CN1277236A - Adhesive for lithium ion cell - Google Patents
Adhesive for lithium ion cell Download PDFInfo
- Publication number
- CN1277236A CN1277236A CN 00117141 CN00117141A CN1277236A CN 1277236 A CN1277236 A CN 1277236A CN 00117141 CN00117141 CN 00117141 CN 00117141 A CN00117141 A CN 00117141A CN 1277236 A CN1277236 A CN 1277236A
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- Prior art keywords
- tackiness agent
- lithium ion
- adhesive
- ion cell
- coupling agent
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The adhesive consists of polyvinylidene fluoride resin 3-15 wt%, N-methyl pyrrolidone or dimethyl acetamide 85-95wt%, and gamma-aminopropyl triethoxy silicane, gamma-propyl methacrylate trimethoxyl silicane or ethylamino amidopropyl trimethoxyl silicane as coupling agent 1-5wt%. Owing to the addition of the coupling agent in certain proportion, the adhesive of the present invention has strengthened bonding adhesive and current collecting body, high adhesion to the positive electrode current collecting body of lithium ion cell, high electrolyte tolerance of adhered layer and no negative effect on the charge and discharge performance of cell.
Description
The present invention relates to secondary cell, the tackiness agent that uses when making lithium-ion secondary cell in more detail.
The manufacturing processed of lithium ion cell electrode pole piece is: behind a certain proportion of negative or positive electrode active substance, conductive agent, PVDF (polyvinylidene difluoride (PVDF)) tackiness agent and solvent N-Methyl pyrrolidone or N,N-DIMETHYLACETAMIDE slurrying thorough mixing, be coated on equably on collector aluminium foil or the Copper Foil, drying, roll, cut out get final product behind the branch certain thickness battery plate.Because the electrode of lithium ion battery adopts the coating method preparation, coating approaches (coat-thickness is generally 0.10-0.20mm), add and adopt non-water system carbonates to make electrolytical solvent, will under high-voltage, work, therefore, require the employed tackiness agent of lithium ion battery must satisfy following condition:
1. electrochemical stability is good, and decomposition voltage reference metallic lithium will be more than 4.5V;
2. can resist the erosion of the organic solvent of polar electrolyte solution, not dissolve, not swelling;
3. solvability is good in organic solvent, can be mixed with the tackiness agent of solution-type, under consumption situation seldom, can in good condition the various powder materials of lithium ion battery be mixed equably and bond together;
4. metal collector there is good adhesive property, dry linting can occur, influence the situation of cycle performance of battery.
5. have flexibility preferably, can prevent electrode reel and use in coiling place dry linting or cracking, and coating can be very thin when guaranteeing to be coated with.
Because the PVDF tackiness agent can be dissolved in the organic solvent, has good electrochemical stability and chemical mediator-resitant property, therefore be applied at large in the electrode moulding of lithium ion battery.But, though PVDF can satisfy lithium ion battery substantially to its tackiness agent performance demands, but still have more performance deficiency, not good enough to the adhesiveproperties of the collector metal of battery and active substance particulate as PVDF, its electrolyte resistance corrosive performance is perfect not to the utmost; Through after the charge and discharge cycles repeatedly, the dry linting phenomenon appears in the pole piece surface of battery easily, reduces the quantity of active substance of the actual participation work of battery, reduces the cycle life of battery.
The objective of the invention is to shortcoming at the prior art existence, a kind of adhesive for lithium ion cell is provided, improve the electrolyte resistance performance of PVDF tackiness agent to the adhesiveproperties and the glue-line of lithium ion cell positive collector aluminium foil, improve the bond properties of cell active materials and battery afflux liquid, reduce the repeatedly dry linting phenomenon after the charge and discharge cycles of battery, improve the cycle life of battery.
