CN109836566A - A kind of adhesive of selfreparing and its preparation method and application - Google Patents
A kind of adhesive of selfreparing and its preparation method and application Download PDFInfo
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- CN109836566A CN109836566A CN201811520010.2A CN201811520010A CN109836566A CN 109836566 A CN109836566 A CN 109836566A CN 201811520010 A CN201811520010 A CN 201811520010A CN 109836566 A CN109836566 A CN 109836566A
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- upy
- adhesive
- selfreparing
- preparation
- isocyanate
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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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- Battery Electrode And Active Subsutance (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses adhesives of a kind of selfreparing and its preparation method and application, preparation method are as follows: mix -4 [1H]-pyrimidone of -6 methyl of 2 amino and hexamethylene diisocyanate in proportion, and it is heated to 45-55 DEG C, 10-20h is kept the temperature, UPy-isocyanate is prepared；Polyethylene glycol, dibutyl tin dilaurate and UPy-isocyanate are dissolved in chloroform, 10-20h is kept the temperature after being heated to 55-65 DEG C after dissolution, UPy-PEG-UPy adhesive is obtained after reflux.The advantage of the invention is that adhesive has good self-reparing capability；The adhesive is used in the electrode fabrication of lithium ion battery, be can use its self-repairability during going lithiumation every time the micro-crack reparation of active material particle surface treating adhesive layer, is avoided the reunion of nano particle, extend the service life of battery.
Description
Technical field
Application the present invention relates to adhesive for being related to a kind of selfreparing and preparation method thereof and in lithium ion battery belongs to
In new energy especially chemical energy storage technical field.
Background technique
Lithium ion battery has outstanding advantages of monomer voltage is high, specific energy is big, has extended cycle life, is environmentally friendly, because
And rapidly in mobile phone, the portable electronic consumers product such as laptop market occupies critical positions, becomes in people's daily life
Indispensable important component.Anode material for lithium-ion batteries now is mainly by cobalt acid lithium, LiFePO4, ternary material
Material, lithium-rich manganese base material etc.；Negative electrode material is mainly graphite, silicon, lithium titanate etc..
In use, electrode material volume during lithiumation can expand lithium ion battery, especially to some logical
It crosses with the alloying of lithium and reaches the big specific capacity electrode material of lithium storage function, such as silicon, tin, etc..The powder and micron of these materials
During use, since charge and discharge repeatedly lead to the expansion repeatedly and contraction of volume, electrode material ruptures and afflux for body
Body loses electrical contact, and the SEI film for also resulting in surface constantly thickens, and eventually leads to the decline of lithium battery performance, service life contracting
It is short.Researcher attempts the service life for improving this kind of electrode with the method for nanosizing, and still, nano particle is swollen repeatedly
It will lead to the rupture of surface treating adhesive layer in swollen, and then contact with each other, electrochemistry sintering, the i.e. reunion of electrochemistry driving occurs.Group
The problem of bulky grain after poly- can repeat above-mentioned powder and micron again.
Summary of the invention
The purpose of the present invention is to provide adhesive of a kind of selfreparing and preparation method thereof and in lithium ion battery
Using the adhesive has self-repair function, can be used to solve alloy-type electrode material volume expansion institute in use
The problem of causing.
The present invention through the following technical solutions to achieve the above objectives:
A kind of adhesive of selfreparing is UPy-PEG-UPy adhesive, and concrete structure formula is as follows:
In formula, n is the natural number between 70~100.
The present invention also provides a kind of preparation method of the adhesive of selfreparing, step includes
Step 1: by -4 [1H]-pyrimidone [2-amino-6-methylpyrimidin-4 (1H)-of -6 methyl of 2 amino
One] and hexamethylene diisocyanate (NCO-C6H12- NCO) it is mixed by the molar ratio of 1:0.8-1.2, and it is heated to 45-55
DEG C, 10-20h is kept the temperature, UPy-isocyanate is prepared；
Step 2: polyethylene glycol (PEG), dibutyl tin dilaurate (DBTDL) and UPy-isocyanate are dissolved
In chloroform, wherein mole between polyethylene glycol (PEG), dibutyl tin dilaurate (DBTDL) and UPy-isocyanate
Than keeping the temperature 10-20h after being heated to 55-65 DEG C after dissolution, obtaining UPy-PEG-UPy after reflux for 1:0.01-0.03:3-5.
