CN106602074A - Negative electrode binder, negative electrode plate and lithium-ion battery of using negative electrode plate - Google Patents
Negative electrode binder, negative electrode plate and lithium-ion battery of using negative electrode plate Download PDFInfo
- Publication number
- CN106602074A CN106602074A CN201611267814.7A CN201611267814A CN106602074A CN 106602074 A CN106602074 A CN 106602074A CN 201611267814 A CN201611267814 A CN 201611267814A CN 106602074 A CN106602074 A CN 106602074A
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- China
- Prior art keywords
- negative electrode
- electrode binder
- negative
- ion battery
- plate
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Classifications
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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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a negative electrode binder, a negative electrode plate and a lithium-ion battery of using the negative electrode plate. The negative electrode binder is a chain copolymer obtained through polymerization reaction of styrene, butyl diethylene, cyclic amide and an acrylonitrile body. The intermolecular action force between the negative electrode binder and graphite, a conductive agent and a current collector is increased by an amide functional group in the negative electrode binder, the binding force of a negative electrode material for the lithium-ion battery is improved, transportation of Li<+> is facilitated through introduction of an acrylonitrile functional group with strong polarity, the phenomenon of dusting of a graphite negative electrode is significantly improved and the long-cycle capacity retention ratio of the lithium-ion battery is improved.
Description
Technical field
The invention belongs to technical field of lithium batteries, it is more particularly related to a kind of negative electrode binder, negative plate and
Its lithium ion battery.
Background technology
Business-like lithium ion battery negative material is mainly graphite, and its gram volume is up to 370mAh/g, cathodic reduction electricity
Position is close to metal Li, and layer structure is stable so that lithium ion battery has that energy density is big, good cycle, memoryless effect
The advantages of answering, but graphite cathode material lithium ion battery easily occur in cyclic process negative pole dry linting, analysis lithium and cause capacity
Decay, especially the inner ring negative plate dry linting of cylindrical battery is more serious.
The reason for graphite cathode material dry linting, is mainly：Copolymerization power/adhesion inside graphite cathode piece is little；Binding agent bullet
Property modulus it is little, the inhibitory action in negative pole charge and discharge process to expanding is little, causes electron transfer path big and graphite is peeled off；It is viscous
To the swelling larger of electrolyte, its mechanical strength is reduced, and causes adhesive failure for knot agent；While binding agent direct current internal driving
Greatly, cause electronics larger from the Charge-transfer resistance that surface treating adhesive is entered inside graphite, cause graphite cathode to analyse lithium, so as to draw
Play capacity attenuation under high magnification fast.
The binding agent that at present graphite cathode is mainly adopted is SBR styrene butadiene rubberses (SBR), non-modified SBR with
The caking property of foil, poorly conductive, are unfavorable for high rate performance, the long circulating performance of lithium ion battery.
In view of this, it is necessory to providing a kind of cohesive force by force and the negative electrode binder of battery performance being significantly improved, born
Pole piece and its lithium ion battery.
The content of the invention
The present invention goal of the invention be：There is provided a kind of cohesive force by force and the negative pole bonding of battery performance can be significantly improved
Agent, negative plate and its lithium ion battery.
In order to realize foregoing invention purpose, the present invention provides a kind of negative electrode binder, by styrene, fourth divinyl, ring-type
The chain copolymer that amide and acrylonitrile body are obtained by polyreaction, its chemical formula is：
Wherein, m1<8.
Improve as one kind of negative electrode binder of the present invention, the cyclic amide is in ring butyrolactam, hexamethylene lactams
One kind.
Improve as one kind of negative electrode binder of the present invention, the alkene nitrile monomer is containing acrylonitrile.
Improve as one kind of negative electrode binder of the present invention, the alkene nitrile monomer is acrylonitrile.
Improve as one kind of negative electrode binder of the present invention, the range of number-average molecular weight of the negative electrode binder is 2 × 105
～3 × 105, particle size range is 100～300nm.
Present invention also offers a kind of negative plate, it includes negative current collector, negative electrode active material, conductive agent and the application
Described negative electrode binder.
Improve as one kind of negative plate of the present invention, the quality of the negative electrode binder is negative electrode active material quality
1.0～8.0%.
Improve as one kind of negative plate of the present invention, the negative electrode active material is graphite.
Improve as one kind of negative plate of the present invention, the conductive agent is the one or two kinds of in SP, KS-6, CNT.
The present invention also provides a kind of lithium ion battery, and it includes positive plate, negative plate and positioned at positive plate and negative plate
Between isolating membrane, wherein the negative plate be herein described negative plate.
