CN102544426A - Method for manufacturing anticorrosive protective membrane for metal lithium-ion battery - Google Patents
Method for manufacturing anticorrosive protective membrane for metal lithium-ion battery Download PDFInfo
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- CN102544426A CN102544426A CN2010105730888A CN201010573088A CN102544426A CN 102544426 A CN102544426 A CN 102544426A CN 2010105730888 A CN2010105730888 A CN 2010105730888A CN 201010573088 A CN201010573088 A CN 201010573088A CN 102544426 A CN102544426 A CN 102544426A
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Abstract
The invention relates to a method for manufacturing an anticorrosive protective membrane for a metal lithium-ion battery. The method comprises the following two steps of: (1) preparing hydrophobic polymer electrolyte; and (2) forming a hydrophobic polymer electrolyte membrane and a cationic membrane on the surface of an NASICON (Natrium Super Ionic Conductor) solid electrolyte sheet to manufacture the anticorrosive protective membrane for the metal lithium-ion battery. According to the method for manufacturing the anticorrosive protective membrane for the metal lithium-ion battery, disclosed by the invention, a layer of the cationic membrane is stacked when the hydrophobic polymer electrolyte membrane is manufactured on the surface of the NASICON solid electrolyte sheet, thus a situation that the NASICON solid electrolyte sheet is corroded and hydrolyzed to powder in aqueous electrolyte for a long term is avoided, and the stability of the NASICON solid electrolyte sheet in the aqueous electrolyte for a long term is largely improved, and when the manufactured anticorrosive protective membrane is applied to the metal lithium-ion battery, the service life of the metal lithium-oil battery is prolonged and the safety of the metal lithium-oil battery is increased.
Description
Technical field
The invention belongs to the lithium metal battery technical field, especially relate to the preparation method of a kind of lithium metal battery with the anti-corrosion protection film.
Background technology
Lithium metal battery have high theoretical electrochemistry equivalent (3800mAh/g) and very low redox potential (3.045V), having vast potential for future development and competitive advantage, is one of developing direction of following high capacity power source.Generally; Lithium metal as negative pole is applied in the organic electrolyte system; But the positive electrode of many high energy only in the aqueous solution electrolysis liquid system competence exertion go out more performance; So in order mating, really to bring into play metal lithium electrode and the large current discharging capability of corresponding positive electrode in aqueous solution electrolysis liquid thereof, to need the application performance of research lithium metal in aqueous solution electrolysis liquid with these high energy are anodal.
For fear of the violent side reaction between lithium metal and the aqueous solution electrolysis liquid, the researcher has attempted numerous methods.Wherein comparatively effectively the transition dielectric substrate between the solid electrolyte sheet of package metals lithium and lithium metal and the solid electrolyte sheet is protected metal lithium electrode.Solid electrolyte sheet mainly is the lithium ion conductor with NASICON structure; This solid electrolyte sheet can be realized the lithium ion transmission between the lithium metal and the aqueous solution; And isolated lithium metal and contact with the direct of the aqueous solution, realized the safety and stability discharge of lithium metal in the aqueous solution through these means.
Find through long term studies; The NASICON solid electrolyte sheet short time is immersed in (in 1 month) in the aqueous solution electrolysis liquid, has good stable property, can play a very good protection to metal lithium electrode; If but the NASICON solid electrolyte sheet is immersed in aqueous solution electrolysis liquid (more than half a year operating time) for a long time; Even neutral aqueous solution electrolyte, still there is slow corrosion in the NASICON solid electrolyte sheet, especially when the acid-base value of aqueous solution electrolysis liquid is higher; NASICON solid electrolyte sheet corrosion rate can obviously be accelerated; The sector-meeting of NASICON solid electrolyte can't be protected the safety and stability discharge of metal lithium electrode in aqueous solution electrolysis liquid because of the hydrolysis corrosion, not only shortens the useful life of metal lithium electrode, and causes the potential safety hazard of metal lithium electrode.
Summary of the invention
The objective of the invention is to overcome the weak point of prior art; The preparation method of a kind of lithium metal battery with the anti-corrosion protection film is provided; This method is in the lithium ion transmission that guarantees between lithium metal and the aqueous solution electrolysis liquid, under isolating metal lithium and the prerequisite that aqueous solution electrolysis liquid directly contacts, can protect the metal lithium electrode in the aqueous solution electrolysis liquid for a long time; Prolong the useful life of metal lithium electrode, make the metal lithium electrode can safety and stability discharge in aqueous solution electrolysis liquid for a long time.
