CN106684433B - The additive and preparation method thereof of negative electrode for lithium ion battery slurry binder - Google Patents
The additive and preparation method thereof of negative electrode for lithium ion battery slurry binder Download PDFInfo
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- CN106684433B CN106684433B CN201611123196.9A CN201611123196A CN106684433B CN 106684433 B CN106684433 B CN 106684433B CN 201611123196 A CN201611123196 A CN 201611123196A CN 106684433 B CN106684433 B CN 106684433B
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
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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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- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 present invention relates to technical field of lithium-ion battery.The invention discloses a kind of additive of negative electrode for lithium ion battery slurry binder, it is prepared by Kynoar, conductive agent and dispersing agent；The invention also discloses a kind of preparation methods of the additive of negative electrode for lithium ion battery slurry binder.Negative electrode slurry binder additives in the present invention can improve the adhesive property of binder, and negative electrode active material preferably being bonded together more evenly can be made after use；The additive of negative electrode binder has positive temperature coefficient effect in the present invention, when temperature increases inside lithium ion cell for some reason（When temperature is increased to 120 DEG C or more）, the positive temperature coefficient effect of negative electrode binder additive plays a role, so that the resistance of cathode rises rapidly, to reduce the electric current of inside lithium ion cell, and then the exothermic reaction of inside lithium ion cell is reduced, to guarantee the safety that lithium ion battery uses.
Description
Technical field
The present invention relates to technical field of lithium-ion battery, viscous more particularly, to a kind of negative electrode for lithium ion battery slurry
Tie the additive and preparation method thereof of agent.
Background technique
In recent years, the fast development in the fields such as portable electronic product, electric car, energy-accumulating power station, to energy storage skill
More stringent requirements are proposed for art.Lithium ion battery becomes the primary selection in these fields due to its high energy density, and
Its energy density is also higher and higher.Higher and higher along with lithium ion battery energy density, the safety problem that it is faced is increasingly
Sternness, the terminal for seriously limiting lithium ion battery with high energy density use.
The safety problem of lithium ion battery is mainly to be generated due to battery thermal runaway.Inside battery is because abnormal heat production is anti-
It answers, internal temperature of battery is caused persistently to increase, then cause more heat production side reactions, battery catches fire is caused even to explode, thus
Seriously threaten the security of the lives and property of user.
In order to improve this problem, people improve the security feature of lithium ion battery using various strategies.It can use
Following method, 1, be by ceramic coating improve diaphragm thermal stability, avoid because diaphragm be heat-shrinked and cause positive and negative anodes to connect
Touching, to slow down thermal runaway reaction；2, the polymer melted at a certain temperature is coated on diaphragm, utilizes melting for polymer
Change, the lithium ion conduction channel between inside battery positive and negative anodes is blocked, to avoid the aggravation of battery thermal runaway.
Method 1 has been used widely at present, and can significantly improve the security feature of lithium ion battery.But by
It is only capable of improving the thermal stability of diaphragm in the diaphragm of coated ceramic, heat production side reaction can not be blocked, therefore its improvement has
Limit.It only can solve the safety problem that energy density is no more than 200wh/kg battery at present；Method 2 can partially contain battery
Thermal runaway reaction, but since lithium ion cell electrode is usually all porous electrode, electrolyte is filled in electrode gap abundant
In；Although the lithium ion conduction between positive and negative anodes is blocked, electrode interior active material still exists with reacting for electrolyte
Continue, thermal accumlation can be further resulted in and cause thermal runaway reaction, method 2 is not applied for high-energy and high-power lithium
Ion battery systems.
Summary of the invention
To solve the above problems, cathode security of lithium ion battery energy can be increased the present invention provides one kind and can be changed
The negative electrode slurry binder additives of binder adhesive property in kind negative electrode slurry.
The present invention also provides a kind of preparation method is simple, binder additives are made, and to improve security performance effective
The preparation method of lithium-ion negative pole binder additives.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of additive of negative electrode for lithium ion battery slurry binder, is made by the raw material of following parts by weight：
6~8 parts of Kynoar, 2~4 parts of conductive agent, 1~2 part of dispersing agent.