Relative to prior art, the present invention has following Advantageous Effects：
Amide-type functional group increases the intermolecular force between negative electrode binder and graphite, conductive agent, collector, carries
The cohesive force of lithium ion battery negative material is risen, and has introduced highly polar alkene nitrile functionality, be conducive to the transmission of Li+, shown
Work improves the phenomenon of graphite cathode dry linting, improves the macrocyclic capability retention of lithium ion battery.
Description of the drawings
With reference to the accompanying drawings and detailed description, the present invention is described in detail, wherein：
Fig. 1 is the cohesive force test comparison figure of embodiment 1 and the negative plate of comparative example 1.
Fig. 2 is embodiment 1 and the battery charging and discharging cycle performance comparison diagram of comparative example 1.
Specific embodiment
In order that the goal of the invention of the present invention, technical scheme and its technique effect become apparent from, below in conjunction with accompanying drawing and tool
Body embodiment, the present invention will be described in further detail.It should be appreciated that the specific embodiment party described in this specification
Formula is not intended to limit the present invention just for the sake of explaining the present invention.
Embodiment 1
Such as：Negative electrode binder used in the present embodiment 1 please specifically selects one for styrene, fourth divinyl, ring butyrolactam
Kind) and acrylonitrile chain copolymer, number-average molecular weight be 2 × 105(a specific numerical value please be provide, it is impossible to for scope),
Particle diameter is 300nm (please provide a specific numerical value, it is impossible to for scope).
1) sodium carboxymethyl cellulose (CMC) is added in deionized water solvent according to paste powder quality 1.5wt.% and is stirred
Dissolving forms glue, and glue is presented transparence, bubble-free, soilless sticking；
2) 2wt.% conductive agent SP, KS-6 are added toward glue, is stirred；
3) add 96wt.% graphite, high-speed stirred to slurry it is uniform, without granule, good fluidity；
4) negative electrode binder SBR 1.5wt.% of the present invention are added in slurry, are stirred；
5) coating, drying, roll-in, cut-parts slitting, wind, enter shell, fluid injection sealing after make battery；
Comparative example 1
Comparative example 1 is substantially the same manner as Example 1, and difference is：The negative electrode binder for adopting is unmodified routine
SBR styrene butadiene rubberses SBR.
Performance test
1) cohesive force test
The cohesive force of negative plate in embodiment 1 and comparative example 1 is tested.
2) cycle performance test
Test is circulated to the battery of embodiment 1 and comparative example 1 under conditions of charging and discharging currents are 15A.
Refer to shown in Fig. 1, the cohesive force of negative plate has reached 0.37N in embodiment 1, bond force curve in drawing process
Steadily, adhesion strength is 16.6N/m；And the cohesive force of negative plate is only 0.22N in comparative example 1, this shows present invention employing
Adhesion strength between negative electrode binder and graphite, conductive agent is more than non-modified conventional SBR binding agents.
This is that, containing amide-type unit in chain structure due to negative electrode binder of the present invention, the O and N in amide is easy
Hydrogen bond, increase binding agent and graphite, conductive agent, the cohesive force on foil surface are formed with-OH, and it is well dispersed.
Refer to shown in Fig. 2, under 15A charging or discharging currents, the battery of embodiment 1 holds under 3C cycling conditions after circulating 300 times
Measure conservation rate and reach 94%, and disassemble rear negative plate and dry linting and analysis lithium phenomenon do not occur, and after comparative example 1 circulates 300 times
Capability retention is only 89%, disassembles rear pole piece dry linting, and this shows following using the battery of embodiment 1 of negative electrode binder of the present invention
Ring performance is substantially better than the cycle performance of the battery of comparative example 1, and significantly improves the serious problem of graphite cathode piece dry linting.
This is because, containing alkene nitrile functionality, the highly polar of alkene nitrile functionality can increase viscous in negative electrode binder of the present invention
Knot agent and the area coverage of graphite material, binding agent is coated on graphite surface, is conducive to Li+Conduction, and, alkene nitrile functionality
With less ion/electromigration resistance, the polarization of battery under the conditions of high current can be reduced, so as to ensure that it is good that battery has
Good capability retention.
Can be seen that relative to prior art with reference to above detailed description of the present invention, the present invention at least has following
Advantageous Effects：
Amide-type functional group increases the intermolecular force between negative electrode binder and graphite, conductive agent, collector, carries
The cohesive force of lithium ion battery negative material is risen, and has introduced highly polar alkene nitrile functionality, be conducive to the transmission of Li+, shown
Work improves the phenomenon of graphite cathode dry linting, improves the macrocyclic capability retention of lithium ion battery.
