CN109638286A - A kind of carboxymethyl cellulose-based binder and its application in lithium battery - Google Patents
A kind of carboxymethyl cellulose-based binder and its application in lithium battery Download PDFInfo
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- CN109638286A CN109638286A CN201811446063.4A CN201811446063A CN109638286A CN 109638286 A CN109638286 A CN 109638286A CN 201811446063 A CN201811446063 A CN 201811446063A CN 109638286 A CN109638286 A CN 109638286A
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- carboxymethyl cellulose
- based binder
- sbr
- thickener
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of carboxymethyl cellulose-based binder, the component including following parts by weight: 5 ~ 10 parts of auxiliary agent of 30 ~ 40 parts of sodium carboxymethylcellulose, modified 10 ~ 20 parts of SBR, 1 ~ 5 part of Tea Saponin, 1 ~ 5 part of thickener and dilution；The binder partial size prepared through the application is thinner, good with the intersolubility of each component, so that pole piece defect is almost nil, the flexibility of binder system also can be improved, solve pole piece problem of Cracking.
Description
Technical field
The present invention relates to the technical fields of lithium battery, more particularly, to a kind of carboxymethyl cellulose-based binder and its in lithium
Application in battery.
Background technique
In recent years, as the further landing of national new energy policy and propulsion, new-energy automobile industry have obtained length
Foot development.But therefore demand of the market to the battery product with high-energy density, high-specific-power is more more and more urgent.Develop high ratio
Energy, the li-ion electrode materials of low cost and related auxiliary material are just becoming the Research Emphasis of major battery core producer and material supplier.
Under the development trend of high-energy density, the material bodies such as positive and negative pole material, diaphragm, electrolyte of current lithium-ion-power cell
System is all constantly upgrading.Other than these main raw material(s)s, some dosages are minimum but vital auxiliary material is producing
Moral character can on also welcome change, such as lithium battery adhesive.
Currently, generally use Kynoar (PVDF) in the large-scale production of lithium ion battery and be used as binder,
PVDF is expensive, also need in application process using it is explosive, to the disagreeableness organic solvent of environment, such as N crassitude
Ketone (NMP) requires strictly, to be also easy to that secondary response occurs with lithium metal, lithium intercalated graphite, especially to the air humidity of production technology
It is at high operating temperatures, to there is the risk of spontaneous thermal runaway.Substitution of the water-soluble binder-sodium carboxymethylcellulose as PVDF
Product are used for electrode material, can avoid the use of NMP, reduce cost, reduce environmental pollution；Production technology there is not ambient humidity simultaneously
It requires, the capacity of battery also can be improved, extend cycle life.
Application publication number is that the Chinese patent of CN107910556A discloses a kind of anode material of lithium battery in existing patent
And preparation method thereof, it is composed of the following raw materials by weight: 100 ~ 110 parts of lithium hydroxide, 20 ~ 30 parts of manganese sulfate,
4 ~ 6 parts of cobalt protoxide, 2 ~ 3 parts of conductive adhesion liquid, 7 ~ 9 parts of zinc oxide, 0.1 ~ 0.2 part of sodium carboxymethylcellulose, sulfuric acid are sub-
0.08 ~ 0.1 part of tin, the positive electrode particle is uniform, has specific capacity height, good cycle, easy to industrialized production etc. excellent
Point.
But sodium carboxymethylcellulose in the prior art exists in mixed system when being mixed with various ingredients
Biggish particulate matter will affect the pliability of pole piece and increase the surface defect of pole piece.
Summary of the invention
The object of the present invention is to provide a kind of carboxymethyl cellulose-based binders, and particle is tiny, and the softness of pole piece can be improved
Property and reduce pole piece surface defect.
Foregoing invention purpose of the invention has the technical scheme that
A kind of carboxymethyl cellulose-based binder, the component including following parts by weight: 30 ~ 40 parts of sodium carboxymethylcellulose is modified
5 ~ 10 parts of auxiliary agent of 10 ~ 20 parts of SBR, 1 ~ 5 part of Tea Saponin, 1 ~ 5 part of thickener and dilution.
