CN108172836A - The preparation method of polyvinylidene fluoride modified composite conducting binding agent - Google Patents
The preparation method of polyvinylidene fluoride modified composite conducting binding agent Download PDFInfo
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- CN108172836A CN108172836A CN201711475472.2A CN201711475472A CN108172836A CN 108172836 A CN108172836 A CN 108172836A CN 201711475472 A CN201711475472 A CN 201711475472A CN 108172836 A CN108172836 A CN 108172836A
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- binding agent
- polyvinylidene fluoride
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- fluoride modified
- modified composite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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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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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of preparation method of polyvinylidene fluoride modified composite conducting binding agent, step is as follows：(1) Kynoar dispersion emulsion is added in into reaction kettle, purges nitrogen deoxygenation, stirring, fluorochemical monomer is added in, heating adds in initiator and molecular weight regulator (2) reaction process and keeps polymerization temperature, mixing speed is constant, and after reaction, cooling discharge obtains composite material；(3) composite material prepared by deionized water, hydrochloric acid, conducting polymer monomer and step (2) is added in reaction tank, ultrasonic disperse weighs initiator and is dissolved in deionized water, it is added into the reaction solution of ultrasonic disperse, it detaches, washs after stirring, it is dry.The present invention utilizes the mode modified polyvinilidene fluoride of fluorochemical monomer graft copolymerization, reduces PVDF crystallinity, improves the adhesiveness and flexibility of Kynoar；By adding in conducting polymer monomer, the electric conductivity of compound binding agent is improved, reduces resistance.
Description
Technical field
The invention belongs to the technical fields of new energy materials, and in particular to a kind of polyvinylidene fluoride modified composite conducting bonds
The preparation method of agent.
Background technology
Lithium ion battery is bigger than energy since its operating voltage is high, quickly-chargeable and many advantages, such as having extended cycle life,
It has been widely used as the power supply of the mobile equipment such as mobile phone, computer, electric vehicle at present.It is mainly by positive and negative anodes, electrolyte, diaphragm and
Shell forms.Wherein electrode is mainly by active material, conductive agent, binding agent and collector composition.The performance of lithium ion battery with
Fabrication Technology of Electrode has very big relationship, such as the performance of binding agent, active material, conductive agent, binding agent ratio etc..
The common binding agent of lithium ion battery is polyvinylidene fluoride resin at present, and Kynoar is due to having higher Jie
Electric constant, stable electrochemical window, and slurry is easily formed, it is widely used in commodity lithium ion battery, but poly- inclined
Vinyl fluoride is high crystalline polymer, and crystallinity is generally 50% or so, and flexibility is poor, and high crystallinity makes it in electrolyte
In be difficult circulation, charge and discharge electric load increase, cause the internal resistance of cell larger；Simultaneously because Kynoar molecular polarity is smaller, it is right
The adhesiveness of metal collector is poor, the problem of causing cycle performance of lithium ion battery low.
At present, domestic and international researcher has made many work of the modification of Kynoar binding agent to lithium electricity, is related to
Patent have：
Patent US5109086A discloses a kind of preparation method of polyvinylidene fluoride copolymer, and the method is used containing 2,3,3,3-
The monomer modified vinylidene of tetrafluoropropene, can improve polyvinylidene fluoride copolymer compliance, shock resistance, resistance to low temperature,
But polymer reaction yield prepared by the method is relatively low.
Patent US6201084B discloses a kind of preparation method of vinylidene thermoplastic copolymer, and this method is using fluorine-containing
Dioxole and the method for vinylidene copolymerization improve the stability and adhesiveness of polymer, but the method is in the presence of poly-
Object complex process is closed, the problems such as polymer yield strength is low.
Patent CN105355922A provides a kind of polybenzazole crosslinking Kynoar binding agent, binding agent by polybenzazole and
Kynoar cross-linked polymeric forms.But the addition increase cost of polybenzazole, and it is anti-to participate in redox in charge and discharge process
It answers and degrades, battery life is caused to decline.
