CN109860596A - A kind of lithium battery silicon-based anode slurry and preparation method thereof - Google Patents
A kind of lithium battery silicon-based anode slurry and preparation method thereof Download PDFInfo
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- CN109860596A CN109860596A CN201811607444.6A CN201811607444A CN109860596A CN 109860596 A CN109860596 A CN 109860596A CN 201811607444 A CN201811607444 A CN 201811607444A CN 109860596 A CN109860596 A CN 109860596A
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Abstract
The invention discloses a kind of lithium battery silicon-based anode slurries and preparation method thereof, and slurry includes following components: 40-100 parts of silicon-based active substance, 0.1-10 parts of conductive agent, 0.5-10 parts of cross-linking type binder, 20-200 parts of deionized water.Active material in the silicon-based anode slurry is evenly dispersed in binder cross-linked network, can effectively improve silicon based anode material during charge and discharge cycles because of volume expansion caused by pole piece dusting, the problems such as poor circulation.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular to a kind of lithium battery silicon-based anode slurry and its preparation side
Method.
Background technique
Currently, in the production of lithium batteries cathode common used material be graphite type material, it have have extended cycle life, be at low cost,
The advantages such as resourceful, but the theoretical specific capacity of graphite is only 372mAh/g, is unable to satisfy the development of lithium battery high-energy density
It is required that；In addition, its intercalation potential is in close proximity to the deposition potential of lithium, when over-charging of battery, easily generated in electrode surface
Li dendrite leads on fire or even explosion, brings huge security risk to battery.It is novel compared with graphite negative electrodes material
Silica-base material has higher specific capacity, such as the theoretical specific capacity of silicon metal negative electrode is up to 4200mAh/g, and has lower
Li insertion extraction current potential, has a safety feature, and having shown alternative graphite type material becomes the trend of negative electrode material of new generation.So
And silica-base material can lead to the powder of detached and SEI of active material along with serious volume expansion during embedding de- lithium
The continuous formation of film, so that battery specific capacity rapid decay, efficiency for charge-discharge is reduced, and cycle life difference etc., this makes high capacity
Silicium cathode material lithium battery application above receive serious limitation.
In order to solve the problems, such as silicium cathode material charge and discharge volume expansion, binder also becomes recent lithium battery research and development work
The object that author pays close attention to, the very important performance of electrode, including cyclical stability and for the first time irreversible capacity, all strongly according to
Rely the performance in binder.
Currently, the binder that scale uses includes that SBR binder and LA133 binder cannot all efficiently solve
The above problem still will appear dusting, volume expansion during charge and discharge cycles, cause to lose between active material effectively to connect
Touching causes the problems such as battery capacity decaying is fast, cycle life is short occur.
Summary of the invention
The purpose of the present invention is aiming at the above shortcomings existing in the prior art and a kind of lithium battery for providing is negative with silicon substrate
Pole slurry and preparation method thereof has better mechanical property, caking property using cross-linking type binder compared with line style binder
It can effectively alleviate silicon based anode material in cyclic process since silicon particle is violent with three-dimensional overall structure protective value
Volume change and caused by pole piece structure destruction, a stable conduction is provided in cyclic process for silicon based anode material
Network and pole piece structure, and then can preferably improve the cycle performance of battery.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of lithium battery silicon-based anode slurry, the negative electrode slurry are mixed by following components by mass fraction:
40-100 parts of silicon-based active substance
0.1-10 parts of conductive agent
0.5-10 parts of cross-linking type binder
20-200 parts of deionized water；Wherein:
The silicon-based active substance is silicon, silicon lithium alloy, silicon boron alloy, silicon-carbon compound, aoxidizes sub- silicon, aoxidizes sub- silicon and carbon
The mixing of one or more of compound；
The conductive agent is mixed for one or more of conductive black, electrically conductive graphite, carbon nanotube, graphene, carbon nano-fiber
It closes；
The cross-linking type binder is crosslinked salt polyacrylate, crosslinked polyvinylpyrrolidone, cross-linked carboxymethyl cellulose, crosslinking
Chitosan, crossslinked sodium alginate, crosslinked starch, cross-linking polyvinyl alcohol, cross-linked polyethylene glycol, crosslinked guar gum, crosslinked polyamide,
The mixing of one or more of crosslinked polyimide, crosslinking styrene-butadiene emulsion.
