CN109860597A - A kind of aqueous compound binding agent of lithium ion battery - Google Patents
A kind of aqueous compound binding agent of lithium ion battery Download PDFInfo
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- CN109860597A CN109860597A CN201910033141.6A CN201910033141A CN109860597A CN 109860597 A CN109860597 A CN 109860597A CN 201910033141 A CN201910033141 A CN 201910033141A CN 109860597 A CN109860597 A CN 109860597A
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- ion battery
- lithium ion
- binding agent
- compound binding
- aqueous compound
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a kind of aqueous compound binding agent of lithium ion battery, the binder includes the cooperation binder of 5~50wt% ethylene vinyl acetate copolymer and 95~50wt%.The aqueous compound binding agent has the characteristics that elongation at break and tensile strength height, caking property are good, it can be used as preparation of the binder for the positive or negative pole in lithium ion battery, when being applied to lithium ion battery, volume change big cathode or positive active material especially during removal lithium embedded, can improve the specific capacity and cyclical stability of lithium ion battery simultaneously.Binder component of the invention is easy to get, it is simple to prepare, can mass production, nontoxic and environmentally friendly.
Description
Technical field
The present invention relates to a kind of electrodes of lithium-ion batteries binders, and in particular to a kind of lithium ion battery is with aqueous compound
Binder belongs to field of lithium ion battery.
Background technique
With the development of science and technology with the requirement of environmental protection, lithium ion battery in life using more and more extensive, to lithium from
The energy density of sub- battery requires also higher and higher, lithium ion battery especially for electric vehicle.Select the activity of height ratio capacity
Substance becomes a kind of method for improving lithium ion battery energy density.But during removal lithium embedded, the active matter of height ratio capacity
Matter usually haves the shortcomings that volume change is big, eventually leads to the sharp-decay of active material to fall off with capacity.Binder is lithium
Indispensable a part in ion battery mainly plays bonding collector, active material and conductive agent in lithium ion battery
Effect, make electrode keep integrality.Its dosage in the battery is although small, but plays very important effect.
Binder used in lithium ion battery is mainly oiliness binder and aqueous binders at present.Oiliness binder is main
For Kynoar (PVDF), solvent used is the organic matter N-Methyl pyrrolidone with volatility and toxicity.PVDF's
Disadvantage is mainly that the larger and active force with active material of environmental pollution is poor, especially to the active material of height ratio capacity.
The active material of height ratio capacity has the characteristics that volume change is big during charge and discharge cycles.It is living when using PVDF as binder
Property substance is easy to fall off from pole piece, leads to capacity attenuation.
The aqueous binders of lithium ion battery are mainly sodium carboxymethylcellulose, polyacrylic acid, butadiene-styrene rubber.Carboxymethyl
Because containing a large amount of polar group, polar group enhances same with the cohesive force of active material for sodium cellulosate and polyacrylic acid
When also enhance intermolecular active force.The rotation that stronger intermolecular force results in strand is poor, and distortional ability is low,
Poor flexibility.Film obtained by such binder has harder and more crisp characteristic.Using this quasi polymer as preparing the viscous of pole piece
When tying agent, gained pole piece is harder, embrittlement.The problems such as pole piece cracking easily occurs when rolling winding.In addition for removal lithium embedded
The big active material of volume change in the process, by the pole piece of this class binder preparation also due to active matter during removal lithium embedded
The volume change of matter and the rupture for leading to binder, active material fall off from pole piece.And butadiene-styrene rubber is although flexible, still
Cohesive force is lower.Additionally due to flexible larger, for nanometer or micron order active material, active material is easy to during removal lithium embedded
Reunite, causes the decaying of specific capacity.
To solve problems, it is necessary to develop a kind of intensity and flexible aqueous binders appropriate, improve lithium-ion electric
The lithium ion battery of the cycle performance and high rate performance in pond, the especially active material containing height ratio capacity.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to which providing one kind can be used for lithium ion battery positive and negative electrode material
The aqueous compound binding agent of material.The binder can be improved the cohesive force between active material, can effectively improve lithium ion battery
Cyclical stability and high rate performance.