The additive that Kynoar can also be used as a kind of improvement binder adhesive property is added in binder, promotes
The compatibility of binder；Meanwhile Kynoar is a kind of organic high molecular polymer with positive temperature coefficient effect, in temperature
Resistance increases rapidly when degree increases；Exist in addition, adding suitable conductive agent in Kynoar and can promote Kynoar
Electric conductivity under normal temperature can be added in slurry specific in the present invention to avoid in binder/binder additives
The problem of reduction negative electrode slurry electric conductivity generated afterwards reduces；Properly add in addition, adding suitable species in Kynoar
The conductive agent of dosage can also adjust the characteristic of its positive temperature coefficient effect, and the temperature for making its resistance increase sharply meets use demand；
The addition of dispersing agent is while dispersing agent to be selected to should also be as selecting to enable conductive agent and Kynoar preferably to combine
Realize the characteristic that can be volatilized under the conditions of certain temperature after dispersion purpose.
Since the additive of negative electrode binder in the present invention has positive temperature coefficient effect under normal circumstances will not shadow
The electric conductivity for ringing cathode, enables to battery to operate normally, when temperature increases inside lithium ion cell for some reason
（When temperature is increased to 120 DEG C or more）, the positive temperature coefficient effect of negative electrode binder additive plays a role, so that the electricity of cathode
Resistance rises rapidly, to reduce the electric current of inside lithium ion cell, and then reduces the exothermic reaction of inside lithium ion cell, thus
Guarantee the safety that lithium ion battery uses；In addition, can restore normally to use, be conducive to after abnormal heating Resolving probiems
It the recycling reparation of problem battery and reuses, contributes for environmental protection.
Preferably, conductive agent is the mixture of one or both of electrically conductive graphite or Ketjen black.
Preferably, conductive agent is 300~400 mesh.
Preferably, dispersing agent is one of polymethyl acrylate or 10~15wt% polyacrylamide solution.
Preferably, the content of electrically conductive graphite is 40~60wt% in conductive agent, surplus is Ketjen black.
The preparation method of the additive of negative electrode for lithium ion battery slurry binder, is made by following steps：
a）Kynoar is toasted 10~50 minutes at 190~230 DEG C, then in 10~50 DEG C of quenching-in waters；
b）Quenched Kynoar is polarized 5~20 minutes under 1~3MV/cm polarized electric field, is then crushed to
200~300 mesh；
c）It by conductive agent and dispersant and is uniformly mixed, is then added through above-mentioned steps treated polyvinylidene fluoride
Alkene continuess to mix uniformly, obtains mixture；
d）It is continually fed into dry hot-air into mixture 10~15 minutes, negative electrode for lithium ion battery slurry is made after cooling
Expect the additive of binder.
Commercially available Kynoar is usually the Kynoar of alpha-crystal form, and the Kynoar of alpha-crystal form is also usually just
Preferably, but the Kynoar of alpha-crystal form does not have positive temperature coefficient effect, and the only Kynoar of beta crystal has positive temperature
Spend coefficient effect, therefore Kynoar needs are pre-processed before use, i.e., it is the Kynoar of alpha-crystal form is more as far as possible
It is converted into the Kynoar of beta crystal, the quenching treatment after high-temperature process is exactly in order to realize this purpose；Heat treatment+quenching
Processing can only make the Kynoar of part alpha-crystal form that crystal form conversion occur, while beta crystal Kynoar obtained is being imitated
It is poor in terms of fruit and crystallite dimension, it is therefore desirable to which that, in addition electric field plan step, the correlation for further improving Kynoar is special
Property.
Preferably, the temperature for the drying hot-air being passed through in step d is 50~60 DEG C.
