CN108832130B - Lithium battery electrode adhesive and preparation method thereof - Google Patents
Lithium battery electrode adhesive and preparation method thereof Download PDFInfo
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- CN108832130B CN108832130B CN201810662854.4A CN201810662854A CN108832130B CN 108832130 B CN108832130 B CN 108832130B CN 201810662854 A CN201810662854 A CN 201810662854A CN 108832130 B CN108832130 B CN 108832130B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
Abstract
The invention discloses a lithium battery electrode adhesive and a preparation method thereof. The composite material comprises the following raw materials in parts by weight: 800 parts of 600-800 parts of acrylate, 40-80 parts of acrylic monomer, 300 parts of 200-200 parts of acrylate polyol, 1-5 parts of cyclohexanone 1, 2-propylene glycol ketal, 0.5-3 parts of carbon nano tube and 0.01-0.1 part of azodiisoheptanonitrile. The lithium battery electrode adhesive prepared by the invention has a good protection function on a lithium battery electrode, can prevent dust and water, does not crack under a low-temperature condition, and has excellent bonding performance.
Description
Technical Field
The invention belongs to the technical field of lithium batteries for electric vehicles, and particularly relates to a lithium battery electrode adhesive and a preparation method thereof.
Background
Along with the enhancement of people's environmental consciousness and the encouragement of country, electric automobile receives people's attention more and more, and electric automobile power main source is the battery, generally is lithium cell or lithium iron phosphate battery, and lithium iron phosphate battery energy density is lower, and is comparatively heavy, has been eliminated by the market gradually.
The lithium battery has higher energy density, but also has a plurality of defects, the discharge of the lithium battery is not as stable as that of the lithium iron phosphate battery, the service life is short, the lithium battery is bonded and fixed by using a large amount of adhesive in the processing process, and water vapor enters the battery in a humid environment to cause the great damage of the battery material. The electrolytic resistance is low.
Patent 201110386395.X discloses an adhesive for a battery, which is prepared from the following materials in percentage by weight: 84-95% of acrylate, 4-15% of acrylic monomer, 0.1-5% of water absorbent and 1-5% of chain initiator; the water absorbent is acetal or ketal; the preparation method comprises the following preparation steps: firstly, adding 84-95% of acrylic ester, 4-15% of acrylic monomer and 1-5% of chain initiator into a container, and mixing; heating to 75-85 deg.C, stirring, reacting for 4.5-5.5 hr, adding 40-180g 1, 6-ethylene glycol diacrylate, and stirring for 1.5-2.5 hr; then stopping heating, and continuing stirring and cooling to room temperature; finally, adding 0.1-5% of water absorbent, and uniformly stirring to prepare the adhesive sticker. Although the adhesive has good waterproof effect, the discharge of the adhesive is unstable, the electrolytic resistance is low, and the service life is short.
Disclosure of Invention
The invention aims to provide an electrode adhesive for a lithium battery.
The invention also aims to provide a preparation method of the lithium battery electrode adhesive.
The lithium battery electrode adhesive comprises the following raw materials in parts by weight: 800 parts of 600-800 parts of acrylate, 40-80 parts of acrylic monomer, 300 parts of 200-200 parts of acrylate polyol, 1-5 parts of cyclohexanone 1, 2-propylene glycol ketal, 0.5-3 parts of carbon nano tube and 0.01-0.1 part of azodiisoheptanonitrile.
The acrylate is methyl acrylate, butyl acrylate or isobutyl acrylate.
The tube diameter of the carbon nano tube is 5-12nm, the average tube diameter is 8nm, and the length-diameter ratio is 800-2000.
The raw material of the adhesive also comprises 1-decene-3-alcohol 1-3 parts.
The raw material of the adhesive also comprises 1-3 parts of cyclopentyl chloromethyl acid.
The preparation method of the lithium battery electrode adhesive comprises the following steps:
(1) according to the weight fraction, taking 800 portions of 600-80 portions of acrylic ester, 40-80 portions of acrylic monomer, 300 portions of 200-200 portions of acrylic ester polyol and 0.01-0.1 portion of azobisisoheptonitrile, adding into a container, mixing and stirring for 10-20 min;
(2) heating to 70-85 deg.C, stirring continuously in the container, and reacting for 4-6 h;
(3) stopping heating, continuously stirring and cooling to room temperature, adding 1-5 parts of cyclohexanone 1, 2-propylene glycol ketal and 0.5-3 parts of carbon nano tube, and stirring for 10-20min to obtain the product.
1-3 parts of 1-decene-3-alcohol is also added in the step (1).
And (3) adding 1-3 parts of cyclopentyl chloroformate.
