CN105633325A - Bonding method for metal/polymer laminated composite membrane and glass-ceramic membrane - Google Patents
Bonding method for metal/polymer laminated composite membrane and glass-ceramic membrane Download PDFInfo
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- CN105633325A CN105633325A CN201410592282.9A CN201410592282A CN105633325A CN 105633325 A CN105633325 A CN 105633325A CN 201410592282 A CN201410592282 A CN 201410592282A CN 105633325 A CN105633325 A CN 105633325A
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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 relates to a bonding method for a metal/polymer laminated composite membrane and a glass-ceramic membrane. The bonding method comprises the following steps: firstly, cleaning and drying a microcrystalline glass-ceramic membrane; secondly, applying a transition layer on a whole surface of the microcrystalline glass-ceramic membrane; thirdly, forming a window in the center of the metal/polymer laminated composite membrane; fourthly, using a hot melt adhesive made of a PP material to prepare a sealing bonding ring; and fifthly, putting the sealing bonding ring on one surface of a polymer layer of the metal/polymer laminated composite membrane, putting the surface, provided with the transition layer, of the microcrystalline glass-ceramic membrane on the sealing bonding ring on the metal/polymer laminated composite membrane, and carrying out hot pressing to form one body so as to complete the bonding process of the metal/polymer laminated composite membrane and the glass-ceramic membrane in the invention. According to the bonding method, the transition layer is integrally applied on the surface, needing to be bonded with the metal/polymer laminated composite membrane, of the microcrystalline glass-ceramic membrane, and mask processing and mask assembling alignment are not needed, so that the technology is simple, and the sealing bonding reliability is high; and the discharge performance of a lithium electrode is improved through the transition layer.
Description
Technical field
The invention belongs to lithium addition technical field, particularly relate to the metal/polymer laminating composite film of a kind of water proof type lithium shield electrode sealing and the adhering method of glass ceramic film.
Background technology
Lithium addition, as the different novel lithium battery system of a kind of and traditional organic system lithium battery, has the advantage that specific energy is high, and wherein water proof type lithium shield electrode is the core component of lithium addition. The Sealing Technology of water proof type lithium shield electrode is extremely important; because it will be directly connected to the reliability that water proof type lithium shield electrode works in aqueous; encapsulation place, once there is cracking or seepage, can cause that battery lost efficacy in long-time storage and discharge process and even blast.
Find through retrieval, application number is 200680037611.7, publication number is CN101313426A, name is called: for the patent of invention of the compliant seal structures of protected active metal anodes, the sealing technique for sticking of water proof type lithium shield electrode disclosed in its description, this technical process is to need the abutting edge preplating layer of metal nitride transition layer SnxN of bonding frame and metal/polymer laminating composite film at devitrified glass ceramics film, introduce this metal nitride transition zone to improve and between devitrified glass ceramics film with metal/polymer laminating composite film, seal bonding reliability. but, in plating transition zone process, need devitrified glass ceramics film is carried out mask protection, to ensure that metal nitride transition layer is only plated in frame and needs bonding position, this process is required for the devitrified glass ceramics film of different area size and designs corresponding difform mask, and needing when coating operation the para-position of mask is accurately adjusted, not only operating process is complicated, and easily causes the destruction of devitrified glass ceramics film.
Summary of the invention
The present invention solves the technical problem existed in known technology and provide that a kind of manufacture method is simple, it is high to seal bonding reliability, it is possible to improve the adhering method of metal/polymer laminating composite film and the glass ceramic film of the discharge performance of lithium electrode.
The present invention includes following technical scheme: be characterized in:
The present invention can also adopt following technical measures:
The present invention has the advantage that and good effect:
1, the present invention is by needing surface entirety plating one layer transition zone bonding with metal/polymer laminating composite film at devitrified glass ceramics film, this transition zone can keep the good interface associativity between devitrified glass ceramics film, aqueous vapor will not be permeated in interface between the two simultaneously, without mask processing and mask assembling para-position, technique is simple, seals bonding reliability high; Transition zone does not only hinder lithium ion to transmit on the integral surface of devitrified glass ceramics film, improves the interface performance between devitrified glass ceramics film and aqueous solution on the contrary, reduces interface impedance, improves the discharge performance of lithium electrode.
