon material layer should be less than 1 μm.
6. a kind of preparation method of lithium ion battery collector, which is characterized in that the preparation method includes the following steps:
(1) by weight, the ratio of conductive carbon material, dispersed component, NMP or alcohol is (0.2~10): (0~5): (85~
99), abundant ultrasonic mixing is uniform, obtains conductive carbon material bed of material slurry.
(2) the conductive carbon material bed of material slurry for obtaining step (1) is coated in institute by Langmuir-Blodget scooping method
State the surface of multicellular metal foil.
(3) the lithium ion battery collector of step (2) preparation is dry in convection oven.
7. preparation method according to claim 6, which is characterized in that the ultrasonic disperse process time is 2-5h.
8. preparation method according to claim 6, which is characterized in that the dispersed component be isopropanol, n-butanol,
The mixtures of the one or two or more kinds of terpinol, ethyl acetate, butyl acetate.
9. preparation method according to claim 6, which is characterized in that drying temperature is 60- in the step (3)
100 DEG C, drying time is 2-5 hour.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110808356A (en) * | 2019-11-14 | 2020-02-18 | 北京乐华锂能科技有限公司 | Preparation method of lithium ion battery pole piece and lithium ion battery pole piece |
CN111403799A (en) * | 2020-03-09 | 2020-07-10 | 广西华政新能源科技有限公司 | Special-shaped lithium battery and vehicle-mounted kettle |
CN113193203A (en) * | 2021-04-14 | 2021-07-30 | 上海大学(浙江·嘉兴)新兴产业研究院 | Silicon-carbon negative plate, preparation method thereof and lithium ion battery |
CN114420891A (en) * | 2021-11-25 | 2022-04-29 | 西安交通大学 | High-voltage lithium ion battery current collector, preparation method and application |
CN116435004A (en) * | 2023-06-13 | 2023-07-14 | 广州纳诺新材料技术有限公司 | Halloysite-containing conductive paste, carbon-coated foil and preparation method and application thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN110808356A (en) * | 2019-11-14 | 2020-02-18 | 北京乐华锂能科技有限公司 | Preparation method of lithium ion battery pole piece and lithium ion battery pole piece |
CN111403799A (en) * | 2020-03-09 | 2020-07-10 | 广西华政新能源科技有限公司 | Special-shaped lithium battery and vehicle-mounted kettle |
CN113193203A (en) * | 2021-04-14 | 2021-07-30 | 上海大学(浙江·嘉兴)新兴产业研究院 | Silicon-carbon negative plate, preparation method thereof and lithium ion battery |
CN113193203B (en) * | 2021-04-14 | 2023-08-29 | 上海大学(浙江·嘉兴)新兴产业研究院 | Silicon-carbon negative electrode plate, preparation method thereof and lithium ion battery |
CN114420891A (en) * | 2021-11-25 | 2022-04-29 | 西安交通大学 | High-voltage lithium ion battery current collector, preparation method and application |
CN114420891B (en) * | 2021-11-25 | 2023-12-19 | 西安交通大学 | High-voltage lithium ion battery current collector, preparation method and application |
CN116435004A (en) * | 2023-06-13 | 2023-07-14 | 广州纳诺新材料技术有限公司 | Halloysite-containing conductive paste, carbon-coated foil and preparation method and application thereof |
CN116435004B (en) * | 2023-06-13 | 2023-08-29 | 广州纳诺新材料技术有限公司 | Halloysite-containing conductive paste, carbon-coated foil and preparation method and application thereof |
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Application publication date: 20190628 |