The invention has the beneficial effects that: the lithium battery electrode adhesive prepared by the invention has a good protection function on a lithium battery electrode, can prevent dust and water, does not crack under a low-temperature condition, and has excellent bonding performance.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The lithium battery electrode adhesive comprises the following raw materials in parts by weight: 700g of methyl acrylate, 60g of acrylic monomer, 250g of acrylic ester polyol, 3g of cyclohexanone 1, 2-propylene glycol ketal, 1g of carbon nano tube and 0.05g of azodiisoheptanonitrile. The tube diameter of the carbon nano tube is 5-12nm, the average tube diameter is 8nm, and the length-diameter ratio is 1200-1400.
The preparation method of the lithium battery electrode adhesive comprises the following steps:
(1) according to the weight fraction, taking 700g of methyl acrylate, 60g of acrylic monomer, 250g of acrylic ester polyol and 0.05g of azobisisoheptonitrile, adding into a container, mixing and stirring for 15 min;
(2) heating to 80 ℃, and continuously stirring in the container for reaction for 5 hours;
(3) stopping heating, continuing stirring and cooling to room temperature, adding 3g of cyclohexanone 1, 2-propylene glycol ketal and 1g of carbon nano tube, and stirring for 15min to obtain the nano-tube.
Example 2
The lithium battery electrode adhesive comprises the following raw materials in parts by weight: 600g of butyl acrylate, 40g of acrylic monomer, 200g of acrylic ester polyol, 1g of cyclohexanone 1, 2-propylene glycol ketal, 0.5g of carbon nano tube and 0.01g of azobisisoheptonitrile. The tube diameter of the carbon nano tube is 5-12nm, the average tube diameter is 8nm, and the length-diameter ratio is 800-1000.
The preparation method of the lithium battery electrode adhesive comprises the following steps:
(1) according to the weight fraction, taking 600g of butyl acrylate, 40g of acrylic monomer, 200g of acrylic ester polyol and 0.01g of azobisisoheptonitrile, adding into a container, mixing and stirring for 10 min;
(2) heating to 70 ℃, and continuously stirring in the container for reacting for 4 hours;
(3) stopping heating, continuing stirring and cooling to room temperature, adding 1g of cyclohexanone 1, 2-propylene glycol ketal and 0.5g of carbon nano tube, and stirring for 10min to obtain the nano-carbon tube.
Example 3
The lithium battery electrode adhesive comprises the following raw materials in parts by weight: 800g of isobutyl acrylate, 80g of acrylic monomer, 300g of acrylic ester polyol, 5g of cyclohexanone 1, 2-propylene ketal, 3g of carbon nano tube and 0.1g of azobisisoheptonitrile. The tube diameter of the carbon nano tube is 5-12nm, the average tube diameter is 8nm, and the length-diameter ratio is 1500-2000.
The preparation method of the lithium battery electrode adhesive comprises the following steps:
(1) according to the weight fraction, 800g of isobutyl acrylate, 80g of acrylic monomer, 300g of acrylic ester polyol and 0.1g of azobisisoheptonitrile are added into a container and mixed for 20 min;
(2) heating to 85 ℃, and continuously stirring in the container for reacting for 6 hours;
(3) stopping heating, continuing stirring and cooling to room temperature, adding 5g of cyclohexanone 1, 2-propylene glycol ketal and 3g of carbon nano tube, and stirring for 20min to obtain the nano-tube.
Example 4
The lithium battery electrode adhesive comprises the following raw materials in parts by weight: 700g of methyl acrylate, 60g of acrylic monomer, 250g of acrylic ester polyol, 3g of cyclohexanone 1, 2-propylene glycol ketal, 1g of carbon nano tube, 0.05g of azodiisoheptonitrile and 2g of 1-decen-3-ol. The tube diameter of the carbon nano tube is 5-12nm, the average tube diameter is 8nm, and the length-diameter ratio is 1200-1400.
The preparation method of the lithium battery electrode adhesive comprises the following steps:
(1) according to the weight fraction, taking 700g of methyl acrylate, 60g of acrylic monomer, 250g of acrylic ester polyol, 0.05g of azobisisoheptonitrile and 2g of 1-decene-3-alcohol, adding into a container, mixing, and stirring for 15 min;
(2) heating to 80 ℃, and continuously stirring in the container for reaction for 5 hours;
(3) stopping heating, continuing stirring and cooling to room temperature, adding 3g of cyclohexanone 1, 2-propylene glycol ketal and 1g of carbon nano tube, and stirring for 15min to obtain the nano-tube.
Example 5
The lithium battery electrode adhesive comprises the following raw materials in parts by weight: 700g of methyl acrylate, 60g of acrylic monomer, 250g of acrylic ester polyol, 3g of cyclohexanone 1, 2-propylene glycol ketal, 1g of carbon nano tube, 0.05g of azodiisoheptanonitrile and 2g of cyclopentyl chloroformate. The tube diameter of the carbon nano tube is 5-12nm, the average tube diameter is 8nm, and the length-diameter ratio is 1200-1400.
