CN106558702A - A kind of negative electrode for lithium ion battery slurry - Google Patents
A kind of negative electrode for lithium ion battery slurry Download PDFInfo
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- CN106558702A CN106558702A CN201611122393.9A CN201611122393A CN106558702A CN 106558702 A CN106558702 A CN 106558702A CN 201611122393 A CN201611122393 A CN 201611122393A CN 106558702 A CN106558702 A CN 106558702A
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- negative electrode
- lithium ion
- ion battery
- kynoar
- parts
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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
-
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
Abstract
The present invention relates to technical field of lithium-ion battery.The invention discloses a kind of negative electrode for lithium ion battery slurry, which is obtained by raw materials such as 20～25 parts of negative active core-shell material, conductive agent, negative electrode binder and solvents；Wherein, negative electrode active material is spherical graphite, and conductive agent is CNT, and solvent is N methyl pyrrolidones.The binding agent added in cathode size in the present invention has preferable adhesive property, can make negative electrode active material preferably being bonded together evenly, while be readily adaptable for use in needing the battery of more high circulation performance；Cathode size binding agent in the present invention can improve the security performance of cathode size so that the lithium ion battery for assembling can be automatically stopped the safety during exothermic reaction ensures lithium ion battery use at high temperature；Cathode size in the present invention has more outstanding cycle performance, and obtained lithium ion battery has higher capacity, while also having the characteristics of blocking exothermic reaction automatically at high temperature.
Description
Technical field
The present invention relates to technical field of lithium-ion battery, more particularly, to a kind of negative electrode for lithium ion battery slurry.
Background technology
In recent years, the fast development in the field such as portable type electronic product, electric automobile, energy-accumulating power station, to energy storage skill
Art is put forward higher requirement.Lithium ion battery becomes the primary selection in these fields due to its high energy density, and
Its energy density also more and more higher.Along with lithium ion battery energy density more and more higher, the safety problem that it faces is increasingly
Sternness, the terminal for seriously limiting lithium ion battery with high energy density are used.
The safety problem of lithium ion battery is produced mainly due to battery thermal runaway.Inside battery is because abnormal heat production is anti-
Should, cause internal temperature of battery persistently to raise, cause then more heat production side reactions, cause battery catches fire even to explode, so as to
The serious security of the lives and property for threatening user.
In order to improve this problem, people improve the security feature of lithium ion battery using various strategies.Can adopt
Following method, 1, be the heat endurance that barrier film is improved by ceramic coating, it is to avoid cause both positive and negative polarity to connect because of barrier film thermal contraction
Touch, so as to slow down thermal runaway reaction；2nd, the polymer for melting at a certain temperature, melting using polymer are coated on barrier film
Change, block the lithium ion conduction passage between inside battery both positive and negative polarity, so as 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 heat endurance of barrier film in the barrier film of coated ceramic, heat production side reaction can not be blocked, therefore its improvement has
Limit.It is only capable of at present solving safety problem of the energy density less than 200wh/kg batteries；Method 2 can partly contain battery
Thermal runaway is reacted, but as lithium ion cell electrode is generally all porous electrode, electrolyte is filled in abundant electrode gap
In；Although the lithium ion conduction between both positive and negative polarity is blocked, electrode interior active material is still existed with the reaction of electrolyte
Proceed, thermal accumlation can be further resulted in and cause thermal runaway reaction, method 2 to be not applied for high-energy and high-power lithium
Ion battery systems.
The content of the invention
To solve the above problems, the invention provides exothermic reaction can be blocked automatically in lithium ion internal abnormality heat production
The lithium ion battery cathode slurry with high safety performance.
For achieving the above object, the technical solution used in the present invention is as follows：
A kind of negative electrode for lithium ion battery slurry, is obtained by the raw material of following weight portion：
80～100 parts of negative active core-shell material, 0.5～3 part of conductive agent, 1.5～6 parts of negative electrode binder, 20～25 parts of solvent；
Negative electrode active material is spherical graphite, and conductive agent is CNT, and solvent is 1-METHYLPYRROLIDONE.