Further improvement lies in that in step 1, -4 [the 1H]-pyrimidone of -6 methyl of 2 amino and two isocyanide of hexa-methylene
Acid esters is mixed by the molar ratio of 1:1.
Further improvement lies in that being heated to 50 DEG C after the mixing in step 1, and keep the temperature 16h preparation UPy-
isocyanate。
Further improvement lies in that in step 2, the polyethylene glycol, dibutyl tin dilaurate and UPy-isocyanate
Between molar ratio be 1:0.02:4.
Further improvement lies in that keeping the temperature 16h after being heated to 60 DEG C in step 2, after dissolution, UPy-PEG- is obtained after reflux
UPy adhesive.
The present invention also provides a kind of application of the adhesive of above-mentioned selfreparing in lithium ion battery.
Further improvement lies in that preparing silicon electrode after UPy-PEG-UPy adhesive is mixed with silicon nano power.
The beneficial effects of the present invention are: the adhesive of preparation has good self-reparing capability；Preparation method is simple, at
This is low；The adhesive is used in the electrode fabrication of lithium ion battery, can use its self-repairability in the mistake for going lithiumation every time
The micro-crack reparation of active material particle surface treating adhesive layer in journey, the reunion of nano particle is avoided, to have better
Cyclical stability and higher coulombic efficiency, extend the service life of battery.
Detailed description of the invention
Fig. 1 is the preparation flow figure of selfreparing adhesive；
Fig. 2 is the infrared absorption spectra of selfreparing adhesive；
Fig. 3 is the optical microscope of selfreparing adhesive films scratch experiment；
Fig. 4 be the silicon electrode prepared after being mixed using UPy-PEG-UPy as adhesive with silicon nano power cyclical stability and
Coulombic efficiency figure.
Specific embodiment
The application is described in further detail with reference to the accompanying drawing, it is necessary to it is indicated herein to be, implement in detail below
Mode is served only for that the application is further detailed, and should not be understood as the limitation to the application protection scope, the field
Technical staff can make some nonessential modifications and adaptations to the application according to above-mentioned application content.
Embodiment 1
A kind of adhesive of selfreparing is UPy-PEG-UPy adhesive, and concrete structure formula is as follows:
In formula, n 70.
A kind of preparation method of the adhesive of selfreparing, step include
Step 1: -4 [1H]-pyrimidone of -6 methyl of 2 amino and hexamethylene diisocyanate are pressed to the molar ratio of 1:0.8
Mixing, and 45 DEG C are heated to, 20h is kept the temperature, UPy-isocyanate is prepared；
Step 2: polyethylene glycol, dibutyl tin dilaurate and UPy-isocyanate are dissolved in chloroform, wherein
Molar ratio between polyethylene glycol, dibutyl tin dilaurate and UPy-isocyanate is 1:0.01:3, is heated to after dissolution
20h is kept the temperature after 55 DEG C, and UPy-PEG-UPy adhesive is obtained after reflux.
Embodiment 2
A kind of adhesive of selfreparing is UPy-PEG-UPy adhesive, and concrete structure formula is as follows:
In formula, n 80.