Therefore, the invention has the advantages that：
（1）Negative electrode slurry binder additives in the present invention can improve the adhesive property of binder, can after use
Make negative electrode active material preferably being bonded together more evenly；
（2）The security performance for improving negative electrode slurry after negative electrode slurry binder additives addition in the present invention, so that group
Lithium ion battery made of dress can be automatically stopped the safety in exothermic reaction guarantee lithium ion battery use at high temperature.
Specific embodiment
Further description of the technical solution of the present invention With reference to embodiment.
Obviously, the described embodiments are merely a part of the embodiments of the present invention, instead of all the embodiments.Based on this
Embodiment in invention, all other reality obtained by those of ordinary skill in the art without making creative efforts
Example is applied, shall fall within the protection scope of the present invention.
Embodiment 1
A kind of additive of negative electrode for lithium ion battery slurry binder, is made by the raw material of following parts by weight：
6 parts of Kynoar, 2 parts of conductive agent, 1 part of dispersing agent；
Conductive agent is the mixture of electrically conductive graphite and Ketjen black, and the content of electrically conductive graphite is 40wt%, Ketjen black in conductive agent
For 60wt%, conductive agent is 300 mesh；
Dispersing agent is 10wt% polyacrylamide solution.
The preparation method of the additive of negative electrode for lithium ion battery slurry binder, is made by following steps：
a）Kynoar is toasted 10 minutes at 190 DEG C, then in 10 DEG C of quenching-in waters；
b）Quenched Kynoar is polarized 5 minutes under 1MV/cm polarized electric field, is then crushed to 200 mesh；
c）It by conductive agent and dispersant and is uniformly mixed, is then added through above-mentioned steps treated polyvinylidene fluoride
Alkene continuess to mix uniformly, obtains mixture；
d）It is continually fed into drying hot-air 10 minutes that temperature is 50 DEG C into mixture, lithium ion battery is made after cooling
With the additive of negative electrode slurry binder.
Embodiment 2
A kind of additive of negative electrode for lithium ion battery slurry binder, is made by the raw material of following parts by weight：
7 parts of Kynoar, 3 parts of conductive agent, 1.5 parts of dispersing agent；
Conductive agent is the mixture of electrically conductive graphite and Ketjen black, and the content of electrically conductive graphite is 50wt%, Ketjen black in conductive agent
For 50wt%, conductive agent is 350 mesh；
Dispersing agent is 12wt% polyacrylamide solution.
The preparation method of the additive of negative electrode for lithium ion battery slurry binder, is made by following steps：
a）Kynoar is toasted 30 minutes at 210 DEG C, then in 30 DEG C of quenching-in waters；
b）Quenched Kynoar is polarized 12 minutes under 2MV/cm polarized electric field, is then crushed to 250 mesh；
c）It by conductive agent and dispersant and is uniformly mixed, is then added through above-mentioned steps treated polyvinylidene fluoride
Alkene continuess to mix uniformly, obtains mixture；
d）It is continually fed into drying hot-air 13 minutes that temperature is 55 DEG C into mixture, lithium ion battery is made after cooling
With the additive of negative electrode slurry binder.
Embodiment 3
A kind of additive of negative electrode for lithium ion battery slurry binder, is made by the raw material of following parts by weight：
7 parts of Kynoar, 34 parts of conductive agent, 1.5 parts of dispersing agent；
Conductive agent is electrically conductive graphite, and conductive agent is 350 mesh；
Dispersing agent is polymethyl acrylate.
The preparation method of the additive of negative electrode for lithium ion battery slurry binder, is made by following steps：
a）Kynoar is toasted 30 minutes at 210 DEG C, then in 30 DEG C of quenching-in waters；
b）Quenched Kynoar is polarized 15 minutes under 2MV/cm polarized electric field, is then crushed to 250 mesh；
c）It by conductive agent and dispersant and is uniformly mixed, is then added through above-mentioned steps treated polyvinylidene fluoride
Alkene continuess to mix uniformly, obtains mixture；
d）It is continually fed into drying hot-air 13 minutes that temperature is 55 DEG C into mixture, lithium ion battery is made after cooling
With the additive of negative electrode slurry binder.
