CN102456920B - Method for preparing solid electrolyte of three-dimensional lithium ion battery based on Si microchannel plate - Google Patents
Method for preparing solid electrolyte of three-dimensional lithium ion battery based on Si microchannel plate Download PDFInfo
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- CN102456920B CN102456920B CN201010523212.XA CN201010523212A CN102456920B CN 102456920 B CN102456920 B CN 102456920B CN 201010523212 A CN201010523212 A CN 201010523212A CN 102456920 B CN102456920 B CN 102456920B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing a solid electrolyte of a three-dimensional lithium ion battery, in particular the method for preparing the solid electrolyte of the three-dimensional lithium ion battery based on a Si microchannel plate, which is characterized in that an organic macromoleclar polymer is guided into a channel with an aperture within a micrometer dimension structure, and belongs to the manufacturing field of microelectronics technology. An organic macromoleclar polymer film is an electrolyte film formed on a wall of the Si microchannel plate based on high aspect ratio. The method has low requirement on equipment, simple process and low production cost; and since the solid electrolyte is based on a high aspect ratio microchannel structure, and the electrolyte film is thinner and in nanoscale, so that the diffusion length of lithium ion in the electrolyte is reduced, and thus the charging speed of the lithium ion battery is improved.
Description
Technical field
The present invention relates to a kind of three-dimensional lithium ion battery method for preparing solid electrolyte, a kind of method for preparing solid electrolyte of the three-dimensional lithium ion battery based on silicon microchannel plate specifically, be that organic high molecular polymer is imported to aperture in the passage of micron-scale structure, belong to microelectronic technique and make field.
Background technology
Lithium ion battery has been widely used in, in the portable electric appts such as mobile phone, notebook computer, being deeply subject to doting on of users, at following electric automobile, also has extraordinary application prospect, will produce deep effect to following people's life.Yet, for power train in vehicle application, due to slower battery charging rate, be that electric automobile is also failed one of practical reason.
The charging rate that improves lithium ion battery, can adopt novel battery structure----three-dimensional structure.As far back as 2003, people have just imagined the mutual 3-d microbatteries structure of arranging of columnar electrode, and the three-dimensional batteries of the both positive and negative polarity formation of arranging by several different modes has been carried out to emulation, in fact, what it was realized is the three-dimensional of electrode, and electrolyte remains two-dimensional structure.In the Advanced materials forthe 3D microbattery article of delivering on Journal of Power Sources for 2006, disclose by the method for spin coating in organic solid electrolyte based introduction channel.It is larger that this method is suitable for bore, the passage that hole depth is more shallow.
Summary of the invention
The object of the invention is for a kind of method for preparing solid electrolyte of the three-dimensional lithium ion battery based on silicon microchannel plate is provided, realize and in the silicon micro-channel of high-aspect-ratio, form the threedimensional solid high molecular polymer electrolytic thin-membrane that one deck is even, absorbent is good.
Object of the present invention can be achieved through the following technical solutions.
A method for preparing solid electrolyte for three-dimensional lithium ion battery based on silicon microchannel plate, its step is as follows:
1) by silicon microchannel plate (having covered nickel metal layer and curing molybdenum layer) preliminary treatment: described silicon microchannel plate is dipped in to 50-70 second in 1% the Triton X-100 aqueous solution.Because silicon and each coating are with organically macromolecule organic solution compatibility is poor, destroy its surface tension, thereby improve conduit wall to electrolytical adsorption capacity;
2) by Kynoar-hexafluoropropylene copolymer (PVDF-HFP) matrix powder 1g, acetone (analyzing pure) solvent 100mL, after mixing by magnetic agitation to evenly, then add the nanometer SiO of 0.1-0.25g
2or Al
2o
3powder, for improving electrolytical ionic conductivity, then continues to stir, and obtains consoluet transparency liquid.
3) by step 1) sample handled well is placed on lens wiping paper, then places them on the sol evenning machine pallet after repacking, opens vacuum, and regulates the size of vacuum, they are adsorbed on pallet;
4) electrolyte solution preparing is dripped in microchannel surface, under the suction-operated of vacuum, in electrolyte solution admission passage, due to the effumability of acetone, remaining material remains in microchannel inwall; By lens wiping paper together mobile example, in all microchannels of sample scope, suck and adsorbing electrolyte;
5) microchannel plate that sucks electrolyte solution is placed at 80 ℃ of temperature of vacuum drying chamber and is dried 30 minutes, acetone is thoroughly volatilized;
6) repeating 4,5 steps, is the solid electrolyte film of 50-300 nanometer until silicon micro-channel inwall forms thickness, thereby has formed the three-dimensional high molecular polymer film of one deck.
