CN106384830A - Adhesive used for electrode of lithium battery - Google Patents
Adhesive used for electrode of lithium battery Download PDFInfo
- Publication number
- CN106384830A CN106384830A CN201611111193.3A CN201611111193A CN106384830A CN 106384830 A CN106384830 A CN 106384830A CN 201611111193 A CN201611111193 A CN 201611111193A CN 106384830 A CN106384830 A CN 106384830A
- Authority
- CN
- China
- Prior art keywords
- graphene
- binding agent
- electrode
- polymer
- lithium cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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 invention discloses an adhesive used for an electrode of a lithium battery and the lithium battery comprising the adhesive. The adhesive is prepared from graphene and a polymer chemically bonded to the graphene, so that a conduction path can be formed by improving dispersion of the graphene. The lithium battery disclosed by the invention can have high capacity and is capable of prolonging the service life of the lithium battery.
Description
Technical field
The present invention relates to a kind of chemical bonding agent class, especially a kind of binding agent for electrode of lithium cell.
Background technology
Portable electron device for information communication is (as personal digital assistant (PDA), mobile phone and notebook electricity
Brain), electric bicycle and lithium secondary battery used in electric automobile there is the electric discharge electricity of at least twice compared with other batteries
Pressure, therefore can present high-energy-density.
Lithium secondary battery comprises organic bath or the polymer dielectric being filled between positive pole and negative pole, described positive pole and
Negative pole comprises to embed the active substance with de-embedding lithium ion, and lithium secondary battery is according to lithium ion in positive pole and negative pole
During embedded/de-embedding, electric energy is produced by redox reaction.
The positive active material of lithium secondary battery for comprising lithium and transition metal and can have and can embed lithium ion
The oxide of structure, such as lithium and cobalt oxides (LiCoO2), lithium nickel oxide (LiNiO2) and lithium nickel cobalt manganese oxide (Li
[NiCoMn]O2Or Li [Ni1-x-yCoxMy]O2).
/ variously-shaped carbons the material and such as including artificial or native graphite or hard carbon of de-embedding lithium can be embedded
The non-carbons material of silicon is studied as negative electrode active material.Because capacity density is 10 times or higher, non-carbon of graphite
Class material can have very high capacity, but because the volume very high compared with carbons material when embedding with de-embedding lithium is swollen
Swollen and shrink, thus it is difficult to the desired volume of non-carbons material.
Therefore, in order to improve high-capacity material and formed lithium battery each element characteristic, such as positive active material,
The characteristic of electrolyte, dividing plate and binding agent, and carried out positive research.
Content of the invention
One or more embodiments include to improve the viscous of described service life of lithium battery characteristic for electrode of lithium cell
Knot agent.
One or more embodiments include the lithium battery containing described binding agent.
According to one or more embodiments, described binding agent includes：Graphene；The titanium dioxide that surface carboxyl groupsization are processed
Titanium；Water-soluble cellulose ether；With the polymer by chemical bonding to described Graphene；The weight ratio of each ingredient
As follows：The polymer of 100 weight portions；The described Graphene of 1 weight portion to 50 weight portions；The institute of 0.05 weight portion to 5 weight portions
State water-soluble cellulose ether；And 0.01 weight portion to 10 weight portions the titanium dioxide that processes of described surface carboxyl groupsization.
According to one or more embodiments, lithium battery includes：Negative pole；Positive pole in the face of described negative pole；With positioned at described
Electrolyte between negative pole and described positive pole, at least one of wherein said negative pole and described positive pole includes described binding agent.Root
According to one or more embodiments, described binding agent comprises：Graphene；With by poly- on chemical bonding to described Graphene
Compound.In some embodiments, described chemical bond is ionic bond or covalent bond.Additionally, in some embodiments, described common
Valence link comprises at least one in ester group, amide groups and acid anhydride.In some embodiments, described ionic bond comprises carboxylic acid
Radical ion and ammonium ion.In some embodiments, described polymer passes through chemical bonding on described Graphene.At some
In embodiment, described chemical bond is ionic bond or covalent bond.Additionally, in some embodiments, described covalent bond comprises ester
At least one in base, amide groups and acid anhydride, and in some embodiments, described ionic bond comprise carboxylic acid ion and
Ammonium ion.