By using above-mentioned technical proposal, sodium carboxymethylcellulose (CMC-Na) be in the world today use scope it is most wide,
The maximum cellulose family of dosage, be glucose polymerization degree be 100 ~ 2000 cellulose derivative, relative molecular mass 242.16,
White fibrous or particulate powder, it is odorless, tasteless, there is hygroscopicity, does not dissolve in organic solvent；Sodium carboxymethylcellulose can be with
Improve the sedimentation of slurry system；Partial size is thinner, preferable with the compatibility of other components, almost prevents insoluble matter；SBR latex particle
Unit is a kind of core-shell structure, is the cross-linked structure of copolymer molecule chain in shell, and shell is hydrophilic polar group and surface
Activating agent, the aqueous group in SBR form cohesive force in conjunction with Al foil substrate, are conducive to dispersibility and Stability of Slurry；Oiliness
Group forms cohesive force in conjunction with negative electrode material, reaches bond effect；But SBR is oxidized easily under high potential, meanwhile,
Dispersed bad, the modification SBR favorable dispersibility of the application of the SBR in electrode system, and performance is stablized, under high potential
It is not easy to be oxidized, and modified SBR is in process, reduces the viscosity of system, prevent that roll banding occurs when film-making；Tea
Saponin is a kind of glycoside compounds by extracting in tea tree seed, is natural surfactant of good performance, in this Shen
Please in, Tea Saponin help to improve compatibility between each component, permeability and, while further suppressing CMC-Na at high temperature
Decomposability；The sliminess of system can be improved in thickener, can viscosity in flexible modulation system according to different demands；Dilution
Auxiliary agent improves the compatibility between each component, enhances the penetrating power of sodium carboxymethylcellulose, preferably with other components into
Row is miscible, and the binder partial size prepared through the application is thinner, good with the intersolubility of each component, so that pole piece defect is almost
It is zero, the flexibility of binder system also can be improved, solves pole piece problem of Cracking.
The present invention is further arranged to: the degree of substitution of the sodium carboxymethylcellulose is 0.5 ~ 0.8.
By using above-mentioned technical proposal, the CMC-Na of degree of substitution range structure in pelletized form, structure is more stable, reduces
The reunion of CMC-Na and other components are substantially reduced the partial size of binder system, are conducive to the performance of chemical property.
The present invention is further arranged to: the modified SBR is that SBR is carried out to silicic acid anhydride, forms SBR-SiO2Rubber cement.
By using above-mentioned technical proposal, SiO is utilized2Silicic acid anhydride is carried out to SBR, so that the surface SBR is more coarse,
And introduce low-surface energy substance and prepare hydrophobic coating, the SBR of hydrophobically modified formation is added in pole piece system, can be effectively prevent
When film-making the phenomenon that roll banding.
The present invention is further arranged to: the thickener includes the component of following parts by weight: 30 ~ 40 parts of esters of acrylic acid,
5 ~ 20 parts of carboxymethyl starch ether, 3 ~ 10 parts of carbomer, 3 ~ 10 parts and 1 ~ 5 part of POSS of xanthan gum.
By using above-mentioned technical proposal, carboxymethyl starch ether is that a certain amount of carboxyl is introduced in starch molecule, institute
It is bigger compared with the molecular weight of common starch with carboxymethyl starch, and show carboxyl intrinsic property such as hydrophily, complexing etc., it can
Suitable for various industries such as thickener, stabilizer, film forming agent, flocculant, binders；Using esters of acrylic acid, carboxymethyl starch
Ether, carbomer, xanthan gum, POSS are blended, and the levelability of gained thickener is preferable, are conducive to infilter other groups in system
In point, in addition to the viscosity to binder system is adjusted, the particle size range of system can be also widened.
The present invention is further arranged to: the viscosity of the thickener is 1000 ~ 5000mpa s.