The weight proportion of adhesive for lithium ion cell of the present invention is as follows:
Polyvinylidene fluoride resin 3--15
N-Methyl pyrrolidone or N,N-DIMETHYLACETAMIDE 85--95
Coupling agent 1--5
Wherein polyvinylidene fluoride resin is the main component of tackiness agent; N-Methyl pyrrolidone or N,N-DIMETHYLACETAMIDE are organic solvents, and its effect is the dissolving polyvinylidene fluoride resin, makes liquid adhesive, so that batch mixing in the battery electrode moulding and coating; Coupling agent is bonding auxiliary agent, is used to improve adhesiveproperties.
The present invention selects γ-An Bingjisanyiyangjiguiwan or γ-methyl-prop diluted acid propyl ester base Trimethoxy silane or amine ethylamine propyl trimethoxy silicane as coupling agent.
Caking agent of the present invention is mainly used in bonding lithium ion cell positive collector.
The contriver finds through exploratory study test, adopts the adhesiveproperties of the tackiness agent that following weight proportion prescription obtains and electrolyte resistance performance the best of glue-line:
Polyvinylidene fluoride resin 10
N-Methyl pyrrolidone or N,N-DIMETHYLACETAMIDE 90
γ-An Bingjisanyiyangjiguiwan 3
The using method of adhesive for lithium ion cell of the present invention is same as the prior art.
The present invention compared with prior art has following advantage:
1, adhesive for lithium ion cell of the present invention is owing to added a certain proportion of coupling agent, strengthened combining of tackiness agent and collection liquid surface, significantly improved the electrolyte resistance performance of tackiness agent adhesiveproperties and institute's adhesive-layer of lithium ion cell positive collector;
2, adhesive for lithium ion cell of the present invention does not have negative influence substantially to the charge-discharge performance of battery.
The invention will be further described below by examples of implementation.
Embodiment 1
15 gram polyvinylidene fluoride resins are dissolved in 90 milliliters of N,N-DIMETHYLACETAMIDEs, are made into tackiness agent, be called tackiness agent No. 1.
15 gram polyvinylidene fluoride resins are dissolved in 90 milliliters of N,N-DIMETHYLACETAMIDEs, add 5 gram γ-propyl methacrylate base Trimethoxy silanes (KH550), be made into tackiness agent, be called tackiness agent No. 2.
For ease of performance test and research, with No. 1, No. 2 tackiness agent bonding with the identical aluminium flakes of lithium ion cell positive collector material: the thin and gluing 8 times equably on the aluminium flake surface, each 5 minutes at interval, dry sample under the condition of 60 ℃ * 4h+180 ℃ * 10min then.
1, the adhesiveproperties of No. 2 tackiness agent bonding samples and electrolyte resistance performance are as shown in table 1.Table 1 is with the bonding strength of the bonding sample of 1, No. 2 tackiness agent and the electrolyte resistance performance (MP of glue-line
a)
Soak to soak among the 68.47%DME in 10 days 1.11 1.87 among No. 2 tackiness agent increases of No. 1 tackiness agent percentage initial state 2.28 4.21 84.65%PC and soaked 7 days 1.35 2.20 62.96% among the 75.89%EC+DEC in 7 days 1.12 1.97
According to table 1 as seen, No. 2 tackiness agent is brought up to 4.21MPa to the bond strength of aluminium flake by 2.28 MPa, has improved 84.65%; The electrolyte resistance performance of No. 2 bonding aluminium flake samples of tackiness agent also increases significantly simultaneously, and the raising of glue-line electrolyte resistance erosional competency is all more than 60%.
Embodiment 2
10 gram polyvinylidene fluoride resins are dissolved in 90 milliliters of N,N-DIMETHYLACETAMIDEs, are made into tackiness agent, be called tackiness agent No. 3.
10 gram polyvinylidene fluoride resins are dissolved in 90 milliliters of N,N-DIMETHYLACETAMIDEs, add 3 gram γ-propyl methacrylate base Trimethoxy silanes, be made into tackiness agent, be called tackiness agent No. 4.