As shown in connection with fig. 1, a kind of preparation method of the adhesive of selfreparing, step include
Step 1: -4 [1H]-pyrimidone of -6 methyl of 2 amino and hexamethylene diisocyanate is mixed by the molar ratio of 1:1
It closes, and is heated to 50 DEG C, keep the temperature 16h, prepare UPy-isocyanate；
Step 2: polyethylene glycol, dibutyl tin dilaurate and UPy-isocyanate are dissolved in chloroform, wherein
Molar ratio between polyethylene glycol, dibutyl tin dilaurate and UPy-isocyanate is 1:0.02:4, is heated to after dissolution
16h is kept the temperature after 60 DEG C, and UPy-PEG-UPy adhesive is obtained after reflux.
Embodiment 3
A kind of adhesive of selfreparing is UPy-PEG-UPy adhesive, and concrete structure formula is as follows:
In formula, n 100.
A kind of preparation method of the adhesive of selfreparing, step include
Step 1: -4 [1H]-pyrimidone of -6 methyl of 2 amino and hexamethylene diisocyanate are pressed to the molar ratio of 1:1.2
Mixing, and 55 DEG C are heated to, 10h is kept the temperature, UPy-isocyanate is prepared；
Step 2: polyethylene glycol, dibutyl tin dilaurate and UPy-isocyanate are dissolved in chloroform, wherein
Molar ratio between polyethylene glycol, dibutyl tin dilaurate and UPy-isocyanate is 1:0.03:5, is heated to after dissolution
10h is kept the temperature after 65 DEG C, and UPy-PEG-UPy adhesive is obtained after reflux.
By taking embodiment 2 as an example, its structure and performance are studied:
As shown in connection with fig. 2, it can see in infrared absorption spectra, 1597 and 1657cm-1And 1932cm-1Three of place
Infrared absorption peak respectively corresponds C=C in UPy, and the vibration of C=O and c h bond illustrate the successful preparation of UPy-PEG-UPy.
As shown in connection with fig. 3, after UPy-PEG-UPy adhesive being made into film, a scratch is introduced using blade on surface
(a), 10min (b) is placed respectively, 15min (c), 20min (d), after 20min (e), 30min (f), scratch is gradually tapered up, finally
It completely disappears.This illustrates that the film has good self-reparing capability.
The present invention also provides application of the adhesive of above-mentioned selfreparing in lithium ion battery, one of which is specifically answered
With embodiment are as follows: prepare silicon electrode after mixing UPy-PEG-UPy adhesive with silicon nano power.
As shown in connection with fig. 4, it can be seen that compared with general aqueous binder PAA, use UPy-PEG-UPy as bonding
The silicium cathode of agent has better cyclical stability and higher coulombic efficiency.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.
Claims (8)
1. a kind of adhesive of selfreparing, which is characterized in that be UPy-PEG-UPy adhesive, concrete structure formula is as follows:
In formula, n is the natural number of 70-100.
2. a kind of preparation method of the adhesive of selfreparing, which is characterized in that step includes
Step 1: -4 [1H]-pyrimidone of -6 methyl of 2 amino and hexamethylene diisocyanate are pressed to the molar ratio of 1:0.8-1.2
Mixing, and it is heated to 45-55 DEG C, 10-20h is kept the temperature, UPy-isocyanate is prepared；
Step 2: polyethylene glycol, dibutyl tin dilaurate and UPy-isocyanate are dissolved in chloroform, wherein poly- second
Molar ratio between glycol, dibutyl tin dilaurate and UPy-isocyanate is 1:0.01-0.03:3-5, is heated after dissolution
10-20h is kept the temperature after to 55-65 DEG C, and UPy-PEG-UPy adhesive is obtained after reflux.
3. a kind of preparation method of the adhesive of selfreparing according to claim 2, it is characterised in that: in step 1, institute
- 4 [1H]-pyrimidone of -6 methyl of 2 amino and hexamethylene diisocyanate is stated to mix by the molar ratio of 1:1.
4. a kind of preparation method of the adhesive of selfreparing according to claim 2, it is characterised in that: in step 1, institute
50 DEG C are heated to after stating mixing, and keeps the temperature 16h preparation UPy-isocyanate.
5. a kind of preparation method of the adhesive of selfreparing according to claim 2, it is characterised in that: in step 2, institute
Stating the molar ratio between polyethylene glycol, dibutyl tin dilaurate and UPy-isocyanate is 1:0.02:4.