Described silicon microchannel plate, its Kong Kuanwei 3-5 micron, hole depth is 100-150 micron.
Step 3) sol evenning machine after the repacking described in, that existing sol evenning machine is reequiped, the flexible pipe being connected with vacuum pump is directly led to pallet, too large owing to directly inhaling vacuum forces, and microchannel is crisp and thin, therefore utilize the feature of pallet absorption planar structure, on pallet, place another pallet, thereby by regulating the position of this pallet, control absorption strength.
Step 3), in, described vacuum degree is between 1Pa to 500Pa.
This method is not high to equipment requirement, and technique is simple, and production cost is low, because this solid electrolyte is based on high-aspect-ratio Micro Channel Architecture, and this dielectric film is thinner, in nanometer scale, shorten the diffusion length of lithium ion in electrolyte, thereby improved the charging rate of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the scanning electron Electronic Speculum figure of silicon microchannel plate;
Fig. 2 is nickel metal layer scanning electron Electronic Speculum figure;
Fig. 3 is molybdenum bisuphide negative material scanning electron Electronic Speculum figure;
Fig. 4 is polymer solid electrolyte scanning electron Electronic Speculum figure;
Fig. 5 is three-dimensional lithium ion battery structural profile schematic diagram.
In figure: 1, positive electrode 2, molybdenum bisuphide negative pole 3, silicon substrate 4, nickel disilicide current collector 5, polymer dielectric.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, further set forth technical characterstic of the present invention.
Embodiment 1
1) by silicon microchannel plate (having covered nickel metal layer and curing molybdenum layer) preliminary treatment: described silicon microchannel plate is dipped in 1% the Triton X-100 aqueous solution to 50 seconds;
2) by Kynoar-hexafluoropropylene copolymer (PVDF-HFP) matrix powder 1g, acetone (analyzing pure) solvent 100mL, after mixing by magnetic agitation to evenly, then add the nanometer SiO of 0.1g
2or Al
2o
3powder, then continue to stir, until obtain dissolving completely transparent and have the liquid of better mobility;
3) by step 1) sample handled well is placed on lens wiping paper, then places them on the sol evenning machine pallet after repacking, opens vacuum, and regulates size to 400 handkerchief of vacuum, they are adsorbed on pallet;
4) the above-mentioned electrolyte solution preparing is dripped in microchannel surface, under the suction-operated of vacuum, in electrolyte solution admission passage, due to the effumability of acetone, remaining material remains in microchannel inwall; By lens wiping paper together mobile example, in all microchannels of sample scope, suck and adsorbing electrolyte;
5) microchannel plate that sucks electrolyte solution is placed at 80 ℃ of temperature of vacuum drying chamber and is dried 30 minutes, acetone is thoroughly volatilized;
6) repeating 4,5 steps, is the solid electrolyte film of 50 nanometers until silicon micro-channel inwall forms thickness, thereby has formed the three-dimensional high molecular polymer film of one deck.
Embodiment 2
1) by silicon microchannel plate (having covered nickel metal layer and curing molybdenum layer) preliminary treatment: described silicon microchannel plate is dipped in 1% the Triton X-100 aqueous solution to 70 seconds;
2) by Kynoar-hexafluoropropylene copolymer (PVDF-HFP) matrix powder 1g, acetone (analyzing pure) solvent 100mL, after mixing by magnetic agitation to evenly, then add the nanometer SiO of 0.25g
2or Al
2o
3powder, then continue to stir, until obtain dissolving completely transparent and have the liquid of better mobility.；
3) by step 1) sample handled well is placed on lens wiping paper, then places them on the sol evenning machine pallet after repacking, opens vacuum, and regulates size to 10 handkerchief of vacuum, they are adsorbed on pallet;
4) the above-mentioned electrolyte solution preparing is dripped in microchannel surface, under the suction-operated of vacuum, in electrolyte solution admission passage, due to the effumability of acetone, remaining material remains in microchannel inwall; By lens wiping paper together mobile example, in all microchannels of sample scope, suck and adsorbing electrolyte;
5) microchannel plate that sucks electrolyte solution is placed at 80 ℃ of temperature of vacuum drying chamber and is dried 30 minutes, acetone is thoroughly volatilized;
6) repeating 4,5 steps, is the solid electrolyte film of 300 nanometers until silicon micro-channel inwall forms thickness, thereby has formed the three-dimensional high molecular polymer film of one deck.