2, the present invention is metal nitride at the transition zone of devitrified glass ceramics film one side plating, owing to metal nitride self chemical property is highly stable, it is to avoid devitrified glass ceramics film works long hours in alkalescence and slightly acidic water solution and to be subject to the corrosion of aqueous solution.
Accompanying drawing explanation
Fig. 1 is the bonding metal/polymer laminating composite film of the present invention and glass ceramic film schematic front view;
Fig. 2 is the water proof type lithium shield electrode internal structure schematic diagram adopting metal/polymer laminating composite film bonding for Fig. 1 and glass ceramic film to make;
Fig. 3 is AC impedance performance test comparison diagram;
Fig. 4 is galvanostatic polarization performance test comparison diagram.
Wherein, 1-transition zone, 2-devitrified glass ceramics film, 3-organic electrolyte, 4-lithium metal, 5-seals bonding circle, 6-metal/polymer laminating composite film, 7-tab, 8-lug.
Detailed description of the invention
For the summary of the invention of the present invention, feature and effect can be disclosed further, describe in detail as follows especially exemplified by following instance.
Metal/polymer laminating composite film and the adhering method of glass ceramic film, be characterized in: step includes:
Step 1: devitrified glass ceramics film is carried out, dries;
Step 2: clean in step 1, dry after devitrified glass ceramics film one side one layer of transition zone of plating;
Step 3: the size according to devitrified glass ceramics film in step 1, opening a window at metal/polymer laminating composite film center, the inner circumferential size of window is bonding integral can be as the criterion whole with the periphery of devitrified glass ceramics film for metal/polymer laminating composite film;
Step 4: according to the position that metal/polymer laminating composite film in step 3 is bonding with devitrified glass ceramics film, makes the bonding circle of sealing by the PUR of PP material;
Step 5: the bonding circle that seals step 4 made is placed in the polymeric layer one side that step 3 has the metal/polymer laminating composite film of window, it is positioned at the periphery of window, devitrified glass ceramics film strips has on the bonding circle of sealing that the one side of transition zone is placed on metal/polymer laminating composite film, at 160 DEG C-170 DEG C, 5-50N/m2Hot pressing 0.5-2min under pressure, completes the bonding process of metal/polymer laminating composite film of the present invention and glass ceramic film.
It is 80-450um, area is 0.5-100cm that described devitrified glass ceramics film includes thickness2, Li that smooth surface is smooth1+xAlxGe2-x(PO4)3(LAGP) solid electrolyte film or Li1+xAlxTi2-x(PO4)3(LATP) solid electrolyte film.
The material of described transition zone includes metal nitride, LiMn2O4Or Li4Ti5O12��
Described metal nitride includes SnxN or TixN material.
The material of the bonding circle of described sealing includes the one of the acrylic acid modified PP PUR of the PP material PUR of thickness 20-70um, the maleic acid modified PP PUR of monolayer or monolayer, or is the white of three layers compound PP material, yellow or black tab.
Described metal/polymer laminating composite film is that 85-150um is thick, using PP as the aluminum-plastic composite membrane of thermoplastic layer.
Embodiment
Step 1: the LAGP devitrified glass ceramics film 2 being 40mm �� 40mm for area, carries out ultrasonic cleaning dedusting oil removing by devitrified glass ceramics film in acetone soln, dries;
Step 2: adopt the Sn thick for one layer of 1um of whole plated surface of Radiofrequency muti-hook probe method LAGP devitrified glass ceramics film one side after cleaning, dryingxN metal nitride coating is as transition zone 1;
Step 3: by area to be 50mm �� 50mm, thickness be 87um, the PP aluminum-plastic composite membrane as hot melt layer as metal/polymer laminating composite film 6, open a window at plastic-aluminum combined center membrane, window area be 39mm �� 39mm;
Step 4: be 40mm �� 40mm by area, thickness is the area that the monolayer-modified PP PUR center of 70um cuts out 39mm �� 39mm, and the housing staying width to be 0.5mm is as sealing bonding circle 5;
Step 5: as it is shown in figure 1, aluminum-plastic composite membrane facing up with PP hot melt layer, be corresponding in turn to placement and seal bonding circle and devitrified glass ceramics film, wherein devitrified glass ceramics film strips has facing down of transition zone to be placed on the bonding circle of sealing, at 165 DEG C, 20N/m2Carry out 1min hot pressing under pressure, complete the sealing bonding process of aluminum-plastic composite membrane and LAGP devitrified glass ceramics film.