The objective of the invention is to realize through following scheme:
A kind of lithium metal battery is characterized in that with the preparation method of anti-corrosion protection film: step is:
Step (1): with mass percent is that the hydrophobic polymer of 10-80wt% and hydrophobicity il electrolyte that mass percent is 20-90wt% are mixed, and forms gel hydrophobic polymer electrolyte; Said hydrophobic polymer is a kind of of vinylidene, copolymer from vinylidene fluoride and hexafluoropropylene, polyacrylate; Said hydrophobicity il electrolyte is made up of quaternary ammonium salt and anion; Quaternary ammonium salt and anionic mass ratio are 1: 1-2, said quaternary ammonium salt are a kind of of imidazoles, piperidines, pyrrolidines, piperazines, and said anion is a kind of of hexafluoro-phosphate radical, two acyl imonium roots;
Step (2): the hydrophobic polymer electrolyte of preparing in (1) is coated on NASICON solid electrolyte sheet surface; Forming thickness is the hydrophobic polymer dielectric film of 0.01mm-5mm; Cover the cationic membrane that a layer thickness is 0.2mm-1mm on hydrophobic polymer dielectric film surface again, promptly process the metal lithium electrode lithium metal battery and use the anti-corrosion protection film.
And the hydrophobic polymer electrolyte that is overlying on NASICON solid electrolyte sheet surface in said (2) is that the hydrophobic polymer electrolyte is cast in NASICON solid electrolyte sheet surface, waters the thickness of fluence control hydrophobic polymer dielectric film through control.
And; The hydrophobic polymer electrolyte that is overlying on NASICON solid electrolyte sheet surface in said (2) is for being cast in gel hydrophobic polymer electrolyte in the mould earlier; Dry back forms the hydrophobic polymer dielectric film, through vacuum pressure the hydrophobic polymer dielectric film is fitted in NASICON solid electrolyte sheet surface again.
And; The hydrophobic polymer electrolyte that is overlying on NASICON solid electrolyte sheet surface in said (2) is for spraying to gel hydrophobic polymer electrolyte on the smooth sheet glass earlier; Dry back forms the hydrophobic polymer dielectric film, through vacuum pressure the hydrophobic polymer dielectric film is fitted in NASICON solid electrolyte sheet surface again.
And; Lithium metal battery according to claim 1 is with the preparation method of anti-corrosion protection film; It is characterized in that: add electrolytic salt in the said hydrophobicity il electrolyte; Said electrolytic salt is a kind of of hexafluorophosphoric acid, two acyl imonium lithium salts, two acyl imonium sodium salt, two acyl imonium sylvite, and the concentration of electrolytic salt is 0.1-3mol/l in the hydrophobicity il electrolyte.
Advantage of the present invention and good effect are:
Stack one deck cationic membrane when the present invention is employed in NASICON solid electrolyte sheet surface preparation hydrophobic polymer dielectric film; Suppressing hydrone and NASICON solid electrolyte sheet surface contacts; Avoided the corrosion in aqueous solution electrolysis liquid for a long time of NASICON solid electrolyte sheet and be hydrolyzed into Powdered; Can realize simultaneously lithium ion at lithium metal battery with the transmission between anti-corrosion protection film and the aqueous solution electrolysis liquid; Significantly improved the NASICON solid electrolyte sheet stability in aqueous solution electrolysis liquid for a long time; Guaranteed that metal lithium electrode has good stable property for a long time in aqueous solution electrolysis liquid, prolonged the useful life and the metal lithium electrode fail safe in aqueous solution electrolysis liquid for a long time of metal lithium electrode.
Description of drawings
Fig. 1 is that the lithium metal battery for preparing of the present invention is with anti-corrosion protection film cross-sectional schematic.
Embodiment
Through specific embodiment the present invention is made further detailed description below, following examples are descriptive, are not determinate, can not limit protection scope of the present invention with this.
Embodiment 1:
Select Solid State Ionics for use, 171 (2004): the NASICON solid electrolyte material of Li-Al-Ti-P-O series or Li-Al-Ge-P-O series or two types of mixtures of material or derivative is processed the NASICON solid electrolyte sheet that thickness is 200 μ m in the 207-213. document.