Patent CN104282912A discloses crosslinked adhesive for lithium battery of a kind of conducting polymer and preparation method thereof,
Improve the transmission rate of electronics.But the method only improves electric conductivity by simple blend mode, and PVDF properties are not carried out
It is modified.
In short, the study on the modification of Kynoar binding agent mainly by with other function monomers be copolymerized or with other substances
Blending expansion, it is big that purpose mainly reduces crystallinity, raising caking property and electric conductivity, the solution resistance caused by PVDF is added
The problems such as.
Invention content
The object of the present invention is to provide a kind of preparation method of polyvinylidene fluoride modified composite conducting binding agent, utilization is fluorine-containing
The mode modified polyvinilidene fluoride of monomer graft copolymerization reduces PVDF crystallinity, effectively controls the hardness of material, improves poly- inclined
The adhesiveness and flexibility of vinyl fluoride；By adding in conducting polymer monomer, the electric conductivity of binding agent is improved, reduces resistance.
The preparation method of polyvinylidene fluoride modified composite conducting binding agent of the present invention, step are as follows：
(1) Kynoar dispersion emulsion is added in into reaction kettle, purges nitrogen deoxygenation, stirring adds in fluorochemical monomer, rises
Temperature adds in initiator and molecular weight regulator, the initiator addition accounts for the 0.3- of fluorochemical monomer proportion to 70-90 DEG C
1wt%, the molecular weight regulator are diethyl malonate, and molecular weight regulator addition accounts for fluorine monomer proportion in lotion
1-5wt%；
(2) polymerization temperature is kept in reaction process, mixing speed is constant, and after a certain period of time, cooling discharge is answered for reaction
Condensation material, it is spare after composite material is washed；
(3) composite wood prepared by deionized water, hydrochloric acid, conducting polymer monomer and step (2) is added in reaction tank
Material, ultrasonic disperse 0.5-1.5h weigh initiator and are dissolved in deionized water, be added into the reaction solution of ultrasonic disperse, stir
After mixing 3-8h, product is detached, and be washed with deionized with centrifuge, it is dry to be bonded to get Kynoar composite conducting
Agent.
Polyvinylidene fluoride modified composite conducting binding agent pH value is 6-8, molecular weight 50-110 ten thousand.
Contain emulsifier in Kynoar dispersion emulsion described in step (1), the addition of emulsifier is in system
The 0.05-0.3wt% of water weight.Emulsifier is perfluoro caprylic acid or perfluoro caprylic acid substitute.
Fluorochemical monomer described in step (1) include perluorooctyl acrylate, dodecafluoroheptyl methacrylate (DFMA),
The one or more of Hexafluorobutyl mathacrylate (HFMA), trifluoroethyl methacrylate (TFEMA)；In the step (1)
Initiator is persulfate or di-tert-butyl peroxide DTBP.
The persulfate is potassium peroxydisulfate, ammonium persulfate or sodium peroxydisulfate, and currently preferred, initiator is over cure
Sour ammonium.
Fluorochemical monomer addition described in step (1) is the 10-30wt% of Kynoar (PVDF) quality in lotion.
Kynoar dispersion emulsion solid content is 20% in the step (1), and preferably fluorochemical monomer addition is PVDF
The 5-20% of quality.
It is 70-90 DEG C to keep polymerization temperature in step (2) in reaction process, and mixing speed 200-450 turns/min, and heat preservation is anti-
It answers 3-6 hours.
The component of conducting polymer monomer described in step (3) is one or both of aniline, pyrroles or thiophene monomer.
Initiator is ammonium persulfate or manganese dioxide in the step (3), and currently preferred initiator is ammonium persulfate.
Conducting polymer monomer is 1 with initiator quality ratio：0.8-1.3.
In step (3), concentration of aniline 0.1-1mol/L, the composite material matter that conducting polymer monomer is prepared with step (2)
Amount is than being 8-9.8:0.2-2.Conducting polymer monomer concentration is 0.1-1mol/L.
Concentration of hydrochloric acid is 0.3-1.5mol/L in step (3).
The polyvinylidene fluoride modified binding agent of the present invention is used for lithium ion battery.