Some embodiments are related to comprise Graphene and by the use of the polymer on described Graphene for the chemical bonding
In the binding agent preparation method of lithium secondary battery, methods described comprises：The Graphene with functional group is added polymer or can
Polymeric material, to form mixture, stirs and heats described mixture to form described binding agent.In some embodiments, institute
Stating functional group is carboxyl, hydroxyl, chlorine acyl group or amido, and in some embodiments, the functional group of described Graphene is carboxyl,
Described carboxyl was modified as chlorine acyl group or amine before adding described Graphene in described polymer or described polymerizable material
Base.
Binding agent for electrode of lithium cell can improve pathway by improving the dispersion of Graphene with low amounts, and carries
The life-span of high lithium battery.
Specific embodiment
Hereafter will be described in detail one or more embodiments.
Included for the binding agent of electrode of lithium cell according to embodiment：The titanium dioxide that surface carboxyl groupsization are processed；Water
Cellulose of solubleness ether；With the polymer by chemical bonding to described Graphene；The weight ratio of each ingredient is as follows：
The polymer of 100 weight portions；The described Graphene of 1 weight portion to 50 weight portions；0.05 weight portion is described water-soluble to 5 weight portions
Property cellulose ether；And 0.01 weight portion to 10 weight portions the titanium dioxide that processes of described surface carboxyl groupsization.
Described binding agent may be used in the negative electrode active material being capable of high power capacity, such as silicon-based active substances, stannum class
The electrode of the lithium battery of active substance or silico-carbo class active substance.Because polymer is chemically bonded on Graphene, binding agent
Thus improve the dispersion of Graphene, due to pathway is defined with low amounts, binding agent thus there is high power capacity, when driving
Because charging and discharging causes in the expansion and contraction process of active substance during lithium battery, due to Graphene mobile binding agent because
Without luming, the tensile strength due to increased binding agent by Graphene maintains pathway, binding agent thus improve
Life-span of lithium battery.
Graphene not only has excellent mechanical strength, heat conductivity and chemical stability, also has the electricity similar to copper
Conductivity, therefore suitable as conductive filler.Graphene for binding agent can be any kind of Graphene, such as monolayer
Graphene, bilayer graphene, multi-layer graphene or its mixed type.Based on the polymer of 100 weight portions, the consumption of Graphene can
Think about 1 to about 30 weight portion, for example, about 5 to about 20 weight portions.
Binding agent can be the aqueous binders being dissolved in the water or be dissolved in the organic binder bond in organic solvent.This
Place, aqueous binders are eco-friendly, and can differently realize the various characteristics of organic binder bond, such as adhesion strength, anti-
Zhang Qiangdu and elasticity.Therefore, as long as obtaining this aqueous or organic binder bond, polymer is just unrestricted.However, can not be using not
It is dissolved in the binding agent of water or organic solvent.
The molecular weight of polymer is unrestricted, as long as polymer includes forming the official of chemical bond with pretreated Graphene
Can group such as hydroxyl, carboxyl or amido, and compatible with the active substance that comprises in electrod composition and other additives with formation
Slurry.And, polymer must have electrochemically stable characteristic in lithium cell charging and electric discharge.
The example of polymer includes polyamic acid, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), starch, hydroxypropyl
Cellulose, regenerated cellulose, phenolic resin, epoxy resin, polyimides (PI), polyamidoimide (PAI), polyacrylic acid,
Polymethylacrylic acid, its copolymer, its modified resin and its condensation polymer with other components.Polymer can be used with single type
Or used by mixing at least two types.
Graphene and polymer chemistry bonding are it is meant that Graphene and polymer pass through ionic bond or covalently bonded.
Binding agent will not only be formed by admixed graphite alkene and polymer, but passes through chemical bonding Graphene and polymer
Graphene will not be lumpd and can satisfactorily disperse and be formed.
According to the embodiment of the present invention, Graphene and polymer pass through ionic bond or covalent bond chemical bonding.
Depending on the functional group selected by polymeric material and pretreated Graphene, gained covalent bond can be ester
At least one in base, amide groups and acid anhydride.
Ionic bond can comprise carboxylic acid ion and ammonium ion.Herein, ammonium ion refers to RNH3 +(R is hydrogen or comprises with C1
Any one to the alkyl of C20, thiazolinyl and alkynyl).