Kynoar (PVDF) hydrophobic polymer is dissolved in N-methyl pyrrolidone (NMP); The solvent that this uses when being hydrophobic polymer and the mixing of hydrophobicity ionic liquid; During it volatilizees fully and removes, form the PVDF hydrophobic polymer solution of mass percent 8% in subsequent process; Take by weighing the basic tributyl imidazoles of 2g one hexafluorophosphoric acid hydrophobicity ionic liquid; And join in the above-mentioned PVDF solution of 6g, after mixing, control the thickness of slurry and the thickness of final film forming through being controlled to the film die area; Pour into in the film die; 80 ℃ of oven dry are one hour in the baking oven, are placed on dry 12h in 120 ℃ the vacuum drying chamber then, promptly obtain 0.01mm-5mm hydrophobic polymer dielectric film 2.
The hydrophobic polymer dielectric film of preparing is directly fitted on the NASICON solid electrolyte film 1 through vacuum pressure; Again the equal facies pattern cationic membrane 3 of the general goodsization of 0.2mm-1mm is directly fitted to hydrophobic polymer film surface through vacuum pressure, promptly make lithium metal battery shown in Figure 1 and use the anti-corrosion protection film with lithium metal battery.
Metal lithium electrode anti-corrosion protection mould shown in Figure 1 is processed pocket-like; Cationic membrane is at outermost layer; The NASICON solid electrolyte sheet is at internal layer, and the general polymer barrier film that one deck lithium ion battery is used wraps the lithium metal that pressing has collector, puts into above-mentioned pocket; In pocket, inject the common liq electrolyte that lithium battery is used; General polymer barrier film and common liq electrolyte have constituted the transition dielectric substrate, seal the isolation between back solid electrolyte sheet and the lithium metal to guarantee pocket, play the anti-corrosion protection effect to lithium metal battery.
Embodiment 2:
Select Solid State Ionics for use, 171 (2004): the NASICON solid electrolyte material of Li-Al-Ti-P-O series or Li-Al-Ge-P-O series or two types of mixtures of material or derivative is processed the NASICON solid electrolyte sheet that thickness is 200 μ m in the 207-213. document.
Kynoar (PVDF) hydrophobic polymer is dissolved in N-methyl pyrrolidone (NMP); The solvent that this uses when being hydrophobic polymer and the mixing of hydrophobicity ionic liquid; It volatilizees fully in subsequent process and removes) in, the PVDF hydrophobic polymer solution of formation mass percent 8%; Take by weighing the basic tributyl imidazoles of 2g one hexafluorophosphoric acid hydrophobicity ionic liquid; And join in the above-mentioned PVDF solution of 6g, after mixing, pour in the one-tenth film die of certain area; Dried one hour for 80 ℃ in the baking oven; Be placed on dry 12h in 120 ℃ the vacuum drying chamber then, control the thickness of slurry and the thickness of final film forming, promptly obtain 0.01mm-5mm hydrophobic polymer dielectric film 2 through being controlled to the film die area.
The NASICON solid electrolyte sheet is put into in the film die; Pour the hydrophobic polymer electrolyte slurry into mould; Directly be poured on the NASICON solid electrolyte film, form the hydrophobic polymer dielectric film, control final film forming thickness through the thickness of control slurry; Again the equal facies pattern cationic membrane 3 of general goodsization is directly fitted on the hydrophobic polymer dielectric film, promptly make metal lithium electrode shown in Figure 1 and use the anti-corrosion protection film with lithium metal battery.
Metal lithium electrode anti-corrosion protection mould shown in Figure 1 is processed pocket-like; Cationic membrane is at outermost layer; The NASICON solid electrolyte sheet is at internal layer, and the general polymer barrier film that one deck lithium ion battery is used wraps the lithium metal that pressing has collector, puts into above-mentioned pocket; In pocket, inject the common liq electrolyte that lithium battery is used; General polymer barrier film and common liq electrolyte have constituted the transition dielectric substrate, seal the isolation between back solid electrolyte sheet and the lithium metal to guarantee pocket, play the anti-corrosion protection effect to lithium metal battery.