1) by silicon microchannel plate (having covered nickel metal layer and curing molybdenum layer) preliminary treatment: described silicon microchannel plate is dipped in 1% the Triton X-100 aqueous solution to 60 seconds;
2) by Kynoar-hexafluoropropylene copolymer (PVDF-HFP) matrix powder 1g, acetone (analyzing pure) solvent 100mL, after mixing by magnetic agitation to evenly, then add the nanometer SiO of 0.2g
2or Al
2o
3powder, then continue to stir, until obtain dissolving completely transparent and have the liquid of better mobility;
3) by step 1) sample handled well is placed on lens wiping paper, then places them on the sol evenning machine pallet after repacking, opens vacuum, and regulates size to 300 handkerchief of vacuum, they are adsorbed on pallet;
4) the above-mentioned electrolyte solution preparing is dripped in microchannel surface, under the suction-operated of vacuum, in electrolyte solution admission passage, due to the effumability of acetone, remaining material remains in microchannel inwall; By lens wiping paper together mobile example, in all microchannels of sample scope, suck and adsorbing electrolyte;
5) microchannel plate that sucks electrolyte solution is placed at 80 ℃ of temperature of vacuum drying chamber and is dried 30 minutes, acetone is thoroughly volatilized;
6) repeating 4,5 steps, is the solid electrolyte film of 100 nanometers until silicon micro-channel inwall forms thickness, thereby has formed the three-dimensional high molecular polymer film of one deck.
1) by silicon microchannel plate (having covered nickel metal layer and curing molybdenum layer) preliminary treatment: described silicon microchannel plate is dipped in 1% the Triton X-100 aqueous solution to 55 seconds;
2) by Kynoar-hexafluoropropylene copolymer (PVDF-HFP) matrix powder 1g, acetone (analyzing pure) solvent 100mL, after mixing by magnetic agitation to evenly, then add the nanometer SiO of 0.15g
2or Al
2o
3powder, then continue to stir, until obtain dissolving completely transparent and have the liquid of better mobility;
3) by step 1) sample handled well is placed on lens wiping paper, then places them on the sol evenning machine pallet after repacking, opens vacuum, and regulates size to 200 handkerchief of vacuum, they are adsorbed on pallet;
4) the above-mentioned electrolyte solution preparing is dripped in microchannel surface, under the suction-operated of vacuum, in electrolyte solution admission passage, due to the effumability of acetone, remaining material remains in microchannel inwall; By lens wiping paper together mobile example, in all microchannels of sample scope, suck and adsorbing electrolyte;
5) microchannel plate that sucks electrolyte solution is placed at 80 ℃ of temperature of vacuum drying chamber and is dried 30 minutes, acetone is thoroughly volatilized;
6) repeating 4,5 steps, is the solid electrolyte film of 150 nanometers until silicon micro-channel inwall forms thickness, thereby has formed the three-dimensional high molecular polymer film of one deck.
As Fig. 1, the three-dimensional high molecular polymer solid electrolyte shown in Fig. 2 and Fig. 3 is prepared relied on skeleton.In the silicon micro-channel structure of Fig. 1, Kong Kuanwei 3-5 micron, hole depth is 100-150 micron.On this basis, preparation layer of metal nickel coating, as the current collector of lithium battery, as shown in Figure 2., prepare the silicon micro-channel inwall deposition molybdenum bisuphide of nickel coating, as the negative pole of lithium battery, as shown in Figure 3.On the basis of Fig. 3, prepare high molecular polymer solid electrolyte.
As shown in Figure 4, this film is a kind of loose spongelike structure, is convenient to imbibition and ion transfer.Because electrolyte solution possesses certain viscosity, microchannel is directly contacted with pallet, can make microchannel be difficult to take off or can make microchannel rupture.Lens wiping paper is placed between microchannel and pallet, can overcomes the problems referred to above, and utilize acetone soln easily to make lens wiping paper separated with microchannel, can not introduce other material or pollution.