By using above-mentioned technical proposal, the adjustable range of viscosities of the thickener is broad, improves being applicable in for product
Range.
The present invention is further arranged to: the dilution auxiliary agent includes the component of following parts by weight: α-sodium olefin sulfonate 1 ~ 5
1.5 ~ 3 parts and 3 ~ 5 parts of JFC bleeding agent of part, isomeric alcohol polyethenoxy ether.
By using above-mentioned technical proposal, α-sodium olefin sulfonate has excellent surface-active, within the scope of a certain concentration
Significantly reduce the surface tension of water；Correspondingly, having excellent dissolubility, wetability, foaming characteristic and resistance to hard water, calcium soap
Dispersion force；With good detergency, the characteristics of detergency does not reduce especially is also showed that in hard water；In addition, also having
Good biodegradability；Isomeric alcohol polyethenoxy ether is colourless or weak yellow liquid, soluble easily in water, has excellent cream
Change, washing detergency, hard water resistance performance, chemical stability and Environmental compatibility are good in wider pH value range, can be used as point
Powder, wetting agent, bleeding agent, detergent；JFC bleeding agent is a kind of extremely strong fluent material of penetration, has good attachment
Power, and fast drying, wearability are strong, while also having good chemical resistance and water resistance；Using α-sodium olefin sulfonate, isomery
Alcohol polyoxyethylene ether and JFC bleeding agent are blended, and the intersolubility of each component in raising system is conducive to.
The present invention is further arranged to: the binder is made of following steps:
(1) weighing；
(2) dilution auxiliary agent is permeated in sodium carboxymethylcellulose, keeps at least 30min, obtains premixed material；
(3) modified SBR, Tea Saponin, 2 ~ 3h of high-speed stirred are then added into premixed material；
(4) thickener is continuously added, 0.5 ~ 1h is stirred.
By using above-mentioned technical proposal, binder is prepared using the formula of the application, in advance to sodium carboxymethylcellulose
Middle addition dilutes auxiliary agent, to improve the intersolubility of sodium carboxymethylcellulose Yu other each components, then again with modification SBR, tea
Saponin is blended, and the fineness of binder system is further improved.
Foregoing invention purpose two of the invention has the technical scheme that
A kind of application of carboxymethyl cellulose-based binder, the binder is suitable for the manufacture field for making lithium battery.
By using above-mentioned technical proposal, according to this application involves formula make binder, and binder is applied
In the field of lithium battery, the quality of pole piece can be significantly improved.
In conclusion advantageous effects of the invention are as follows:
1. disclosing a kind of novel carboxymethyl cellulose-based binder, the binder system particle is tiny, and pole piece can be improved
Flexibility and the surface defect for reducing pole piece；
2. the binder of the application is the doping vario-property SBR based on sodium carboxymethylcellulose, modified SBR favorable dispersibility, property
It can stablize, also be not easy to be oxidized under high potential, and modified SBR is in process, reduce the viscosity of system, prevent
Roll banding only occurs when film-making；
3. the application is will to dilute auxiliary agent to penetrate into sodium carboxymethylcellulose, be conducive to improve sodium carboxymethylcellulose and other groups
The compatibility divided, improves the fineness uniformity of binder system.
Specific embodiment
Invention is further described in detail with reference to embodiments.
Preparation:
One, modified SBR, is made of following steps:
(1) in parts by weight, the hydroxy silicon oil that 3 ~ 5 drops are instilled into 30 ~ 40 parts of SBR, dilutes SBR, keeps infiltration 30min；
(2) 5 ~ 10 parts of SiO are continuously added2, carrying out high-speed stirred is in thick gel.
Two, thickener is made of following steps:
(1) according to parts by weight, 30 ~ 40 parts of esters of acrylic acid, 5 ~ 20 parts of carboxymethyl starch ether, carbomer 3 ~ 10 ingredient: are weighed
3 ~ 10 parts and 1 ~ 5 part of POSS of part, xanthan gum；
(2) carboxymethyl starch ether is added to esters of acrylic acid, adjusting revolving speed is 150r/min, stirs 1 ~ 1.5h；
(3) POSS, carbomer and xanthan gum are continuously added, revolving speed is improved to 200 ~ 220r/min, obtains thickener.