Preferably, negative electrode binder is by 10～14 weight account polyethylene alcohol, the acid of 2～3 parts by weight of polypropylene, 4～5 weight
Part sodium carboxymethylcellulose, 1～2 weight portion sodium alginate and 3～5 parts by weight binder additives are obtained；Binding agent therein
Additive presses 6～9 by Kynoar, Ketjen black and PMA：2～5：1.5～2.5 weight is than being obtained.
In the present invention using HMW polyvinyl alcohol, molecular weight more than 1600000, the poly- second of this HMW
Enol has more preferable adhesive property compared to the polyvinyl alcohol of low-molecular-weight, as which has longer chain and more hydroxyls
Base, can form higher hydrogen bond action so that its adhesive property is better than low molecular weight polyethylene alcohol and active material between, while
Also apparently higher than polyacrylic acid；Polyacrylic acid effect in height ratio capacity negative pole is more outstanding, and appropriate addition polyacrylic acid can be with
Improve cementation of the binding agent in height ratio capacity negative pole；Sodium alginate has more stable characteristic as binding agent, viscous
In knot agent, appropriate addition sodium alginate can improve the stability of binding agent, be prevented from electrode efflorescence, improve circulating battery
Energy.
Kynoar can also be added in binding agent as a kind of additive for improving binding agent adhesive property, promote
The compatibility of binding agent；Meanwhile, Kynoar is a kind of organic high molecular polymer with positive temperature coefficient effect, in temperature
When degree is raised, resistance increases rapidly；Exist in addition, adding appropriate conductive agent in Kynoar and can promote Kynoar
Electric conductivity under normal temperature, specific to the present invention in, can avoid being added in slurry in binding agent/binder additives
What is produced afterwards reduces the problem that cathode size electric conductivity is reduced；Additionally, add suitable species in Kynoar properly adding
The conductive agent of dosage can also adjust the characteristic of its positive temperature coefficient effect so as to which the temperature that resistance increases sharply meets use demand；
The addition of dispersant is in order that conductive agent and Kynoar preferably can be combined, while should also be as selecting from dispersant
The characteristic that can be volatilized under the conditions of uniform temperature after realizing dispersion purpose.
As the additive of negative electrode binder in the present invention has positive temperature coefficient effect, under normal circumstances, which will not shadow
The electric conductivity of negative pole is rung, battery is enabled to and is normally run, when temperature is raised inside lithium ion cell for some reason
（When temperature is increased to more than 120 DEG C）, the positive temperature coefficient effect of negative electrode binder additive plays a role so that the electricity of negative pole
Resistance is rapid to be risen, so as to reduce the electric current of inside lithium ion cell, and then the exothermic reaction of reduction inside lithium ion cell, so as to
Ensure the safety that lithium ion battery is used；Additionally, after abnormal heating Resolving probiems, normal use can be recovered, be conducive to
The recovery reparation of problem battery and reuse, be that environmental protection is contributed.
Preferably, Ketjen black is 200～400 mesh.
Preferably, binder additives are obtained by following steps：
a）Kynoar is toasted 20～40 minutes at 180～240 DEG C, then in 10～30 DEG C of quenching-in waters；
b）Kynoar after quenching is polarized 4～10 minutes under 0.5～1.5MV/cm polarized electric fields, is then crushed to
200～400 mesh；
c）By conductive agent and dispersant and it is well mixed, the Kynoar being subsequently adding Jing after above-mentioned steps process, after
It is continuous to be well mixed, obtain mixture；
d）It is continually fed into in mixture and is dried hot-air 20～30 minutes, negative electrode for lithium ion battery slurry is obtained after cooling and is glued
The additive of knot agent.
Commercially available Kynoar is typically the Kynoar of alpha-crystal form, and the Kynoar of alpha-crystal form is also generally just
It is suitable, but the Kynoar of alpha-crystal form does not have positive temperature coefficient effect, and the only Kynoar of beta crystal has positive temperature
Degree coefficient effect, therefore Kynoar needed using front being pre-processed, will alpha-crystal form Kynoar it is as far as possible many
The Kynoar of beta crystal is converted into, the Quenching Treatment after high-temperature process is exactly to realize this purpose；Heat treatment+quenching
Process can only make part alpha-crystal form Kynoar occur crystal formation conversion, while the beta crystal Kynoar for being obtained effect
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, in binder additives preparation process d, the temperature for being dried hot-air being passed through is 50～60 DEG C.