The present invention adopts the following technical scheme:
To achieve the above object, one aspect of the present invention provides a kind of aqueous compound binding agent of lithium ion battery, described
Binder includes the cooperation binder of 5~50wt% ethylene vinyl acetate copolymer and 95~50wt%；The binder tool
There is the features such as cohesive force is strong, tensile strength and elongation at break are high.
The ethylene-vinyl acetate copolymer uses emulsion copolymers, and wherein vinyl acetate content (is often referred to quality
Percentage) it is 80%.
Further, mass ratio 1:9~1:1 of the ethylene vinyl acetate copolymer and cooperation binder.
The preferably highly polar polymer of cooperation binder, further preferred polyacrylic acid, polyacrylate, carboxymethyl are fine
The combination of one or more of plain sodium, sodium alginate, carboxylated chitosan, polyethyleneimine and polyvinyl alcohol is tieed up, but unlimited
In these types of polymer.
Another aspect of the present invention provides a kind of application of aqueous compound binding agent in lithium ion battery, the lithium from
Sub- battery includes that anode pole piece, cathode pole piece, electrolyte and diaphragm, wherein anode pole piece and cathode pole piece include described aqueous
Compound binding agent.
The positive or negative pole pole piece the preparation method comprises the following steps: positive or negative pole active material, conductive agent and institute will be contained
The electrode slurry for stating binder carries out coating and pole piece is made, and the aqueous compound binding agent described in electrode slurry accounts for 1~
20wt%.
Further, the positive active material can be the positive electrode of all known lithium ion batteries, such as single
Matter sulphur, more lithium sulfides, organic sulfur compound, sulfenyl composite material, cobalt acid lithium, LiMn2O4, nickel-cobalt-manganese ternary material or LiFePO4,
But not limited to this；The negative electrode active material can be the negative electrode active material of all known lithium ion batteries, as graphite,
Soft carbon, hard carbon, lithium titanate, silicon, silicon-carbon, silicon stannum alloy, tin, tin carbon or germanium, but not limited to this.
Beneficial effects of the present invention:
Using the synergistic effect of ethylene vinyl acetate copolymer and cooperation binder, binder and pole piece can be improved simultaneously
The adhesive property of middle active material particle, conductive agent and collector.It can be big using binder of the present invention when preparing lithium ion battery
Width promotes the cyclical stability of lithium ion battery, especially for the big active material of volume change during embedding lithium/de- lithium.
Binder each component price provided by the invention is low, preparation is simple, can mass production, nontoxic and environmentally friendly advantage.
Detailed description of the invention
Fig. 1 is the cycle performance figure of the lithium ion battery prepared in embodiment 1 and comparative example 1；
Fig. 2 is the high rate performance figure of the lithium ion battery prepared in embodiment 1；
Fig. 3 is the cycle performance figure of the lithium ion battery prepared in embodiment 2 and comparative example 2；
Fig. 4 is the high rate performance figure of lithium ion battery prepared in embodiment 2.
Specific embodiment
Below in conjunction with embodiment, the present invention is described in more detail.Specific example described herein is only used
Of the invention in explaining, protection scope of the present invention is not limited to these embodiments.
In following each embodiments, the preparation method comprising the aqueous compound binding agent of ethylene vinyl acetate copolymer
It is: the acetic acid ethylene by the polyacrylic acid aqueous solution (number-average molecular weight is 450,000) of 0.7g 10wt% with 0.3g 10wt%
Ester copolymer emulsion is mixed, up to the aqueous compoiste adhering agent emulsion of 10wt% lithium ion battery after being uniformly dispersed.Pole piece
The load capacity of middle active material is 1mg/cm2。
Embodiment 1
By 0.35g porous silicon and 0.05g conductive agent Super-P ground and mixed it is uniform after, be added in above-mentioned binder, it is mechanical
Uniform slurry is prepared in stirring.This slurry is coated on copper foil and is dried.Pole piece after drying, which is cut into diameter, is
The sequin of 14mm is to electrode with lithium piece in glove box, and the pole piece of preparation is working electrode, is assembled into 2032 buttons electricity
Pond.Wherein electrolyte is the fluorinated ethylene carbonate containing 1mol/L lithium hexafluoro phosphate, dimethyl carbonate and methyl ethyl carbonate (body
Product is than being 1:1:1) solution.