A kind of preparation method of lithium battery silicon-based anode slurry, method includes the following steps:
(1) cross-linking type binder is add to deionized water according to the proportion, stirs 10-60min, obtains binder solution；
(2) silicon-based active substance is added according to the proportion in the binder solution obtained to step (1) and conductive agent is dispersed
0.5-12h obtains the lithium battery silicon-based anode slurry；Wherein:
It is described according to the proportion, mass fraction be 40-100 parts of silicon-based active substance, 0.1-10 parts of conductive agent, cross-linking type binder
0.5-10 parts, 20-200 parts of deionized water；
The silicon-based active substance is silicon, silicon lithium alloy, silicon boron alloy, silicon-carbon compound, aoxidizes sub- silicon, aoxidizes sub- silicon and carbon
The mixing of one or more of compound；
The conductive agent is mixed for one or more of conductive black, electrically conductive graphite, carbon nanotube, graphene, carbon nano-fiber
It closes；
The cross-linking type binder is crosslinked salt polyacrylate, crosslinked polyvinylpyrrolidone, cross-linked carboxymethyl cellulose, crosslinking
Chitosan, crossslinked sodium alginate, crosslinked starch, cross-linking polyvinyl alcohol, cross-linked polyethylene glycol, crosslinked guar gum, crosslinked polyamide,
The mixing of one or more of crosslinked polyimide, crosslinking styrene-butadiene emulsion.
The beneficial effects of the present invention are:
Compared with prior art, the lithium battery silicon-based anode slurry prepared with cross-linking type binder, caking property is strong, and the three of generation
Dimension network structure can effectively alleviate silicon based anode material pole piece powder caused by huge volume change in charge and discharge process
Change and peel off, maintain electrical connectivity and mechanical integrity of the pole piece in cyclic process, to effectively promote the circulation of battery
Performance.
Specific embodiment
Following embodiment does not limit the present invention convenient for better understanding the present invention.
Embodiment 1
5 parts of crosslinked salt polyacrylates are added in 40 parts of deionized waters, 20min is stirred, obtains binder solution；To binder
40 parts of silicon are added in solution and 5 parts of conductive blacks carry out dispersion 1h, obtain lithium battery silicon-based anode slurry.
Embodiment 2
10 parts of crosslinking styrene-butadiene emulsions are added in 200 parts of deionized waters, 60min is stirred, obtains binder solution；To binder
100 parts of silicon lithium alloys are added in solution and 10 parts of electrically conductive graphites carry out dispersion 12h, obtain lithium battery silicon-based anode slurry.
Embodiment 3
2 parts of crosslinked salt polyacrylates are added in 90 parts of deionized waters, 40min is stirred, obtains binder solution；To binder
60 parts of silicon-carbon compounds are added in solution and 1.2 parts of carbon nanotubes carry out dispersion 6h, obtain lithium battery silicon-based anode slurry.
Embodiment 4
4 parts of cross-linked carboxymethyl celluloses are added in 90 parts of deionized waters, 60min is stirred, obtains binder solution；To bonding
The sub- silicon of 60 parts of oxidations is added in agent solution and 2.4 parts of graphenes carry out dispersion 6h, obtains lithium battery silicon-based anode slurry.
Embodiment 5
6 parts of crosslinked polyimides are added in 120 parts of deionized waters, 40min is stirred, obtains binder solution；To binder
The compound and 4.8 parts of carbon nano-fibers that the sub- silicon of 80 parts of oxidations and carbon are added in solution carry out dispersion 8h, obtain lithium battery silicon
Base negative electrode slurry.