Therefore, the invention has the advantages that：
（1）The binding agent added in cathode size in the present invention has preferable adhesive property, can make negative electrode active material
More preferable being bonded together evenly, while be readily adaptable for use in needing the battery of more high circulation performance；
（2）Cathode size binding agent in the present invention can improve the security performance of cathode size so that the lithium for assembling from
Sub- battery can be automatically stopped the safety during exothermic reaction ensures lithium ion battery use at high temperature；
（3）Cathode size in the present invention has more outstanding cycle performance, and obtained lithium ion battery has higher appearance
Amount, while also having the characteristics of blocking exothermic reaction automatically at high temperature.
Specific embodiment
Technical scheme is further described with reference to specific embodiment.
Obviously, described embodiment is only a part of embodiment of the present invention, rather than the embodiment of whole.Based on this
Embodiment in invention, all other reality that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example is applied, the scope of protection of the invention is belonged to.
Embodiment 1
A kind of negative electrode for lithium ion battery slurry, is obtained by the raw material of following weight portion：
80 parts of negative active core-shell material, 0.5 part of conductive agent, 1.5 parts of negative electrode binder, 20 parts of solvent；
Negative electrode active material is spherical graphite, and conductive agent is CNT, and solvent is 1-METHYLPYRROLIDONE；
Negative electrode binder is by 10 weight account polyethylene alcohol, the acid of 2 parts by weight of polypropylene, 4 weight portion sodium carboxymethylcelluloses, 1 weight
Part sodium alginate and 3 parts by weight binder additives are obtained；Binder additives therein are by Kynoar, Ketjen black and gather
Methyl acrylate presses 6：2：Than being obtained, Ketjen black is 200 mesh to 1.5 weight；
Preferably, binder additives are obtained by following steps：
a）Kynoar is toasted 20 minutes at 180 DEG C, then in 10 DEG C of quenching-in waters；
b）Kynoar after quenching is polarized 4 minutes under 0.5MV/cm polarized electric fields, 200 mesh are then crushed to；
c）By conductive agent and dispersant and it is well mixed, the Kynoar being subsequently adding Jing after above-mentioned steps process, after
It is continuous to be well mixed, obtain mixture；
d）50 DEG C are continually fed into in mixture and are dried hot-air 20 minutes, negative electrode for lithium ion battery slurry after cooling, is obtained
The additive of binding agent.
Embodiment 2
A kind of negative electrode for lithium ion battery slurry, is obtained by the raw material of following weight portion：
88 parts of negative active core-shell material, 1.5 parts of conductive agent, 3 parts of negative electrode binder, 22 parts of solvent；
Negative electrode active material is spherical graphite, and conductive agent is CNT, and solvent is 1-METHYLPYRROLIDONE；
Negative electrode binder is by 12 weight account polyethylene alcohol, the acid of 2 parts by weight of polypropylene, 4 weight portion sodium carboxymethylcelluloses, 1 weight
Part sodium alginate and 4 parts by weight binder additives are obtained；Binder additives therein are by Kynoar, Ketjen black and gather
Methyl acrylate presses 7：3：Than being obtained, Ketjen black is 250 mesh to 1.5 weight；
Preferably, binder additives are obtained by following steps：
a）Kynoar is toasted 30 minutes at 200 DEG C, then in 20 DEG C of quenching-in waters；
b）Kynoar after quenching is polarized 6 minutes under 1MV/cm polarized electric fields, 300 mesh are then crushed to；
c）By conductive agent and dispersant and it is well mixed, the Kynoar being subsequently adding Jing after above-mentioned steps process, after
It is continuous to be well mixed, obtain mixture；
d）55 DEG C are continually fed into in mixture and are dried hot-air 25 minutes, negative electrode for lithium ion battery slurry after cooling, is obtained
The additive of binding agent.