Comparative example 1
Polyacrylic acid is made into the aqueous solution of 10wt%.0.35g porous silicon and 0.05g conductive agent Super-P grinding is mixed
After closing uniformly, it is added in 1g 10wt% polyacrylic acid aqueous solution, mechanical stirring prepares uniform slurry.This slurry is coated with
It is on copper foil and dry.Pole piece after drying is cut into the sequin that diameter is 14mm, is to electricity with lithium piece in glove box
The pole piece of pole, preparation is working electrode, is assembled into 2032 button cells.
Test condition: in embodiment 1 and comparative example 1, the blue electric battery test system of button cell (model specification:
CT2001A charge-discharge test) is carried out, charging/discharging voltage range is 0.01V~1.2V, respectively in 0.05A/g, 0.1A/g, 0.2A/
It is tested under the current density condition of g, 0.5A/g, 1A/g, 2A/g and 5A/g.Fig. 1 is the cycle performance of embodiment 1 and comparative example 1
Figure.(preceding two circle activates under the current density of 0.05A/g), the circulation for the first time of embodiment 1 under the conditions of the charge and discharge of 0.5A/g
Specific discharge capacity reach 3670mAh/g, close to theoretical specific capacity (theoretical specific capacity 4200mAh/g).Carry out 100 circulations
Afterwards, specific discharge capacity is stablized, and the specific discharge capacity of comparative example 1 is decayed rapidly after circulation 75 times.In embodiment 1, circulation 100
Specific capacity conservation rate is 87% after secondary, and the specific capacity conservation rate of comparative example 1 only has 26%.Fig. 2 is the forthright again of embodiment 1
It can figure.For embodiment 1 under the current density of 5A/g, specific capacity is still up to 1000mAh/g.Fig. 1 and Fig. 2 illustrates proposed by the present invention
The cyclical stability and high rate performance of electrode can be improved in binder.
Embodiment 2
By sulfur-bearing active material (elemental sulfur/Ketjen black compound, weight ratio 7:3) 0.8g, conductive agent Super-P
0.1g is mixed with the aqueous compound binding agent of 1g 10wt%, and mechanical stirring obtains uniform slurry.This slurry is coated on carbon-coated aluminum foils
It goes up and dries.In glove box, using the pole piece prepared as working electrode, lithium piece is to be assembled into 2032 button cells to electrode.
Wherein electrolyte is the mixing of the 1,3- dioxolanes and dimethoxymethane of double fluoroform Huang imide lis of 1.0mol/L
Solution (volume ratio 1:1).
Comparative example 2
By sulfur-bearing active material (elemental sulfur/Ketjen black compound, weight ratio 7:3) 0.8g, conductive agent Super-P
0.1g is mixed with the PVDF binder (solvent is N-Methyl pyrrolidone) of 1g 10wt%, and mechanical stirring obtains uniform slurry.It will
This slurry is coated on aluminium foil and drying.In glove box, using the pole piece prepared as working electrode, lithium piece is to electrode, group
Dress up 2032 button cells.Wherein electrolyte is the 1,3- dioxolanes and two of double fluoroform Huang imide lis of 1.0mol/L
The mixed solution (volume ratio 1:1) of methoxyl group methane.