Following methods can be used for forming chemical bond.For example, in order to be bonded with polymer chemistry, pre- place is carried out to Graphene
Reason is to introduce functional group, such as carboxyl (- COOH), hydroxyl (- OH), amido (- NH on the surface of Graphene2) or chlorine acyl group
(COCl).For example, it is possible to strong acid etc. pass through wet etching or with plasma or vacuum ultraviolet rays by dry etching to
The surface of Graphene introduces the functional group as carboxyl (- COOH), and introduces Graphene and the polymerizable thing of functional group by mixing
The polymer of matter (for example, the polymer of monomer, oligomer, low-molecular-weight) or synthesis carries out chemical reaction and produces chemical bond.For
It is easy to the type according to polymer and produce chemical bond, can be by other method, such as acid treatment, the graphite to introducing carboxyl
Alkene is modified, and is bonded with polymer chemistry.
Mainly there are two methods chemical bonding Graphene and polymer.First method is by pretreated graphite alkylene
Learn the method after being bonded to the monomer that polyreaction can occur or oligomer, polymer being formed by polyreaction, second method
It is the method that the polymer of pretreated Graphene and synthesis is directly carried out chemical reaction.First method can manufacture respectively
Plant binding agent, second method includes relatively simple manufacture process.According to an embodiment, Graphene and polymer use
Two kinds of method chemical bondings.
If pretreated Graphene is only with polymer mixed to use as binding agent, then be difficult to when manufacturing electrode
Chemical bond is produced between pretreated Graphene and polymer.Even if causing physical connection, adhesion and chemical bond phase
Weaker than also, therefore Graphene can lump.And, if only passing through admixed graphite alkene to form binding agent with polymer, battery
Characteristic also will not be improved.
Thus, binding agent is formed by chemical bonding Graphene and polymer, by improving the dispersion of Graphene
Define pathway, therefore, increased the amount of active substance, it is achieved thereby that high power capacity.And, even if when driving lithium electricity
During causing active mass expansion and shrink due to charging and discharging during pond, also maintain pathway and no Graphene
Caking, therefore the life characteristic of lithium battery can be improved.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses the present invention.
Multiple modifications to these embodiments will be apparent from for those skilled in the art, as defined herein
General Principle can be realized without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention
It is not intended to be limited to embodiment illustrated herein, and be to fit to consistent with principles disclosed herein and features of novelty
Scope the widest.
Claims (7)
1. a kind of binding agent for electrode of lithium cell, wherein said binding agent comprises：
Graphene；
The titanium dioxide that surface carboxyl groupsization are processed；
Water-soluble cellulose ether；With
Polymer by chemical bonding to described Graphene；The weight ratio of each ingredient is as follows：
The polymer of 100 weight portions；
The described Graphene of 1 weight portion to 50 weight portions；
The described water-soluble cellulose ether of 0.05 weight portion to 5 weight portions；And
The titanium dioxide that the described surface carboxyl groupsization of 0.01 weight portion to 10 weight portions are processed.
2. the binding agent for electrode of lithium cell according to claim 1, wherein said chemical bond is ionic bond or covalent
Key.
3. the binding agent for electrode of lithium cell according to claim 2, wherein said covalent bond includes ester group, amide groups
With at least one in acid anhydride.
4. the binding agent for electrode of lithium cell according to claim 2, wherein said ionic bond includes carboxylic acid ion
And ammonium ion.
5. the binding agent for electrode of lithium cell according to claim 1, wherein said Graphene is single-layer graphene, double
Layer graphene, multi-layer graphene or their mixture.
6. the binding agent for electrode of lithium cell according to claim 1, the consumption of wherein said Graphene is based on 100 weights
The described polymer of amount part is 1 to 30 weight portion.