Embodiment 3
A kind of negative electrode for lithium ion battery slurry, is obtained by the raw material of following weight portion：
95 parts of negative active core-shell material, 1.7 parts of conductive agent, 4 parts of negative electrode binder, 23 parts of solvent；
Negative electrode active material is spherical graphite, and conductive agent is CNT, and solvent is 1-METHYLPYRROLIDONE；
Negative electrode binder by 13 weight account polyethylene alcohol, the acid of 2.5 parts by weight of polypropylene, 4.5 weight portion sodium carboxymethylcelluloses,
1.5 weight portion sodium alginates and 4 parts by weight binder additives are obtained；Binder additives therein are by Kynoar, section
Qin is black and PMA presses 8：4：Than being obtained, Ketjen black is 350 mesh to 2 weight；
Preferably, binder additives are obtained by following steps：
a）Kynoar is toasted 35 minutes at 220 DEG C, then in 25 DEG C of quenching-in waters；
b）Kynoar after quenching is polarized 8 minutes under 1.2MV/cm polarized electric fields, 300 mesh are then crushed to；
c）By conductive agent and dispersant and it is well mixed, the Kynoar being subsequently adding Jing after above-mentioned steps process, after
It is continuous to be well mixed, obtain mixture；
d）55 DEG C are continually fed into in mixture and are dried hot-air 25 minutes, negative electrode for lithium ion battery slurry after cooling, is obtained
The additive of binding agent.
Embodiment 4
A kind of negative electrode for lithium ion battery slurry, is obtained by the raw material of following weight portion：
100 parts of negative active core-shell material, 3 parts of conductive agent, 6 parts of negative electrode binder, 25 parts of solvent；
Negative electrode active material is spherical graphite, and conductive agent is CNT, and solvent is 1-METHYLPYRROLIDONE；
Negative electrode binder is by 14 weight account polyethylene alcohol, the acid of 3 parts by weight of polypropylene, 5 weight portion sodium carboxymethylcelluloses, 2 weight
Part sodium alginate and 5 parts by weight binder additives are obtained；Binder additives therein are by Kynoar, Ketjen black and gather
Methyl acrylate presses 9：5：Than being obtained, Ketjen black is 400 mesh to 2.5 weight；
Preferably, binder additives are obtained by following steps：
a）Kynoar is toasted 40 minutes at 240 DEG C, then in 30 DEG C of quenching-in waters；
b）Kynoar after quenching is polarized 10 minutes under 1.5MV/cm polarized electric fields, 400 mesh are then crushed to；
c）By conductive agent and dispersant and it is well mixed, the Kynoar being subsequently adding Jing after above-mentioned steps process, after
It is continuous to be well mixed, obtain mixture；
d）60 DEG C are continually fed into in mixture and are dried hot-air 30 minutes, negative electrode for lithium ion battery slurry after cooling, is obtained
The additive of binding agent.
In the various embodiments described above, NM cathode size preparation method and negative electrode binder preparation method are using existing
Technology, those of ordinary skill in the art are understood that its preparation technology.
The additive of the negative electrode binder in the present invention can promote the adhesive property of binding agent in a binder；It is also simultaneously
Most of all, the cathode size by obtained in adding the binding agent of this kind of additive has certain security performance, can suppress
The exothermic reaction of battery, so as to ensure that the lithium ion battery being prepared has the security performance of excellent results, reduces producing life
Produce using dangerous probability；Its concrete principle is as follows：As the additive of negative electrode binder in the present invention has positive temperature coefficient
Effect, under normal circumstances, which does not interfere with the electric conductivity of negative pole, enables to battery and normally runs, when in lithium ion battery
Portion for some reason temperature raise when（When temperature is increased to more than 120 DEG C）, the positive temperature coefficient of negative electrode binder additive
Effect plays a role so that the resistance of negative pole rises rapidly, so as to reduce the electric current of inside lithium ion cell, and then reduce lithium from
The exothermic reaction of sub- inside battery, so as to ensure safety that lithium ion battery is used；Additionally, after abnormal heating Resolving probiems,
Normal use can be recovered, be conducive to the recovery reparation of problem battery and reused, be that environmental protection is contributed.
It should be appreciated that to those skilled in the art, can be improved according to the above description or be become
Change, and all these modifications and variations should all belong to the protection domain of claims of the present invention.
Claims (5)
1. a kind of negative electrode for lithium ion battery slurry, it is characterised in that be obtained by the raw material of following weight portion：
80～100 parts of negative active core-shell material, 0.5～3 part of conductive agent, 1.5～6 parts of negative electrode binder, 20～25 parts of solvent；
Negative electrode active material is spherical graphite, and conductive agent is CNT, and solvent is 1-METHYLPYRROLIDONE.