6. a kind of preparation method of the adhesive of selfreparing according to claim 2, it is characterised in that: molten in step 2
16h is kept the temperature after being heated to 60 DEG C after solution, and UPy-PEG-UPy adhesive is obtained after reflux.
7. application of the adhesive of selfreparing described in any one of claims 1-6 in lithium ion battery.
8. application of the adhesive of selfreparing according to claim 7 in lithium ion battery, it is characterised in that: by UPy-
PEG-UPy adhesive prepares silicon electrode after mixing with silicon nano power.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811520010.2A CN109836566A (en) | 2018-12-12 | 2018-12-12 | A kind of adhesive of selfreparing and its preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811520010.2A CN109836566A (en) | 2018-12-12 | 2018-12-12 | A kind of adhesive of selfreparing and its preparation method and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234337A (en) * | 2020-02-27 | 2020-06-05 | 江苏大学 | Epoxidized natural rubber composite material with self-repairing function and preparation method thereof |
| CN111848907A (en) * | 2020-07-06 | 2020-10-30 | 上海交通大学 | Supermolecule polyurethane impact-resistant material containing multiple hydrogen bonds and preparation method thereof |
| CN112169013A (en) * | 2019-07-05 | 2021-01-05 | 香港城市大学 | Particle stacking type biological adhesive and preparation and application thereof |
| CN114142034A (en) * | 2021-10-29 | 2022-03-04 | 西安交通大学 | Negative self-healing adhesive and preparation method and application thereof |
| WO2023197508A1 (en) * | 2022-04-14 | 2023-10-19 | 中国科学院宁波材料技术与工程研究所 | Supramolecular hot-melt adhesive and preparation method therefor |
Citations (2)
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| CN104892871A (en) * | 2015-06-16 | 2015-09-09 | 厦门大学 | Hydrogel with self-repairing function and preparation method of hydrogel |
| CN106279619A (en) * | 2016-08-25 | 2017-01-04 | 华南理工大学 | A kind of based on hydrogen bond action thermal drivers selfreparing method for producing elastomers |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892871A (en) * | 2015-06-16 | 2015-09-09 | 厦门大学 | Hydrogel with self-repairing function and preparation method of hydrogel |
| CN106279619A (en) * | 2016-08-25 | 2017-01-04 | 华南理工大学 | A kind of based on hydrogen bond action thermal drivers selfreparing method for producing elastomers |
Non-Patent Citations (2)
| Title |
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| JUNFENG YANG ET AL.: "Self-healing strategy for Si nanoparticles towards practical application as anode materials for Li-ion batteries", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
| 李聪等: "离子液体-脲基嘧啶酮混合型低收缩率单体的制备及应用", 《影像科学与光化学》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112169013A (en) * | 2019-07-05 | 2021-01-05 | 香港城市大学 | Particle stacking type biological adhesive and preparation and application thereof |
| CN112169013B (en) * | 2019-07-05 | 2022-07-29 | 香港城市大学 | Particle stacking type biological adhesive as well as preparation and application thereof |
| CN111234337A (en) * | 2020-02-27 | 2020-06-05 | 江苏大学 | Epoxidized natural rubber composite material with self-repairing function and preparation method thereof |
| CN111848907A (en) * | 2020-07-06 | 2020-10-30 | 上海交通大学 | Supermolecule polyurethane impact-resistant material containing multiple hydrogen bonds and preparation method thereof |
| CN114142034A (en) * | 2021-10-29 | 2022-03-04 | 西安交通大学 | Negative self-healing adhesive and preparation method and application thereof |
| WO2023197508A1 (en) * | 2022-04-14 | 2023-10-19 | 中国科学院宁波材料技术与工程研究所 | Supramolecular hot-melt adhesive and preparation method therefor |
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