Embodiment 4
A kind of additive of negative electrode for lithium ion battery slurry binder, is made by the raw material of following parts by weight：
7 parts of Kynoar, 3 parts of conductive agent, 1.5 parts of dispersing agent；
Conductive agent is Ketjen black, and conductive agent is 350 mesh；
Dispersing agent is polymethyl acrylate.
The preparation method of the additive of negative electrode for lithium ion battery slurry binder, is made by following steps：
a）Kynoar is toasted 30 minutes at 210 DEG C, then in 30 DEG C of quenching-in waters；
b）Quenched Kynoar is polarized 10 minutes under 2MV/cm polarized electric field, is then crushed to 250 mesh；
c）It by conductive agent and dispersant and is uniformly mixed, is then added through above-mentioned steps treated polyvinylidene fluoride
Alkene continuess to mix uniformly, obtains mixture；
d）It is continually fed into drying hot-air 13 minutes that temperature is 30 DEG C into mixture, lithium ion battery is made after cooling
With the additive of negative electrode slurry binder.
Embodiment 5
A kind of additive of negative electrode for lithium ion battery slurry binder, is made by the raw material of following parts by weight：
8 parts of Kynoar, 4 parts of conductive agent, 2 parts of dispersing agent；
Conductive agent is the mixture of electrically conductive graphite and Ketjen black, and the content of electrically conductive graphite is 60wt%, Ketjen black in conductive agent
For 40wt%, conductive agent is 400 mesh；
Dispersing agent is one of 15wt% polyacrylamide solution.
The preparation method of the additive of negative electrode for lithium ion battery slurry binder, is made by following steps：
a）Kynoar is toasted 50 minutes at 230 DEG C, then in 50 DEG C of quenching-in waters；
b）Quenched Kynoar is polarized 20 minutes under 3MV/cm polarized electric field, is then crushed to 300 mesh；
c）It by conductive agent and dispersant and is uniformly mixed, is then added through above-mentioned steps treated polyvinylidene fluoride
Alkene continuess to mix uniformly, obtains mixture；
d）It is continually fed into drying hot-air 15 minutes that temperature is 60 DEG C into mixture, lithium ion battery is made after cooling
With the additive of negative electrode slurry binder.
Additive amount can promote bonding in 15~25wt% to the additive of negative electrode binder in the present invention in a binder
The adhesive property of agent；It is simultaneously also most of all, the negative electrode slurry as made from the binder for adding this kind of additive has one
Fixed security performance is able to suppress the exothermic reaction of battery, to guarantee that the lithium ion battery being prepared has excellent results
Security performance, reduce to generate producing and using dangerous probability；Its concrete principle is as follows：Due to negative electrode binder in the present invention
There is additive positive temperature coefficient effect will not influence the electric conductivity of cathode under normal circumstances, enable to battery normal
Operation, when temperature increases inside lithium ion cell for some reason（When temperature is increased to 120 DEG C or more）, negative electrode binder
The positive temperature coefficient effect of additive plays a role, so that the resistance of cathode rises rapidly, to reduce inside lithium ion cell
Electric current, and then reduce inside lithium ion cell exothermic reaction, to guarantee the safety that lithium ion battery uses；In addition,
It after abnormal heating Resolving probiems, can restore normally to use, be conducive to the recycling reparation of problem battery and reuse, for environmental protection
It contributes.
It should be understood that those skilled in the art, can be improved or be become according to the above description
It changes, and all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (6)
1. a kind of additive of negative electrode for lithium ion battery slurry binder, it is characterised in that by the raw material system of following parts by weight
?：
6~8 parts of Kynoar, 2~4 parts of conductive agent, 1~2 part of dispersing agent；
The additive of the negative electrode for lithium ion battery slurry binder is made by following steps：
a）Kynoar is toasted 10~50 minutes at 190~230 DEG C, then in 10~50 DEG C of quenching-in waters；
b）Quenched Kynoar is polarized 5~20 minutes under 1~3MV/cm polarized electric field, then it is crushed to 200~
300 mesh；
c）It by conductive agent and dispersant and is uniformly mixed, is then added through above-mentioned steps treated Kynoar, after
It is continuous to be uniformly mixed, obtain mixture；
d）Dry hot-air is continually fed into mixture 10~15 minutes, it is viscous that negative electrode for lithium ion battery slurry is made after cooling
Tie the additive of agent.