The preparation method of the lithium battery electrode adhesive comprises the following steps:
(1) according to the weight fraction, taking 700g of methyl acrylate, 60g of acrylic monomer, 250g of acrylic ester polyol and 0.05g of azobisisoheptonitrile, adding into a container, mixing and stirring for 15 min;
(2) heating to 80 ℃, and continuously stirring in the container for reaction for 5 hours;
(3) stopping heating, continuously stirring and cooling to room temperature, adding 3g of cyclohexanone 1, 2-propylene glycol ketal, 1g of carbon nano tube and 2g of cyclopentyl chloroformate, and stirring for 15min to obtain the nano-carbon material.
Example 6
The lithium battery electrode adhesive comprises the following raw materials in parts by weight: 700g of methyl acrylate, 60g of acrylic monomer, 250g of acrylic ester polyol, 3g of cyclohexanone 1, 2-propylene glycol ketal, 1g of carbon nano tube, 0.05g of azobisisoheptonitrile and 0.5g of overbased branched-C6-19-fatty acid calcium salt (CAS: 68551-41-7). The tube diameter of the carbon nano tube is 5-12nm, the average tube diameter is 8nm, and the length-diameter ratio is 1200-1400.
The preparation method of the lithium battery electrode adhesive comprises the following steps:
(1) according to the weight fraction, taking 700g of methyl acrylate, 60g of acrylic monomer, 250g of acrylic ester polyol and 0.05g of azobisisoheptonitrile, adding into a container, mixing and stirring for 15 min;
(2) heating to 80 ℃, and continuously stirring in the container for reaction for 5 hours;
(3) stopping heating, continuing stirring and cooling to room temperature, adding 3g of cyclohexanone 1, 2-propylene glycol ketal, 1g of carbon nano tube and 0.5g of high-alkalinity branched chain-C6-19-fatty acid calcium salt, and stirring for 15min to obtain the product.
Example 7
The lithium battery electrode adhesive comprises the following raw materials in parts by weight: 700g of methyl acrylate, 60g of acrylic monomer, 250g of acrylic ester polyol, 3g of cyclohexanone 1, 2-propylene glycol ketal, 1g of carbon nano tube, 0.5g of erbium oxide and 0.05g of azodiisoheptanonitrile. The tube diameter of the carbon nano tube is 5-12nm, the average tube diameter is 8nm, and the length-diameter ratio is 1200-1400.
The preparation method of the lithium battery electrode adhesive comprises the following steps:
(1) according to the weight fraction, taking 700g of methyl acrylate, 60g of acrylic monomer, 250g of acrylic ester polyol and 0.05g of azobisisoheptonitrile, adding into a container, mixing and stirring for 15 min;
(2) heating to 80 ℃, and continuously stirring in the container for reaction for 5 hours;
(3) stopping heating, continuing stirring and cooling to room temperature, adding 3g of cyclohexanone 1, 2-propylene glycol ketal, 1g of carbon nano tube and 0.5g of erbium oxide, and stirring for 15min to obtain the nano-tube.
Experimental example 1:
the adhesive prepared in the embodiment 1-7 is adopted to bond an aluminum sheet which has the same material as the current collector of the positive electrode of the lithium battery, the surface of the aluminum sheet is uniformly coated with glue for 10 times, each time is separated by 4 minutes, then the sample is dried for 4 hours at 50 ℃, finally the sample is dried for 15 minutes at 150 ℃, and the adhesive strength of the dried adhesive is tested; the dried samples were immersed in PC electrolyte and DME electrolyte for 7 days, respectively, and the adhesive strength was measured and the decrease in the adhesive strength was calculated. The test results are shown in tables 1-3:
TABLE 1
Note: represents P <0.05 compared to the example 1 group.
As can be seen from table 1, the adhesive strengths of examples 1 to 3 were not significantly different, and the adhesive strengths of examples 4 to 7 were significantly higher than that of example 1.
TABLE 2
Note: represents P <0.05 compared to the example 1 group; represents P < 0.01.
As can be seen from Table 2, the adhesive strength of examples 1 to 3 did not significantly differ after the PC was soaked for 7 days,
the bonding strength of examples 4-7 was significantly higher than that of example 1; the reduction in adhesive strength of examples 1 to 3 was not significantly different, and the reduction in adhesive strength of examples 4 to 7 was significantly lower than that of example 1.
TABLE 3
Note: represents P <0.05 compared to the example 1 group; represents P < 0.01.
As can be seen from Table 3, the adhesive strength of examples 1-3 did not differ significantly after DME immersion for 7 days,
the bonding strength of examples 4-7 was significantly higher than that of example 1; the reduction in adhesive strength of examples 1 to 3 was not significantly different, and the reduction in adhesive strength of examples 4 to 7 was significantly lower than that of example 1.