This electrolyte is carried out to imbibition test, find that absorbent is good.Meanwhile, the method for this vacuum liquid-absorbing absorption is suitable for the solution that other have certain viscosity.
The framework of whole battery as shown in Figure 5, take molybdenum bisuphide in negative pole, and we can select different positive electrodes to carry out integrant battery., in microchannel, first prepare after iron phosphate lithium positive pole meanwhile, also can prepare macromolecule organic solid electrolyte based according to above-mentioned processing step, then adopt the method for electrophoresis to prepare carbon graphite negative pole.Compatibility when its difference is prepared by electrophoretic techniques and between the electrolyte having prepared.
Claims (3)
1. a method for preparing solid electrolyte for the three-dimensional lithium ion battery based on silicon microchannel plate, is characterized in that: its step is as follows:
1) by silicon microchannel plate preliminary treatment: described silicon microchannel plate is dipped in to 50-70 second in 1% the Triton X-100 aqueous solution;
2) by Kynoar-hexafluoropropylene copolymer matrix powder 1g, acetone solvent 100mL, after mixing by magnetic agitation to evenly, then add the nanometer SiO of 0.1-0.25g
2or Al
2o
3then powder continues to stir, until obtain dissolving completely transparent and have the liquid of better mobility;
3) sample of step 1) being handled well is placed on lens wiping paper, then places them on the sol evenning machine pallet after repacking, opens vacuum, and regulates the size of vacuum, and they are adsorbed on pallet;
4) electrolyte solution preparing is dripped in microchannel surface, under the suction-operated of vacuum, in electrolyte solution admission passage; By lens wiping paper together mobile example, in all microchannels of sample scope, suck and adsorbing electrolyte;
5) microchannel plate that sucks electrolyte solution is placed at 80 ℃ of temperature of vacuum drying chamber and is dried 30 minutes, acetone is thoroughly volatilized;
6) repeating step 4) and step 5), until silicon micro-channel inwall forms thickness, be the solid electrolyte film of 50-300 nanometer, thereby formed the three-dimensional high molecular polymer film of one deck;
Sol evenning machine after repacking described in described step 3), is that existing sol evenning machine is reequiped, and the flexible pipe being connected with vacuum pump is directly led to pallet, places another pallet on pallet.
2. the method for preparing solid electrolyte of a kind of three-dimensional lithium ion battery based on silicon microchannel plate according to claim 1, is characterized in that: described silicon microchannel plate, and its Kong Kuanwei 3-5 micron, hole depth is 100-150 micron.
3. the method for preparing solid electrolyte of a kind of three-dimensional lithium ion battery based on silicon microchannel plate according to claim 1, is characterized in that: in step 3), described in open vacuum vacuum degree between 1Pa to 500Pa.
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| CN102456920B true CN102456920B (en) | 2014-02-26 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1459669A (en) * | 2002-05-17 | 2003-12-03 | 中国科学院微电子中心 | Method of improving easy broken base wafer glue coating technology |
| CN1581530A (en) * | 2004-05-21 | 2005-02-16 | 中国科学院上海硅酸盐研究所 | Method for preparing large-area ferroelectric film |
| CN1894812A (en) * | 2003-10-14 | 2007-01-10 | 特拉维夫大学远景技术发展公司 | Three-dimensional thin-film microbattery |
| CN101538704A (en) * | 2009-03-20 | 2009-09-23 | 华东师范大学 | Method of electroless nickel plating on silicon substrate microchannel |
-
2010
- 2010-10-28 CN CN201010523212.XA patent/CN102456920B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1459669A (en) * | 2002-05-17 | 2003-12-03 | 中国科学院微电子中心 | Method of improving easy broken base wafer glue coating technology |
| CN1894812A (en) * | 2003-10-14 | 2007-01-10 | 特拉维夫大学远景技术发展公司 | Three-dimensional thin-film microbattery |
| CN1581530A (en) * | 2004-05-21 | 2005-02-16 | 中国科学院上海硅酸盐研究所 | Method for preparing large-area ferroelectric film |
| CN101538704A (en) * | 2009-03-20 | 2009-09-23 | 华东师范大学 | Method of electroless nickel plating on silicon substrate microchannel |
Non-Patent Citations (1)
| Title |
|---|
| D.Golodnitsky et al."Advanced materials for the 3D microbattery".《Journal of power sources》.2006,第153卷(第2期),第281-287页. |
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