Comparative example 1
5 parts of polyacrylates are added in 40 parts of deionized waters, 20min is stirred, obtains binder solution；To binder solution
40 parts of silicon of middle addition and 5 parts of conductive blacks carry out dispersion 1h, obtain lithium battery silicon-based anode slurry.
Comparative example 2
4 parts of carboxymethyl celluloses are added in 90 parts of deionized waters, 60min is stirred, obtains binder solution；It is molten to binder
The sub- silicon of 60 parts of oxidations is added in liquid and 2.4 parts of graphenes carry out dispersion 6h, obtains lithium battery silicon-based anode slurry.
Slurry in embodiment 1-5 and comparative example 1-2 is coated on to the one side of copper foil by the way of micro- gravure roller coating, is applied
Cathode pole piece is made with a thickness of being dried in vacuo at 100 μm, 60 DEG C for 24 hours in cloth, forms button cell with lithium piece, test battery exists
Circulation experiment under the conditions of 0.5C measures first charge discharge efficiency and capacity attenuation situation is as shown in table 1:
| First effect/% | Recycle 30 capacity retention ratio/% | Recycle 50 capacity retention ratio/% | Recycle 200 capacity retention ratio/% | |
| Comparative example 1 | 78.1 | 26.9 | - | - |
| Comparative example 2 | 83.2 | 65.2 | 35.7 | 20.2 |
| Embodiment 1 | 82.4 | 70.5 | 40.6 | 26.7 |
| Embodiment 2 | 83.2 | 69.1 | 50.1 | 40.8 |
| Embodiment 3 | 93.2 | 95.7 | 80.4 | 66.8 |
| Embodiment 4 | 92.7 | 96.2 | 84.2 | 68.9 |
| Embodiment 5 | 94.1 | 94.6 | 80.1 | 67.6 |
As can be seen from Table 1, compared with comparative example, use silicon-based anode slurry as pole piece using lithium battery made from the embodiment of the present invention,
When on lithium battery, the first charge-discharge efficiency and cycle performance of lithium battery can be effectively improved.
Claims (2)
1. a kind of lithium battery silicon-based anode slurry, which is characterized in that the negative electrode slurry is mixed by following components by mass fraction
It forms:
40-100 parts of silicon-based active substance
0.1-10 parts of conductive agent
0.5-10 parts of cross-linking type binder
20-200 parts of deionized water；Wherein:
The silicon-based active substance is silicon, silicon lithium alloy, silicon boron alloy, silicon-carbon compound, aoxidizes sub- silicon and aoxidize sub- silicon and carbon
The mixing of one or more of compound；
The conductive agent is that one or more of conductive black, electrically conductive graphite, carbon nanotube, graphene and carbon nano-fiber are mixed
It closes；
The cross-linking type binder is crosslinked salt polyacrylate, crosslinked polyvinylpyrrolidone, cross-linked carboxymethyl cellulose, crosslinking
Chitosan, crossslinked sodium alginate, crosslinked starch, cross-linking polyvinyl alcohol, cross-linked polyethylene glycol, crosslinked guar gum, crosslinked polyamide,
The mixing of one or more of crosslinked polyimide and crosslinking styrene-butadiene emulsion.