Experimental example 2:
lithium batteries for experiments were prepared by bonding the negative electrode materials of the common lithium batteries with the adhesives of examples 1 to 7, and the batteries were tested for repeated charge and discharge characteristics, with a capacity of 0.2 coulomb, and the experiments were repeated 5 times. And (4) obtaining the charge-discharge efficiency for the first time and after 50 times.
Charge-discharge efficiency (discharge capacity/charge capacity) × 100 (%);
the test results of the charge and discharge characteristics are shown in table 4:
TABLE 4
Note: represents P <0.05 compared to the example 1 group.
As can be seen from table 4, the first charge-discharge efficiency and the charge-discharge efficiency values after 50 times in examples 1 to 3 were not significantly different from each other, and the first charge-discharge efficiency and the charge-discharge efficiency values after 50 times in examples 4 to 7 were significantly higher than those in example 1.
Claims (4)
1. The lithium battery electrode adhesive is characterized by comprising the following raw materials in parts by weight: 800 parts of acrylate 600-containing material, 40-80 parts of acrylic monomer, 300 parts of acrylate polyol 200-containing material, 1-5 parts of cyclohexanone 1, 2-propylene glycol ketal, 0.5-3 parts of carbon nano tube, 0.01-0.1 part of azodiisoheptanonitrile, and 1-3 parts of 1-decene-3-alcohol or cyclopentyl chloroformate.
2. The lithium battery electrode binder of claim 1, wherein the acrylate is methyl acrylate, butyl acrylate, or isobutyl acrylate.
3. The lithium battery electrode adhesive as recited in claim 1, wherein the carbon nanotubes have a tube diameter of 5-12nm, an average tube diameter of 8nm, and an aspect ratio of 800-2000.
4. The method for preparing an electrode binder for a lithium battery according to claim 1, comprising the steps of:
(1) according to the weight fraction, taking 800 portions of 600-80 portions of acrylic ester, 40-80 portions of acrylic monomer, 300 portions of 200-200 portions of acrylic ester polyol and 0.01-0.1 portion of azobisisoheptonitrile, adding into a container, mixing and stirring for 10-20 min;
(2) heating to 70-85 deg.C, stirring continuously in the container, and reacting for 4-6 h;
(3) stopping heating, continuously stirring and cooling to room temperature, adding 1-5 parts of cyclohexanone 1, 2-propylene glycol ketal and 0.5-3 parts of carbon nano tube, and stirring for 10-20min to obtain the product;
1-3 parts of 1-decene-3-alcohol is added in the step (1) or 1-3 parts of cyclopentyl chloroformate is also added in the step (3).
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| CN112063355A (en) * | 2020-08-28 | 2020-12-11 | 广东安德力新材料有限公司 | Adhesive for power battery aluminum plastic film and processing technology thereof |
| CN112009057B (en) * | 2020-08-28 | 2023-03-28 | 广东安德力新材料有限公司 | Composite aluminum-plastic film for power battery |
| CN114583171A (en) * | 2022-01-20 | 2022-06-03 | 贵阳学院 | Lithium battery electrode adhesive and preparation method thereof |
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| CN102516905A (en) * | 2011-11-29 | 2012-06-27 | 宁波蓝鼎电子科技有限公司 | Adhesive for batteries and preparation method for adhesive |
| CN104479619A (en) * | 2014-12-11 | 2015-04-01 | 乐凯胶片股份有限公司 | Adhesive composition and solar cell rear panel |
| CN105462523A (en) * | 2016-01-05 | 2016-04-06 | 吉林大学 | Method for preparing high-adhesion water-borne adhesive based on polymer compound |
| CN107474748A (en) * | 2017-07-24 | 2017-12-15 | 成都纳硕科技有限公司 | A kind of new optic-solidified adhesive |
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2018
- 2018-06-25 CN CN201810662854.4A patent/CN108832130B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102325853A (en) * | 2008-12-12 | 2012-01-18 | 汉高公司 | Reactive hot melt adhesive |
| CN102516905A (en) * | 2011-11-29 | 2012-06-27 | 宁波蓝鼎电子科技有限公司 | Adhesive for batteries and preparation method for adhesive |
| CN104479619A (en) * | 2014-12-11 | 2015-04-01 | 乐凯胶片股份有限公司 | Adhesive composition and solar cell rear panel |
| CN105462523A (en) * | 2016-01-05 | 2016-04-06 | 吉林大学 | Method for preparing high-adhesion water-borne adhesive based on polymer compound |
| CN107474748A (en) * | 2017-07-24 | 2017-12-15 | 成都纳硕科技有限公司 | A kind of new optic-solidified adhesive |
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