It is replaced in the step (1) by being passed through nitrogen, makes oxygen content≤20ppm in reaction kettle.
The present invention finally obtains super high molecular weight, crystallinity is low, fine grain, height using emulsion polymerization and solution deposit
The polyvinylidene fluoride composite material of viscosity, high conduction performance has consumption of binder with the lithium ion battery of the polymer
Less, the advantages of peel strength is high, and energy density is big, good conductivity, and circulation volume conservation rate is high.
Compared with prior art, the invention has the advantages that：
(1) by controlling the addition type and addition of acrylate containing fluorine monomer, the soft of material can effectively be controlled
Hardness improves the flexibility of pole piece, and fluoro-containing group, the ester group isopolarity group in acrylate containing fluorine can improve material
To the adhesion property of collector.
(2) introducing of conducting polymer monomer improves the electric conductivity of binding agent, reduces the degree of polarization of anode, subtracts
Lack the dosage of conductive agent, reduce resistance.
Specific embodiment
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely illustrative this
Invention, without limiting protection scope of the present invention.
Embodiment 1
A kind of lithium ion battery preparation method of polyvinylidene fluoride modified compound binding agent, includes the following steps：
(1) it is 20%wt Kynoar dispersion emulsion and 10g metering systems that 500ml solid contents are added in into four-hole boiling flask
Sour trifluoro ethyl ester (TFEMA), emulsifier content is 1.25g wherein in lotion, purges nitrogen deoxygenation, is stirred with 200r/min, is risen
Temperature adds in 0.1g initiators and 0.5g molecular weight regulators to 75 DEG C；
(2) it is 75 DEG C, mixing speed 200r/min that polymerization temperature is kept in reaction process, and insulation reaction 4 hours cools down and
Material, it is spare after composite material is washed；
(3) hydrochloric acid solution, 15g aniline monomers and the step (2) of a concentration of 1mol/L of 500ml is added in four-hole boiling flask
The composite material 85g of preparation, ultrasonic disperse 1h weigh 12g ammonium persulfates and are dissolved in 50ml deionized waters, before being poured slowly into
In the reaction solution for stating ultrasonic disperse, after stirring 4h, product is detached, and be washed with deionized with centrifuge, it is dry to get
Kynoar composite conducting binding agent.
Embodiment 2
A kind of lithium ion battery preparation method of polyvinylidene fluoride modified compound binding agent, includes the following steps：
(1) it is 20%wt Kynoar dispersion emulsion and 30g metering systems that 500ml solid contents are added in into four-hole boiling flask
Sour trifluoro ethyl ester (TFEMA), emulsifier content is 1.25g wherein in lotion, purges nitrogen deoxygenation, is stirred with 200r/min, is risen
Temperature adds in 0.1g initiators and 0.5g molecular weight regulators to 75 DEG C,
(2) it is 75 DEG C, mixing speed 200r/min that polymerization temperature is kept in reaction process, and insulation reaction 4 hours cools down and
Material, it is spare after composite material is washed.
(3) hydrochloric acid solution, 15g aniline monomers and the step (2) of a concentration of 1mol/L of 500ml is added in four-hole boiling flask
The composite material 85g of preparation, ultrasonic disperse 1h weigh 12g ammonium persulfates and are dissolved in 50ml deionized waters, before being poured slowly into
In the reaction solution for stating ultrasonic disperse, after stirring 4h, product is detached, and be washed with deionized with centrifuge, it is dry to get
Kynoar composite conducting binding agent.
Embodiment 3
The lithium ion battery preparation method of polyvinylidene fluoride modified compound binding agent, includes the following steps：
(1) it is 20%wt Kynoar dispersion emulsion and 10g metering systems that 500ml solid contents are added in into four-hole boiling flask
Sour trifluoro ethyl ester (TFEMA), emulsifier content is 1.25g wherein in lotion, purges nitrogen deoxygenation, is stirred with 200r/min, is risen
Temperature adds in 0.1g initiators and 0.5g molecular weight regulators to 75 DEG C,
(2) it is 70 DEG C, mixing speed 200r/min that polymerization temperature is kept in reaction process, and insulation reaction 6 hours cools down and
Material, it is spare after composite material is washed.