According to above-mentioned principle, the present invention can also carry out appropriate change and modification to above-mentioned embodiment.Therefore, this
It is bright to be not limited to specific embodiment disclosed and described above, some modifications and changes of the present invention should also be as falling into this
In the scope of the claims of invention.Although additionally, some specific terms used in this specification, these terms
Merely for convenience of description, not to any restriction of present invention composition.
Claims (10)
1. a kind of negative electrode binder, it is characterised in that：By styrene, fourth divinyl, cyclic amide and acrylonitrile body by polymerization
The chain copolymer for obtaining is reacted, its chemical formula is：
Wherein, m1<8.
2. negative electrode binder according to claim 1, it is characterised in that：The cyclic amide is ring butyrolactam, hexamethylene
One kind in lactams.
3. negative electrode binder according to claim 1, it is characterised in that：The alkene nitrile monomer is containing acrylonitrile.
4. negative electrode binder according to claim 1, it is characterised in that：The alkene nitrile monomer is acrylonitrile.
5. negative electrode binder according to claim 1, it is characterised in that：The range of number-average molecular weight of the negative electrode binder
For 2 × 105～3 × 105, particle size range is 100～300nm.
6. a kind of negative plate, including negative current collector and negative electrode active material layer, it is characterised in that：The negative electrode active material layer
Including the arbitrary negative electrode binder of negative electrode active material, conductive agent and claim 1-5.
7. negative plate according to claim 6, it is characterised in that：The quality of the negative electrode binder is negative electrode active material
The 1.0～8.0% of quality.
8. negative plate according to claim 6, it is characterised in that：The negative electrode active material is graphite.
9. negative plate according to claim 6, it is characterised in that：The conductive agent be SP, KS-6, CNT in one kind or
Two kinds of person.
10. a kind of lithium ion battery, it includes positive plate, negative plate and the isolating membrane between positive plate and negative plate,
It is characterized in that：The negative plate is negative plate described in claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611267814.7A CN106602074A (en) | 2016-12-31 | 2016-12-31 | Negative electrode binder, negative electrode plate and lithium-ion battery of using negative electrode plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611267814.7A CN106602074A (en) | 2016-12-31 | 2016-12-31 | Negative electrode binder, negative electrode plate and lithium-ion battery of using negative electrode plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106602074A true CN106602074A (en) | 2017-04-26 |
Family
ID=58581915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611267814.7A Pending CN106602074A (en) | 2016-12-31 | 2016-12-31 | Negative electrode binder, negative electrode plate and lithium-ion battery of using negative electrode plate |
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| Country | Link |
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| CN (1) | CN106602074A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110429278A (en) * | 2019-07-10 | 2019-11-08 | 中盐安徽红四方锂电有限公司 | A kind of negative electrode slurry and preparation method thereof for low temp lithium ion battery |
| CN111816870A (en) * | 2019-04-10 | 2020-10-23 | 惠州市赛能电池有限公司 | Lithium battery negative electrode binder and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010080447A (en) * | 1999-11-19 | 2010-04-08 | Dai Ichi Kogyo Seiyaku Co Ltd | Lithium polymer secondary battery |
| CN102117914A (en) * | 2009-12-30 | 2011-07-06 | 比亚迪股份有限公司 | Battery aqueous adhesive, and electrode and battery using same |
| CN103262304A (en) * | 2010-11-29 | 2013-08-21 | 住友化学株式会社 | Electrode mixture paste, electrode, and non-aqueous electrolyte rechargeable battery |
-
2016
- 2016-12-31 CN CN201611267814.7A patent/CN106602074A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010080447A (en) * | 1999-11-19 | 2010-04-08 | Dai Ichi Kogyo Seiyaku Co Ltd | Lithium polymer secondary battery |
| CN102117914A (en) * | 2009-12-30 | 2011-07-06 | 比亚迪股份有限公司 | Battery aqueous adhesive, and electrode and battery using same |
| CN103262304A (en) * | 2010-11-29 | 2013-08-21 | 住友化学株式会社 | Electrode mixture paste, electrode, and non-aqueous electrolyte rechargeable battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111816870A (en) * | 2019-04-10 | 2020-10-23 | 惠州市赛能电池有限公司 | Lithium battery negative electrode binder and preparation method and application thereof |
| CN111816870B (en) * | 2019-04-10 | 2022-03-29 | 惠州市赛能电池有限公司 | Lithium battery negative electrode binder and preparation method and application thereof |
| CN110429278A (en) * | 2019-07-10 | 2019-11-08 | 中盐安徽红四方锂电有限公司 | A kind of negative electrode slurry and preparation method thereof for low temp lithium ion battery |
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| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20190326 |
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