Test condition: the blue electric battery test system of the button cell in embodiment 2 and comparative example 2 (model specification:
CT2001A charge-discharge test) is carried out, charging/discharging voltage range is 1.8V~2.8V, and current density is respectively 0.1C, 0.2C,
0.5C, 1C and 2C (1C=1675mA/g).Fig. 3 is the cycle performance figure of embodiment 2 and comparative example 2.In the current density of 0.5C
Under (preceding two circle activated under the current density of 0.1C), specific discharge capacity still has a 620mAh/g after circulation 100 times, and comparative example
Specific discharge capacity only has 380mAh/g after circulation 100 times in 2.Fig. 4 is the high rate performance figure of embodiment 2.In different charge and discharges
Under electric current density, binder proposed by the present invention still has superior performance.Under the conditions of 2C, still there is putting for 501mAh/g
Electric specific capacity.Illustrate that the electrochemical cycle stability and high rate performance of battery can be improved in binder proposed by the present invention.
Claims (9)
1. a kind of aqueous compound binding agent of lithium ion battery, it is characterised in that: the binder includes 5~50wt% ethylene vinegar
The cooperation binder of vinyl acetate copolymer and 95~50wt%.
2. the aqueous compound binding agent of lithium ion battery according to claim 1, it is characterised in that: the ethylene vinyl acetate
Ethylene copolymer uses emulsion copolymers, and wherein vinyl acetate content is 80%.
3. the aqueous compound binding agent of lithium ion battery according to claim 1, it is characterised in that: the cooperation bonding
Agent is polyacrylic acid, polyacrylate, sodium carboxymethylcellulose, sodium alginate, carboxylated chitosan, polyethyleneimine and poly- second
The combination of one or more of enol.
4. the aqueous compound binding agent of lithium ion battery according to claim 1, it is characterised in that: the cooperation bonding
The mass ratio of agent and ethylene-vinyl acetate copolymer is 9:1~1:1.
5. application of the aqueous compound binding agent according to any one of claims 1-4 in lithium ion battery, which is characterized in that
Preparation of the aqueous compound binding agent as binder for the positive or negative pole in lithium ion battery.
6. application of the aqueous compound binding agent in lithium ion battery as claimed in claim 5, which is characterized in that will when preparation
Electrode slurry containing positive or negative pole active material, conductive agent and the binder carries out coating and pole piece is made, in electrode slurry
Aqueous compound binding agent described in material accounts for 1~20wt%.
7. application of the aqueous compound binding agent in lithium ion battery as claimed in claim 6, which is characterized in that it is described just
Pole active material is the positive active material of any lithium ion battery, including elemental sulfur, more lithium sulfides, organic sulfur compound, sulphur
Based composites, cobalt acid lithium, LiMn2O4, nickel-cobalt-manganese ternary material, LiFePO4.
8. application of the aqueous compound binding agent in lithium ion battery as claimed in claim 6, which is characterized in that described is negative
Pole active material be any lithium ion battery negative electrode active material, including graphite, soft carbon, hard carbon, lithium titanate, silicon, silicon-carbon,
Silicon stannum alloy, tin, tin carbon, germanium.
9. a kind of lithium ion battery, which is characterized in that made using aqueous compound binding agent according to any one of claims 1-4
Positive or negative pole is made for binder.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910033141.6A CN109860597A (en) | 2019-01-14 | 2019-01-14 | A kind of aqueous compound binding agent of lithium ion battery |
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| CN201910033141.6A CN109860597A (en) | 2019-01-14 | 2019-01-14 | A kind of aqueous compound binding agent of lithium ion battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057184A (en) * | 2019-12-30 | 2020-04-24 | 宣城研一新能源科技有限公司 | Preparation method of aqueous binder for negative pole piece |
| CN111180733A (en) * | 2020-01-03 | 2020-05-19 | 南方科技大学 | Three-dimensional network water-based composite binder and application thereof in lithium ion battery |
| CN112563483A (en) * | 2020-12-14 | 2021-03-26 | 广西卓能新能源科技有限公司 | Positive active material slurry of lithium ion battery and preparation method |
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Application publication date: 20190607 |