Adopt embodiment 1 make seal with metal/polymer laminating composite film bonding after devitrified glass ceramics film as the sealer of lithium metal 4; one layer of organic electrolyte 3 is had between lithium metal and devitrified glass ceramics film; lug 8 is drawn from metal/polymer laminating composite film; sealed by tab 7, define lithium addition water proof type lithium shield electrode. It is carried out enclosed package by the metal/polymer laminating composite film of waterproof material by whole water proof type lithium shield electrode structure, only has the Sn being plated in devitrified glass ceramics filmxIn aqueous, the another side of devitrified glass ceramics film, organic electrolyte, lithium metal, metal collector are all sealed N metal nitride coating, form physical isolation with extraneous aqueous solution, as shown in Figure 3. Devitrified glass ceramics film water molecule cannot pass through devitrified glass ceramics film and arrive the surface of lithium metal, and lithium ion can depart from from the surface of lithium metal under the effect of electric field, and migrates in aqueous solution via electrolyte and devitrified glass ceramics film. It is plated on the integral surface of devitrified glass ceramics film and does not only hinder lithium ion to transmit, improve the interface performance between devitrified glass ceramics film and aqueous solution on the contrary, reduce interface impedance, improve the discharge performance of lithium electrode.
The lithium addition water proof type lithium shield electrode that the bonding metal/polymer laminating composite film of the present invention and devitrified glass ceramics film are made is 3.5%NaCl solution at test aqueous solution with currently known water proof type lithium shield electrode respectively, carries out AC impedance performance and galvanostatic polarization performance test under test 25 DEG C of environment of temperature; In Fig. 3, b curve is the AC impedance performance curve of the lithium addition water proof type lithium shield electrode that the bonding metal/polymer laminating composite film of the present invention is made with devitrified glass ceramics film, and a curve is the AC impedance performance curve of the lithium addition water proof type lithium shield electrode that currently known bonding metal/polymer laminating composite film is made with devitrified glass ceramics film; Test result shows, the impedance of the lithium addition water proof type lithium shield electrode that the bonding metal/polymer laminating composite film of the present invention and devitrified glass ceramics film are made declines to some extent; In Fig. 4, b curve is the galvanostatic polarization performance curve of the lithium addition water proof type lithium shield electrode that the bonding metal/polymer laminating composite film of the present invention is made with devitrified glass ceramics film, and a curve is the galvanostatic polarization performance curve of the lithium addition water proof type lithium shield electrode that currently known bonding metal/polymer laminating composite film is made with devitrified glass ceramics film. Test result shows, the polarization value of the lithium addition water proof type lithium shield electrode that the bonding metal/polymer laminating composite film of the present invention and devitrified glass ceramics film are made declines to some extent. Result of the test shows that the performance of the lithium addition water proof type lithium shield electrode that the bonding metal/polymer laminating composite film of the present invention and devitrified glass ceramics film make is improved.
The metal/polymer laminating composite film adopting the present invention bonding soaks 3 months in 3.5%NaCl solution with the water proof type lithium shield electrode that devitrified glass ceramics film is made; take out and dry; inert-atmosphere glove box is dissected flexible-packaged lithium electrode; do not find that lithium metal is corroded; lithium shows that still light is as new; show that the method is not only completely waterproof, and it is fine to seal adhesive effect.
The preparation principle of material of the present invention:
The present invention is by needing surface entirety plating one layer transition zone bonding with metal/polymer laminating composite film at the devitrified glass ceramics film with lithium ion conducting function, it is not necessary to mask processing and mask assembling para-position, technique is simple, seals bonding reliability high.
Devitrified glass ceramics film only has the decay resistance of relatively senior middle school at neutral aqueous solution, and in alkalescence and slightly acidic water solution, long-time immersion is easily subject to corrosion, and metal nitride (particularly SnxN material) in alkalescence or acidic aqueous solution, all there is extraordinary chemical stability. Metal nitride is formed transition at devitrified glass ceramics face to all surfaces of aqueous solution one side as transition zone plating by the present invention further, devitrified glass ceramics film is played a very good protection, makes water proof type lithium shield electrode can work long hours in alkalescence and slightly acidic water solution and be not subjected to the corrosion failure of aqueous solution; By it have been experienced that, metal nitride does not only hinder lithium ion to transmit on the integral surface of devitrified glass ceramics film, improve the interface performance between devitrified glass ceramics film and aqueous solution on the contrary, reduce interface impedance, improve the discharge performance of lithium electrode.