2. a kind of preparation method of silicon-based anode slurry of lithium battery described in claim 1, which is characterized in that this method include with
Lower step:
(1) cross-linking type binder is add to deionized water according to the proportion, stirs 10-60min, obtains binder solution；
(2) silicon-based active substance is added according to the proportion in the binder solution obtained to step (1) and conductive agent is dispersed
0.5-12h obtains the lithium battery silicon-based anode slurry；Wherein:
It is described according to the proportion, mass fraction be 40-100 parts of silicon-based active substance, 0.1-10 parts of conductive agent, cross-linking type binder
0.5-10 parts, 20-200 parts of deionized water；
The silicon-based active substance is silicon, silicon lithium alloy, silicon boron alloy, silicon-carbon compound, aoxidizes sub- silicon and aoxidize sub- silicon and carbon
The mixing of one or more of compound；
The conductive agent is that one or more of conductive black, electrically conductive graphite, carbon nanotube, graphene and carbon nano-fiber are mixed
It closes；
The cross-linking type binder is crosslinked salt polyacrylate, crosslinked polyvinylpyrrolidone, cross-linked carboxymethyl cellulose, crosslinking
Chitosan, crossslinked sodium alginate, crosslinked starch, cross-linking polyvinyl alcohol, cross-linked polyethylene glycol, crosslinked guar gum, crosslinked polyamide,
The mixing of one or more of crosslinked polyimide and crosslinking styrene-butadiene emulsion.
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| CN110311121A (en) * | 2019-07-10 | 2019-10-08 | 洛阳联创锂能科技有限公司 | A kind of lithium ion battery otide containing lighium silicium cathode material and preparation method thereof |
| CN110429280A (en) * | 2019-07-22 | 2019-11-08 | 昆山博益鑫成高分子材料有限公司 | A kind of silicon-based anode using crosslinking type aqueous adhesive |
| CN110459733A (en) * | 2019-08-15 | 2019-11-15 | 中国科学院大学 | A kind of preparation method of lithium ion battery negative electrode |
| CN112018391A (en) * | 2020-07-29 | 2020-12-01 | 浙江中科玖源新材料有限公司 | Crosslinked net-shaped silicon-carbon negative electrode binder and silicon-carbon negative electrode sheet |
| CN112680148A (en) * | 2020-12-11 | 2021-04-20 | 广东微电新能源有限公司 | Binder, preparation method of binder, electrode plate and secondary battery |
| CN116759576A (en) * | 2023-06-07 | 2023-09-15 | 广东吉美帮新材料有限公司 | Lithium battery electrode coating slurry containing modified polyacrylic acid binder, and preparation method and application thereof |
| CN117334875A (en) * | 2023-11-09 | 2024-01-02 | 武汉中科先进材料科技有限公司 | Silicon-carbon composite anode material and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110311121A (en) * | 2019-07-10 | 2019-10-08 | 洛阳联创锂能科技有限公司 | A kind of lithium ion battery otide containing lighium silicium cathode material and preparation method thereof |
| CN110429280A (en) * | 2019-07-22 | 2019-11-08 | 昆山博益鑫成高分子材料有限公司 | A kind of silicon-based anode using crosslinking type aqueous adhesive |
| CN110459733A (en) * | 2019-08-15 | 2019-11-15 | 中国科学院大学 | A kind of preparation method of lithium ion battery negative electrode |
| CN112018391A (en) * | 2020-07-29 | 2020-12-01 | 浙江中科玖源新材料有限公司 | Crosslinked net-shaped silicon-carbon negative electrode binder and silicon-carbon negative electrode sheet |
| CN112680148A (en) * | 2020-12-11 | 2021-04-20 | 广东微电新能源有限公司 | Binder, preparation method of binder, electrode plate and secondary battery |
| CN116759576A (en) * | 2023-06-07 | 2023-09-15 | 广东吉美帮新材料有限公司 | Lithium battery electrode coating slurry containing modified polyacrylic acid binder, and preparation method and application thereof |
| CN116759576B (en) * | 2023-06-07 | 2024-01-26 | 广东吉美帮新材料有限公司 | Lithium battery electrode coating slurry containing modified polyacrylic acid binder, and preparation method and application thereof |
| CN117334875A (en) * | 2023-11-09 | 2024-01-02 | 武汉中科先进材料科技有限公司 | Silicon-carbon composite anode material and preparation method thereof |
| CN117334875B (en) * | 2023-11-09 | 2024-03-26 | 武汉中科先进材料科技有限公司 | Silicon-carbon composite anode material and preparation method thereof |
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