(3) hydrochloric acid solution, 15g aniline monomers and the step (2) of a concentration of 1mol/L of 500ml is added in four-hole boiling flask
The composite material 85g of preparation, ultrasonic disperse 1h weigh 12g ammonium persulfates and are dissolved in 50ml deionized waters, before being poured slowly into
In the reaction solution for stating ultrasonic disperse, after stirring 4h, product is detached, and be washed with deionized with centrifuge, it is dry to get
Kynoar composite conducting binding agent.
Experiment
First, the Kynoar that embodiment 1-3 is prepared and the existing commercial products country trade mark 1, the external trade mark 2 into
Row viscosity test, DSC test crystallinity, molecular weight test, and the Kynoar that embodiment 1-3 is prepared carries out anode
Peel test force, flexibility test are carried out after piece coating, the results are shown in Table 1.
Flexible test：The pole piece of the size uniformity prepared is closely wound on the different stainless steel bar of diameter,
Then it is observed by × 200 high magnified glasses, whether coating surface has micro-crack.
1 PVDF properties of product of table compare
By experiment as can be seen that the more domestic trade mark 1 of Kynoar, 2 knot of the external trade mark that embodiment 1-3 is prepared
Brilliant degree is declined, and peeling force has larger promotion, and flexibility test performance is qualified.
2nd, it prepared by the Kynoar that embodiment 1,2,3 obtains and the existing commercial products country trade mark 1, the external trade mark 2
Lithium ion battery (cylinder 18650, anode：Cobalt acid lithium), electro-chemical test is carried out, including inner walkway, charge and discharge and cycle
Performance test, the results are shown in Table 2.
2 PVDF properties of product of table compare
| Internal resistance (m Ω) | First charge-discharge efficiency | Cyclical stability (70% attenuation) | |
| Embodiment 1 | 18 | 98.69% | 558 |
| Embodiment 2 | 18 | 98.02% | 556 |
| Embodiment 3 | 18 | 98.73% | 559 |
| The domestic trade mark 1 | 22 | 98.72% | 558 |
| The external trade mark 2 | 22 | 98.01% | 557 |
Claims (10)
1. a kind of preparation method of polyvinylidene fluoride modified composite conducting binding agent, which is characterized in that step is as follows：
(1) Kynoar dispersion emulsion is added in into reaction kettle, purges nitrogen deoxygenation, stirring adds in fluorochemical monomer, is warming up to
70~90 DEG C, add in initiator and molecular weight regulator, the initiator addition account for fluorochemical monomer proportion 0.3~
1wt%, the molecular weight regulator are diethyl malonate, and molecular weight regulator addition accounts for fluorine monomer proportion in lotion
1~5wt%；
(2) polymerization temperature is kept in reaction process, mixing speed is constant, and after a certain period of time, cooling discharge obtains composite wood for reaction
Material, it is spare after composite material is washed；
(3) composite material prepared by deionized water, hydrochloric acid, conducting polymer monomer and step (2) is added in reaction tank, is surpassed
Sound disperses 0.5~1.5h, weighs initiator and is dissolved in deionized water, is added into the reaction solution of ultrasonic disperse, and stirring 3~
After 8h, product is detached, and be washed with deionized with centrifuge, it is dry to get Kynoar composite conducting binding agent.
2. the preparation method of polyvinylidene fluoride modified composite conducting binding agent according to claim 1, which is characterized in that institute
The polyvinylidene fluoride modified composite conducting binding agent pH value stated is 6~8, molecular weight 50~1,100,000.
3. the preparation method of polyvinylidene fluoride modified composite conducting binding agent according to claim 1, which is characterized in that step
Suddenly contain emulsifier in the Kynoar dispersion emulsion described in (1), the addition of emulsifier is water weight in system
0.05~0.3wt%.