Three, auxiliary agent is diluted, is made of following steps:
(1) 1 ~ 5 part of α-sodium olefin sulfonate, 1.5 ~ 3 parts and 3 ~ 5 parts of JFC bleeding agent of isomeric alcohol polyethenoxy ether ingredient: are weighed；
(2) α-sodium olefin sulfonate, isomeric alcohol polyethenoxy ether and JFC bleeding agent are added in agitator tank, adjusting mixing speed is
100r/min obtains dilution auxiliary agent.
Embodiment one:
(1) ingredient: 30 parts of sodium carboxymethylcellulose, modified 10 parts of SBR, 1 part of Tea Saponin, 1 part of thickener and dilution auxiliary agent 5
Part；
(2) dilution auxiliary agent is permeated in sodium carboxymethylcellulose, keeps at least 30min, obtains premixed material；
(3) modified SBR, Tea Saponin, 2 ~ 3h of high-speed stirred are then added into premixed material；
(4) thickener is continuously added, 0.5 ~ 1h is stirred.
Embodiment two:
(1) ingredient: 32 parts of sodium carboxymethylcellulose, modified 12 parts of SBR, 2 parts of Tea Saponin, 2 parts of thickener and dilution auxiliary agent 6
Part；
(2) dilution auxiliary agent is permeated in sodium carboxymethylcellulose, keeps at least 30min, obtains premixed material；
(3) modified SBR, Tea Saponin, 2 ~ 3h of high-speed stirred are then added into premixed material；
(4) thickener is continuously added, 0.5 ~ 1h is stirred.
Embodiment three:
(1) ingredient: 34 parts of sodium carboxymethylcellulose, modified 14 parts of SBR, 3 parts of Tea Saponin, 3 parts of thickener and dilution auxiliary agent 7
Part；
(2) dilution auxiliary agent is permeated in sodium carboxymethylcellulose, keeps at least 30min, obtains premixed material；
(3) modified SBR, Tea Saponin, 2 ~ 3h of high-speed stirred are then added into premixed material；
(4) thickener is continuously added, 0.5 ~ 1h is stirred.
Example IV:
(1) ingredient: 38 parts of sodium carboxymethylcellulose, modified 18 parts of SBR, 4 parts of Tea Saponin, 4 parts of thickener and dilution auxiliary agent 9
Part；
(2) dilution auxiliary agent is permeated in sodium carboxymethylcellulose, keeps at least 30min, obtains premixed material；
(3) modified SBR, Tea Saponin, 2 ~ 3h of high-speed stirred are then added into premixed material；
(4) thickener is continuously added, 0.5 ~ 1h is stirred.
Embodiment five:
(1) ingredient: 40 parts of sodium carboxymethylcellulose, modified 20 parts of SBR, 5 parts of Tea Saponin, 5 parts of thickener and dilution auxiliary agent
10 parts；
(2) dilution auxiliary agent is permeated in sodium carboxymethylcellulose, keeps at least 30min, obtains premixed material；
(3) modified SBR, Tea Saponin, 2 ~ 3h of high-speed stirred are then added into premixed material；
(4) thickener is continuously added, 0.5 ~ 1h is stirred.
Comparative example: with application publication number in existing patent for CN107910556A Chinese patent as a comparison case.
Detection method:
(1) flexibility: by pole piece by folding three times, then energy density is detected.
(2) surface defects detection: using the flaw of the vision-based detection pole piece of Chuan Shi new science and technology company research and development.