No. 3, No. 4 tackiness agent are used for bonding and the identical aluminium flake of lithium ion cell positive collector material: the thin and gluing 8 times equably on the aluminium flake surface, each 5 minutes at interval, dry sample under the condition of 60 ℃ * 4h+180 ℃ * 10min then.
The adhesiveproperties of 3, No. 4 tackiness agent bonding samples and electrolyte resistance performance are as shown in table 2.
Table 2 is with the bonding strength and the electrolyte resistance performance (MP of the bonding sample of 3, No. 4 tackiness agent
a)
Soak to soak among the 40.35%DME in 10 days 1.14 1.60 among No. 4 tackiness agent increases of No. 3 tackiness agent percentage initial state 2.30 4.31 87.39%PC and soaked 7 days 1.39 1.91 41.48% among the 94.01%EC+DEC in 7 days 1.17 2.27
By the data of table 2 as can be known, No. 4 tackiness agent have improved 87.39% than No. 3 tackiness agent to the bond strength of aluminium flake, have improved nearly one times; Though the electrolyte resistance performance of tackiness agent is relevant with the electrolytic solution kind, the electrolyte resistance performance of No. 4 tackiness agent obviously makes moderate progress.
Embodiment 3
3 gram polyvinylidene fluoride resins are dissolved in 95 milliliters of N,N-DIMETHYLACETAMIDEs, are made into tackiness agent, be called tackiness agent No. 5.
3 gram polyvinylidene fluoride resins are dissolved in 95 milliliters of N,N-DIMETHYLACETAMIDEs, add 1 gram γ-propyl methacrylate base Trimethoxy silane, be made into tackiness agent, be called tackiness agent No. 6.
The pole piece that No. 5, No. 6 tackiness agent is used to make the lithium ion cell positive simulated battery, promptly by 85: 7: 8 mixed positive active material, No. 5 or No. 6 tackiness agent and conductive agent, be coated on the aluminium foil equably well-mixed slurry respectively then, at 100 ℃ of anode pole pieces of promptly making lithium ion battery down in dry 60 minutes behind the thorough removal solvent, make the lithium ion cell positive simulated battery respectively with these pole pieces.Table 3 has contrasted the discharge performance that adopts the anodal simulated battery of 5, No. 6 tackiness agent respectively.Table 3 adopts the discharge performance (unit: mAh/g) of the lithium ion cell positive simulated battery of 5, No. 6 tackiness agent
No. 6 tackiness agent of No. 5 tackiness agent of cycle index
1 121.0 118.1
2 114.4 111.7
3 113.1 107.4
4 109.7 105.8
5 104.5 102.9
By table 3 as seen, contrast adopts the discharge performance of the anodal simulated battery of No. 5, No. 5 tackiness agent to find, the anodal simulated battery discharge performance that has added coupling agent does not have considerable change, promptly behind the coupling agent charge-discharge performance of battery is not had substantially the influence of passiveness in the tackiness agent.
Claims (2)
1, a kind of adhesive for lithium ion cell is characterized in that weight proportion is as follows:
Polyvinylidene fluoride resin 3--15
N-Methyl pyrrolidone or N,N-DIMETHYLACETAMIDE 85--95
Coupling agent 1-5
Coupling agent is γ-An Bingjisanyiyangjiguiwan or γ-methyl-prop diluted acid propyl ester base Trimethoxy silane or amine ethylamine propyl trimethoxy silicane.