7. the binding agent for electrode of lithium cell according to claim 1, wherein said polymer is included selected from polyamides
Amino acid, polyvinyl alcohol, carboxymethyl cellulose, starch, hydroxypropyl cellulose, regenerated cellulose, phenolic resin, epoxy resin, poly-
Acid imide, polyamidoimide, polyacrylic acid, polymethylacrylic acid, their copolymer, their modified resin and they
At least one in the group of condensation polymer composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611111193.3A CN106384830A (en) | 2016-12-06 | 2016-12-06 | Adhesive used for electrode of lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611111193.3A CN106384830A (en) | 2016-12-06 | 2016-12-06 | Adhesive used for electrode of lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106384830A true CN106384830A (en) | 2017-02-08 |
Family
ID=57959635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611111193.3A Pending CN106384830A (en) | 2016-12-06 | 2016-12-06 | Adhesive used for electrode of lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106384830A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1728427A (en) * | 2004-07-29 | 2006-02-01 | 肇庆市风华锂电池有限公司 | Adhesion agent of anode, pulp for anode obtained, lithium battery ,and preparation method |
| CN103199257A (en) * | 2012-01-10 | 2013-07-10 | 三星Sdi株式会社 | Binder for electrode of lithium battery and lithium battery containing the binder |
| CN103242595A (en) * | 2012-02-09 | 2013-08-14 | 三星Sdi株式会社 | Composite binder for battery, and anode and battery including the composite |
| CN105489898A (en) * | 2015-12-31 | 2016-04-13 | 深圳市贝特瑞新能源材料股份有限公司 | Conductive waterborne binder and preparation method therefor, and lithium ion battery |
-
2016
- 2016-12-06 CN CN201611111193.3A patent/CN106384830A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1728427A (en) * | 2004-07-29 | 2006-02-01 | 肇庆市风华锂电池有限公司 | Adhesion agent of anode, pulp for anode obtained, lithium battery ,and preparation method |
| CN103199257A (en) * | 2012-01-10 | 2013-07-10 | 三星Sdi株式会社 | Binder for electrode of lithium battery and lithium battery containing the binder |
| CN103242595A (en) * | 2012-02-09 | 2013-08-14 | 三星Sdi株式会社 | Composite binder for battery, and anode and battery including the composite |
| CN105489898A (en) * | 2015-12-31 | 2016-04-13 | 深圳市贝特瑞新能源材料股份有限公司 | Conductive waterborne binder and preparation method therefor, and lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mai et al. | Self‐healing materials for energy‐storage devices | |
| Zou et al. | A review of the design of advanced binders for high‐performance batteries | |
| Ryu et al. | Room‐temperature crosslinkable natural polymer binder for high‐rate and stable silicon anodes | |
| Yuan et al. | A review of functional binders in lithium–sulfur batteries | |
| Jeong et al. | Mussel-inspired self-healing metallopolymers for silicon nanoparticle anodes | |
| Gao et al. | Regulating polysulfide redox kinetics on a self‐healing electrode for high‐performance flexible lithium‐sulfur batteries | |
| Preman et al. | Progress of 3D network binders in silicon anodes for lithium ion batteries | |
| Choi et al. | Recent progress on polymeric binders for silicon anodes in lithium-ion batteries | |
| Chen et al. | Self‐healing materials for next‐generation energy harvesting and storage devices | |
| CN103199257B (en) | Binding agent for electrode of lithium cell and the lithium battery comprising the binding agent | |
| Deng et al. | Design criteria for silicon‐based anode binders in half and full cells | |
| Jin et al. | A self‐healable polyelectrolyte binder for highly stabilized sulfur, silicon, and silicon oxides electrodes | |
| Pan et al. | Polymer Binders Constructed through Dynamic Noncovalent Bonds for High‐Capacity Silicon‐Based Anodes | |
| Chen et al. | Cross-linked hyperbranched polyethylenimine as an efficient multidimensional binder for silicon anodes in lithium-ion batteries | |
| Lee et al. | In situ cross-linked carboxymethyl cellulose-polyethylene glycol binder for improving the long-term cycle life of silicon anodes in Li ion batteries | |
| Zhu et al. | Progress of binder structures in silicon-based anodes for advanced lithium-ion batteries: A mini review | |
| WO2018195897A1 (en) | Composite binder for lithium-ion battery and preparation method therefor | |
| CN103534843A (en) | Coated particles for lithium battery cathodes | |
| Wang et al. | Self-healing double-cross-linked supramolecular binders of a polyacrylamide-grafted soy protein isolate for Li–S batteries | |
| Lee et al. | Poly (aniline-co-anthranilic acid) as an electrically conductive and mechanically stable binder for high-performance silicon anodes | |
| Yu et al. | Bifunctional hydrogen-bonding cross-linked polymeric binder for high sulfur loading cathodes in lithium/sulfur batteries | |
| JP6980217B2 (en) | Binders for active material compositions containing cellulosic conductive polymers and lithium-ion batteries manufactured from them | |
| US20200403244A1 (en) | Binder, composition, electrode material, and method for making electrode material | |
| Song et al. | Constructing a resilient hierarchical conductive network to promote cycling stability of SiOx anode via binder design | |
| Nam et al. | Ion-conductive self-healing polymer network based on reversible imine bonding for Si electrodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170208 |