2. the additive of negative electrode for lithium ion battery slurry binder according to claim 1, it is characterised in that：Described
Conductive agent is the mixture of one or both of electrically conductive graphite or Ketjen black.
3. the additive of negative electrode for lithium ion battery slurry binder according to claim 1, it is characterised in that：Described
Conductive agent is 300~400 mesh.
4. the additive of negative electrode for lithium ion battery slurry binder according to claim 1, it is characterised in that：Described
Dispersing agent is one of polymethyl acrylate or 10~15wt% polyacrylamide solution.
5. the additive of negative electrode for lithium ion battery slurry binder according to claim 3, it is characterised in that：Described
The content of electrically conductive graphite is 40~60wt% in conductive agent, and surplus is Ketjen black.
6. the additive of negative electrode for lithium ion battery slurry binder according to claim 1, it is characterised in that：The step
The temperature for the drying hot-air being passed through in rapid d is 50~60 DEG C.
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| US10790538B2 (en) | 2017-08-11 | 2020-09-29 | Industrial Technology Research Institute | Negative electrode and lithium ion battery |
| TWI789413B (en) * | 2017-08-11 | 2023-01-11 | 財團法人工業技術研究院 | Negative electrode and lithium ion battery |
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| US4340786A (en) * | 1979-04-03 | 1982-07-20 | Tester Norman W | Piezo-electric film manufacture |
| CN102629686A (en) * | 2012-03-29 | 2012-08-08 | 郑州大学 | Electrode material of drainage rechargeable and dischargeable lithium ion and aqueous solution rechargeable and dischargeable lithium ion battery |
| CN103094578A (en) * | 2013-01-18 | 2013-05-08 | 东莞新能源科技有限公司 | Method for producing flexible package lithium ion battery negative plates |
| CN103788550A (en) * | 2014-01-08 | 2014-05-14 | 重庆大学 | PVDF-HFP/CB (poly(vinylidene fluoride-hexafluoropropylene)/carbon black) piezoelectric composite film and preparation method thereof |
| CN105552355A (en) * | 2015-12-16 | 2016-05-04 | 山东精工电子科技有限公司 | High-rate lithium-ion battery and preparation method thereof |
| CN105788863A (en) * | 2016-02-29 | 2016-07-20 | 杭州电子科技大学 | Preparation method for polyvinylidene fluoride thin film electret |
-
2016
- 2016-12-08 CN CN201611123196.9A patent/CN106684433B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340786A (en) * | 1979-04-03 | 1982-07-20 | Tester Norman W | Piezo-electric film manufacture |
| CN102629686A (en) * | 2012-03-29 | 2012-08-08 | 郑州大学 | Electrode material of drainage rechargeable and dischargeable lithium ion and aqueous solution rechargeable and dischargeable lithium ion battery |
| CN103094578A (en) * | 2013-01-18 | 2013-05-08 | 东莞新能源科技有限公司 | Method for producing flexible package lithium ion battery negative plates |
| CN103788550A (en) * | 2014-01-08 | 2014-05-14 | 重庆大学 | PVDF-HFP/CB (poly(vinylidene fluoride-hexafluoropropylene)/carbon black) piezoelectric composite film and preparation method thereof |
| CN105552355A (en) * | 2015-12-16 | 2016-05-04 | 山东精工电子科技有限公司 | High-rate lithium-ion battery and preparation method thereof |
| CN105788863A (en) * | 2016-02-29 | 2016-07-20 | 杭州电子科技大学 | Preparation method for polyvinylidene fluoride thin film electret |
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