4. the preparation method of polyvinylidene fluoride modified composite conducting binding agent according to claim 1, which is characterized in that step
Suddenly fluorochemical monomer described in (1) includes perluorooctyl acrylate, dodecafluoroheptyl methacrylate, methacrylic acid hexafluoro fourth
One or more of ester or trifluoroethyl methacrylate；Initiator is persulfate or di-t-butyl in the step (1)
Peroxide.
5. the preparation method of polyvinylidene fluoride modified composite conducting binding agent according to claim 1, which is characterized in that step
Suddenly 10~30wt% of the fluorochemical monomer addition described in (1) for Kynoar quality in lotion.
6. the preparation method of polyvinylidene fluoride modified composite conducting binding agent according to claim 1, which is characterized in that step
Suddenly it is 70~90 DEG C, 200~450 turns/min of mixing speed to keep polymerization temperature in (2) in reaction process, and insulation reaction 3~6 is small
When.
7. the preparation method of polyvinylidene fluoride modified composite conducting binding agent according to claim 1, which is characterized in that step
Suddenly the component of conducting polymer monomer described in (3) is one or both of aniline, pyrroles or thiophene monomer.
8. the preparation method of polyvinylidene fluoride modified composite conducting binding agent according to claim 1, which is characterized in that institute
It is ammonium persulfate or manganese dioxide to state initiator in step (3).
9. the preparation method of polyvinylidene fluoride modified composite conducting binding agent according to claim 7, which is characterized in that step
Suddenly conducting polymer monomer and composite material mass ratio prepared by step (2) are 8~9.8 in (3):0.2~2；Conducting polymer
Monomer is 1 with initiator quality ratio：0.8~1.3.
10. the preparation method of polyvinylidene fluoride modified composite conducting binding agent according to claim 1, which is characterized in that
Concentration of hydrochloric acid is 0.3~1.5mol/L in step (3).
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| CN201711475472.2A CN108172836B (en) | 2017-12-29 | 2017-12-29 | Preparation method of polyvinylidene fluoride modified composite conductive adhesive |
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| CN201711475472.2A CN108172836B (en) | 2017-12-29 | 2017-12-29 | Preparation method of polyvinylidene fluoride modified composite conductive adhesive |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755579A (en) * | 2018-12-29 | 2019-05-14 | 山东华夏神舟新材料有限公司 | The preparation method of the positive composite conducting binder of lithium ion battery |
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|---|---|---|---|---|
| CN1212076A (en) * | 1996-02-27 | 1999-03-24 | 埃尔夫阿托化学有限公司 | Binders for electrodes and their production method |
| CN103492441A (en) * | 2012-02-03 | 2014-01-01 | 西奥公司 | Acrylonitrile grafted to pvdf |
| WO2014140457A1 (en) * | 2013-03-12 | 2014-09-18 | Arkema France | Process for free-radical grafting of unsaturated monomers onto fluoropolymers |
| CN104282912A (en) * | 2014-09-30 | 2015-01-14 | 中国东方电气集团有限公司 | Conducting polymer cross-linked adhesive for lithium battery and preparation method of adhesive |
-
2017
- 2017-12-29 CN CN201711475472.2A patent/CN108172836B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1212076A (en) * | 1996-02-27 | 1999-03-24 | 埃尔夫阿托化学有限公司 | Binders for electrodes and their production method |
| CN103492441A (en) * | 2012-02-03 | 2014-01-01 | 西奥公司 | Acrylonitrile grafted to pvdf |
| WO2014140457A1 (en) * | 2013-03-12 | 2014-09-18 | Arkema France | Process for free-radical grafting of unsaturated monomers onto fluoropolymers |
| CN104282912A (en) * | 2014-09-30 | 2015-01-14 | 中国东方电气集团有限公司 | Conducting polymer cross-linked adhesive for lithium battery and preparation method of adhesive |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755579A (en) * | 2018-12-29 | 2019-05-14 | 山东华夏神舟新材料有限公司 | The preparation method of the positive composite conducting binder of lithium ion battery |
| CN109755579B (en) * | 2018-12-29 | 2020-12-01 | 山东华夏神舟新材料有限公司 | Preparation method of positive electrode composite conductive adhesive for lithium ion battery |
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