2. a kind of negative electrode for lithium ion battery slurry according to claim 1, it is characterised in that：Described negative electrode binder
By 10～14 weight account polyethylene alcohol, the acid of 2～3 parts by weight of polypropylene, 4～5 weight portion sodium carboxymethylcelluloses, 1～2 weight portion
Sodium alginate and 3～5 parts by weight binder additives are obtained；Binder additives therein by Kynoar, Ketjen black and
PMA presses 6～9：2～5：1.5～2.5 weight is than being obtained.
3. a kind of negative electrode for lithium ion battery slurry according to claim 2, it is characterised in that：Described Ketjen black is
200～400 mesh.
4. a kind of negative electrode for lithium ion battery slurry according to claim 1 and 2, it is characterised in that described binding agent adds
Plus agent is obtained by following steps：
a）Kynoar is toasted 20～40 minutes at 180～240 DEG C, then in 10～30 DEG C of quenching-in waters；
b）Kynoar after quenching is polarized 4～10 minutes under 0.5～1.5MV/cm polarized electric fields, is then crushed to
200～400 mesh；
c）By conductive agent and dispersant and it is well mixed, the Kynoar being subsequently adding Jing after above-mentioned steps process, after
It is continuous to be well mixed, obtain mixture；
d）It is continually fed into in mixture and is dried hot-air 20～30 minutes, negative electrode for lithium ion battery slurry is obtained after cooling and is glued
The additive of knot agent.
5. a kind of negative electrode for lithium ion battery slurry according to claim 4, it is characterised in that：The binder additives
In preparation process d, the temperature for being dried hot-air being passed through is 50～60 DEG C.
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| CN107546362A (en) * | 2017-07-17 | 2018-01-05 | 上海工程技术大学 | A kind of electrode with pyroelectric effect and its preparation method and application |
| CN107611516A (en) * | 2017-07-17 | 2018-01-19 | 上海工程技术大学 | A kind of internal temperature of battery real-time management method |
| CN109524623A (en) * | 2018-11-16 | 2019-03-26 | 山东华亿比科新能源股份有限公司 | A kind of lithium battery composite graphite and bend resistance negative electrode tab and preparation method thereof |
| CN112133882A (en) * | 2020-08-31 | 2020-12-25 | 渤海大学 | Solvent-free preparation method of electrode for electrochemical energy storage device |
| CN113078320A (en) * | 2021-03-26 | 2021-07-06 | 山东大学 | Melamine modified graphite negative electrode material and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107546362A (en) * | 2017-07-17 | 2018-01-05 | 上海工程技术大学 | A kind of electrode with pyroelectric effect and its preparation method and application |
| CN107611516A (en) * | 2017-07-17 | 2018-01-19 | 上海工程技术大学 | A kind of internal temperature of battery real-time management method |
| CN107611516B (en) * | 2017-07-17 | 2020-06-26 | 上海工程技术大学 | Method for managing internal temperature of battery in real time |
| CN109524623A (en) * | 2018-11-16 | 2019-03-26 | 山东华亿比科新能源股份有限公司 | A kind of lithium battery composite graphite and bend resistance negative electrode tab and preparation method thereof |
| CN109524623B (en) * | 2018-11-16 | 2021-07-20 | 山东华亿比科新能源股份有限公司 | Preparation method of anti-bending negative plate of lithium battery |
| CN112133882A (en) * | 2020-08-31 | 2020-12-25 | 渤海大学 | Solvent-free preparation method of electrode for electrochemical energy storage device |
| CN112133882B (en) * | 2020-08-31 | 2022-11-15 | 渤海大学 | Solvent-free preparation method of electrode for electrochemical energy storage device |
| CN113078320A (en) * | 2021-03-26 | 2021-07-06 | 山东大学 | Melamine modified graphite negative electrode material and preparation method and application thereof |
| CN113078320B (en) * | 2021-03-26 | 2022-08-02 | 山东大学 | Melamine modified graphite negative electrode material and preparation method and application thereof |
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Application publication date: 20170405 |