2,, it is characterized in that weight proportion is as follows according to the described adhesive for lithium ion cell of claim 1:
Polyvinylidene fluoride resin 10
N-Methyl pyrrolidone or N,N-DIMETHYLACETAMIDE 90
γ-An Bingjisanyiyangjiguiwan 3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00117141A CN1120210C (en) | 2000-06-08 | 2000-06-08 | Adhesive for lithium ion cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00117141A CN1120210C (en) | 2000-06-08 | 2000-06-08 | Adhesive for lithium ion cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1277236A true CN1277236A (en) | 2000-12-20 |
| CN1120210C CN1120210C (en) | 2003-09-03 |
Family
ID=4586535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00117141A Expired - Fee Related CN1120210C (en) | 2000-06-08 | 2000-06-08 | Adhesive for lithium ion cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1120210C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9444084B2 (en) | 2010-12-15 | 2016-09-13 | Solvay (China) Co., Ltd. | Fluoropolymer compositions |
| US9518155B2 (en) | 2012-04-16 | 2016-12-13 | Rhodia Operations | Fluoropolymer compositions |
| CN107845812A (en) * | 2016-09-18 | 2018-03-27 | 宁德新能源科技有限公司 | Anode pole piece and preparation method thereof and secondary cell |
| CN109004231A (en) * | 2018-08-28 | 2018-12-14 | 武汉理工大学 | Lithium-sulfur cell binder and corresponding lithium sulfur battery anode material, lithium-sulfur cell |
| CN109390550A (en) * | 2018-10-24 | 2019-02-26 | 遵义源创生产力促进中心有限公司 | A kind of positive pole aluminium foil collector performance improvement method |
| CN109742402A (en) * | 2019-01-08 | 2019-05-10 | 福建师范大学 | A kind of preparation method of enhancement type polyvinylidene difluoroethylene lithium battery conductive adhesive |
| CN111952668A (en) * | 2020-08-13 | 2020-11-17 | 梅州市量能新能源科技有限公司 | Electrolyte, lithium ion battery and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3121943B2 (en) * | 1992-12-02 | 2001-01-09 | 呉羽化学工業株式会社 | Vinylidene fluoride copolymer |
| CN1060792C (en) * | 1995-10-27 | 2001-01-17 | 复旦大学 | Electricity-conduct adhesion agent and mfg. method thereof |
| KR19990081865A (en) * | 1996-01-22 | 1999-11-15 | 베아트리체 델로스탈 | Attachment method of fluorinated resin to metal |
| WO1999026308A1 (en) * | 1997-11-19 | 1999-05-27 | Mitsubishi Denki Kabushiki Kaisha | Bonding agent for cells and cell using the same |
-
2000
- 2000-06-08 CN CN00117141A patent/CN1120210C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9444084B2 (en) | 2010-12-15 | 2016-09-13 | Solvay (China) Co., Ltd. | Fluoropolymer compositions |
| US9518155B2 (en) | 2012-04-16 | 2016-12-13 | Rhodia Operations | Fluoropolymer compositions |
| CN107845812A (en) * | 2016-09-18 | 2018-03-27 | 宁德新能源科技有限公司 | Anode pole piece and preparation method thereof and secondary cell |
| CN109004231A (en) * | 2018-08-28 | 2018-12-14 | 武汉理工大学 | Lithium-sulfur cell binder and corresponding lithium sulfur battery anode material, lithium-sulfur cell |
| CN109390550A (en) * | 2018-10-24 | 2019-02-26 | 遵义源创生产力促进中心有限公司 | A kind of positive pole aluminium foil collector performance improvement method |
| CN109742402A (en) * | 2019-01-08 | 2019-05-10 | 福建师范大学 | A kind of preparation method of enhancement type polyvinylidene difluoroethylene lithium battery conductive adhesive |
| CN111952668A (en) * | 2020-08-13 | 2020-11-17 | 梅州市量能新能源科技有限公司 | Electrolyte, lithium ion battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1120210C (en) | 2003-09-03 |
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| C14 | Grant of patent or utility model | ||
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Owner name: CHAOZHOU ZHENGLONG BATTERY INDUSTRY CO., LTD. Free format text: FORMER NAME: SOUTHERN CHINA UNIVERSITY OF TECHNOLOGY |
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| CP03 | Change of name, title or address |
Address after: 515644 Guangdong Caitang County of Chaoan Province Overseas Chinese Industrial Zone Patentee after: Chaozhou Zhenglong Battery Industry Co., Ltd. Address before: 510640 Guangdong city of Guangzhou province Tianhe District Wushan Patentee before: South China University of Technology |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20030903 Termination date: 20180608 |