The testing result of flexibility is as shown in the table:
| Sample | Specific discharge capacity (mAh/g) | Specific discharge capacity (mAh/g) after 100 charge and discharge cycles |
| Embodiment one | 1560 | 1420 |
| Embodiment two | 1580 | 1430 |
| Embodiment three | 1590 | 1450 |
| Example IV | 1600 | 1460 |
| Embodiment five | 1580 | 1450 |
| Comparative example | 870 | 0 |
Through upper table it is found that after folding three times, comparative example has been broken off, and can not be connected, and the various kinds in embodiment
Product can be connected, and can still release more specific capacity, and flexibility is good, and cycle performance is excellent.
The testing result of surface defect is as shown in the table:
| Sample | Surface condition |
| Embodiment one | Zero defect |
| Embodiment two | Zero defect |
| Embodiment three | Zero defect |
| Example IV | Zero defect |
| Embodiment five | Zero defect |
| Comparative example | It drops off；There is pin hole |
By upper table it is found that each sample all has good surface quality in embodiment, it is seen that its constituent component particle is tiny, equal
It is even, and the pole piece defect of comparative example method preparation is serious, bad product rate is higher, and service life is shorter, is unfavorable for extensive
Production.
The embodiment of present embodiment is presently preferred embodiments of the present invention, not limits protection of the invention according to this
Range, therefore: the equivalence changes that all structures under this invention, shape, principle are done, should all be covered by protection scope of the present invention it
It is interior.
Claims (8)
1. a kind of carboxymethyl cellulose-based binder, it is characterised in that the component including following parts by weight: sodium carboxymethylcellulose
5 ~ 10 parts of auxiliary agent of 30 ~ 40 parts, modified 10 ~ 20 parts of SBR, 1 ~ 5 part of Tea Saponin, 1 ~ 5 part of thickener and dilution.
2. a kind of carboxymethyl cellulose-based binder according to claim 1, it is characterised in that: the carboxymethyl cellulose
The degree of substitution of sodium is 0.5 ~ 0.8.
3. a kind of carboxymethyl cellulose-based binder according to claim 1, it is characterised in that: the modified SBR be by
SBR carries out silicic acid anhydride, forms SBR-SiO2Rubber cement.
4. a kind of carboxymethyl cellulose-based binder according to claim 1, it is characterised in that: the thickener includes such as
The component of lower parts by weight: 30 ~ 40 parts of esters of acrylic acid, 5 ~ 20 parts of carboxymethyl starch ether, 3 ~ 10 parts of carbomer, xanthan gum 3 ~
10 parts and 1 ~ 5 part of POSS.
5. a kind of carboxymethyl cellulose-based binder according to claim 4, it is characterised in that: the viscosity of the thickener
For 1000 ~ 5000mpa s.
6. a kind of carboxymethyl cellulose-based binder according to claim 1, it is characterised in that the dilution auxiliary agent includes
The component of following parts by weight: 1 ~ 5 part of α-sodium olefin sulfonate, 1.5 ~ 3 parts of isomeric alcohol polyethenoxy ether and JFC bleeding agent 3 ~ 5
Part.
7. a kind of carboxymethyl cellulose-based binder according to claim 1, it is characterised in that made of following steps:
(1) weighing；
(2) dilution auxiliary agent is permeated in sodium carboxymethylcellulose, keeps at least 30min, obtains premixed material；
(3) modified SBR, Tea Saponin, 2 ~ 3h of high-speed stirred are then added into premixed material；
(4) thickener is continuously added, 0.5 ~ 1h is stirred.
8. a kind of application of carboxymethyl cellulose-based binder as described in claim 1 ~ 7 any one, it is characterised in that: should
Binder is suitable for the manufacture field for making lithium battery.
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| CN112803000A (en) * | 2019-11-14 | 2021-05-14 | 孚能科技(赣州)股份有限公司 | Composition for battery negative plate coating, battery negative plate coating slurry, and preparation method and application thereof |
| CN113088232A (en) * | 2021-05-14 | 2021-07-09 | 河北星辰工程科技有限公司 | Slow-bonding agent and slow-bonding prestressed steel bar |
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| Publication number | Publication date |
|---|---|
| CN109638286B (en) | 2021-03-30 |
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