Although above the preferred embodiments of the present invention being described; but the invention is not limited in above-mentioned detailed description of the invention; above-mentioned detailed description of the invention is merely schematic; it is not restrictive; those of ordinary skill in the art is under the enlightenment of the present invention; without departing under present inventive concept and scope of the claimed protection situation, it is also possible to make a lot of form. These belong within protection scope of the present invention.
Claims (6)
1. the adhering method of metal/polymer laminating composite film and glass ceramic film, it is characterised in that: comprise the following steps:
Step 1: devitrified glass ceramics film is carried out, dries;
Step 2: clean in step 1, dry after devitrified glass ceramics film one side one layer of transition zone of plating;
Step 3: the size according to devitrified glass ceramics film in step 1, opening a window at metal/polymer laminating composite film center, the inner circumferential size of window is bonding integral can be as the criterion whole with the periphery of devitrified glass ceramics film for metal/polymer laminating composite film;
Step 4: according to the position that metal/polymer laminating composite film in step 3 is bonding with devitrified glass ceramics film, makes the bonding circle of sealing by the PUR of PP material;
Step 5: the bonding circle that seals step 4 made is placed in the polymeric layer one side that step 3 has the metal/polymer laminating composite film of window, it is positioned at the periphery of window, devitrified glass ceramics film strips has on the bonding circle of sealing that the one side of transition zone is placed on metal/polymer laminating composite film, at 160 DEG C-170 DEG C, 5-50N/m2Hot pressing 0.5-2min under pressure, completes the bonding process of metal/polymer laminating composite film of the present invention and glass ceramic film.
2. the adhering method of metal/polymer laminating composite film and glass ceramic film according to claim 1, it is characterised in that: it be 80-450um, area is 0.5-100cm that described devitrified glass ceramics film includes thickness2LAGP solid electrolyte film or LATP solid electrolyte film.
3. the adhering method of metal/polymer laminating composite film and glass ceramic film according to claim 1, it is characterised in that: the material of described transition zone includes metal nitride, LiMn2O4Or Li4Ti5O12��
4. the adhering method of metal/polymer laminating composite film and glass ceramic film according to claim 1, it is characterised in that: described metal nitride includes SnxN or TixN material.
5. the adhering method of metal/polymer laminating composite film and glass ceramic film according to claim 1, it is characterized in that: the material of the bonding circle of described sealing includes the one of the acrylic acid modified PP PUR of the PP material PUR of thickness 20-70um, the maleic acid modified PP PUR of monolayer or monolayer, or is the white of three layers compound PP material, yellow or black tab.
6. the adhering method of metal/polymer laminating composite film and glass ceramic film according to claim 1, it is characterised in that: described metal/polymer laminating composite film is that 85-150um is thick, using PP as the aluminum-plastic composite membrane of thermoplastic layer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410592282.9A CN105633325A (en) | 2014-10-29 | 2014-10-29 | Bonding method for metal/polymer laminated composite membrane and glass-ceramic membrane |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410592282.9A CN105633325A (en) | 2014-10-29 | 2014-10-29 | Bonding method for metal/polymer laminated composite membrane and glass-ceramic membrane |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010051620A1 (en) * | 1999-12-29 | 2001-12-13 | American Home Products Corporation | Tricyclic protein kinase inhibitors |
| CN101313426A (en) * | 2005-08-09 | 2008-11-26 | 波利普拉斯电池有限公司 | Compliant seal structures for protected active metal anodes |
| CN102969516A (en) * | 2012-12-14 | 2013-03-13 | 中国电子科技集团公司第十八研究所 | Preparation method of thin type micro-crystalline glass ceramic chip metal lithium battery |
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- 2014-10-29 CN CN201410592282.9A patent/CN105633325A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010051620A1 (en) * | 1999-12-29 | 2001-12-13 | American Home Products Corporation | Tricyclic protein kinase inhibitors |
| CN101313426A (en) * | 2005-08-09 | 2008-11-26 | 波利普拉斯电池有限公司 | Compliant seal structures for protected active metal anodes |
| CN102969516A (en) * | 2012-12-14 | 2013-03-13 | 中国电子科技集团公司第十八研究所 | Preparation method of thin type micro-crystalline glass ceramic chip metal lithium battery |
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