Operation principle of the present invention:
The present invention is through being covered with double-layer films on the NASICON solid electrolyte sheet; Effectively avoided the corrosion in aqueous solution electrolysis liquid for a long time of NASICON solid electrolyte sheet and be hydrolyzed into Powdered, can realize simultaneously lithium ion at lithium metal battery with the transmission between anti-corrosion protection film and the aqueous solution electrolysis liquid.Wherein thin film is the hydrophobic polymer dielectric film, and another layer film is a cation-exchange membrane.This two membranes except realize lithium ion by electrode to the transmission of aqueous solution electrolysis liquid direction, also played the different protection effect respectively.
Wherein the effect of hydrophobic polymer dielectric film is to utilize the repellency of hydrophobic polymer film to moisture; The resistance that moisturizes and spread; Reduce the speed of contact with moisture solid electrolyte; In water-repellent layer, form moisture concentration (or activity) gradient, reduced the concentration (or activity) of moisture, reached the effect that reduces the corrosion of NASICON solid electrolyte on the solid electrolyte surface.
The protective effect of cationic membrane is to prevent the hydrophobic polymer film when direct contact water solution, and diffusion slowly takes place ionic liquid composition wherein, gets in the aqueous solution.When not having cationic membrane to exist, though ionic liquid composition diffusion process is very slow, along with the prolongation of time, hydrophobic polymer diaphragm composition takes place obviously to change and ineffective.But cationic existence has been arranged; Ion liquid anion can't pass through, and the cation in the ionic liquid has surpassed the cation volume that cationic membrane can exchange because volume is bigger; So also can't pass through, so just guarantee that ionic liquid can not diffuse into the aqueous solution in a large number.Common cationic membrane is to allow simple cations such as H+, Li+, Na+, K+, Mg2+, Ca2+ to pass through, but complicated big volume cation can't pass through, and for example the cation in the ionic liquid can't pass through; The cationic membrane that the better cationic membrane of performance only allows the simple cations of small size such as H+, Li+, Na+ to pass through.
Claims (5)
1. a lithium metal battery is with the preparation method of anti-corrosion protection film, and it is characterized in that: step is:
Step (1): with mass percent is that the hydrophobic polymer of 10-80wt% and hydrophobicity il electrolyte that mass percent is 20-90wt% are mixed, and forms gel hydrophobic polymer electrolyte; Said hydrophobic polymer is a kind of of vinylidene, copolymer from vinylidene fluoride and hexafluoropropylene, polyacrylate; Said hydrophobicity il electrolyte is made up of quaternary ammonium salt and anion; Quaternary ammonium salt and anionic mass ratio are 1: 1-2, said quaternary ammonium salt are a kind of of imidazoles, piperidines, pyrrolidines, piperazines, and said anion is a kind of of hexafluoro-phosphate radical, two acyl imonium roots;
Step (2): the hydrophobic polymer electrolyte of preparing in (1) is coated on NASICON solid electrolyte sheet surface; Forming thickness is the hydrophobic polymer dielectric film of 0.01mm-5mm; Cover the cationic membrane that a layer thickness is 0.2mm-1mm on hydrophobic polymer dielectric film surface again, promptly process the metal lithium electrode lithium metal battery and use the anti-corrosion protection film.
2. lithium metal battery according to claim 1 is with the preparation method of anti-corrosion protection film; It is characterized in that: the hydrophobic polymer electrolyte that is overlying on NASICON solid electrolyte sheet surface in said (2) is that the hydrophobic polymer electrolyte is cast in NASICON solid electrolyte sheet surface, waters the thickness of fluence control hydrophobic polymer dielectric film through control.
3. lithium metal battery according to claim 1 is with the preparation method of anti-corrosion protection film; It is characterized in that: the hydrophobic polymer electrolyte that is overlying on NASICON solid electrolyte sheet surface in said (2) is for being cast in gel hydrophobic polymer electrolyte in the mould earlier; Dry back forms the hydrophobic polymer dielectric film, through vacuum pressure the hydrophobic polymer dielectric film is fitted in NASICON solid electrolyte sheet surface again.
4. lithium metal battery according to claim 1 is with the preparation method of anti-corrosion protection film; It is characterized in that: the hydrophobic polymer electrolyte that is overlying on NASICON solid electrolyte sheet surface in said (2) is for spraying to gel hydrophobic polymer electrolyte on the smooth sheet glass earlier; Dry back forms the hydrophobic polymer dielectric film, through vacuum pressure the hydrophobic polymer dielectric film is fitted in NASICON solid electrolyte sheet surface again.
5. the preparation method of anti-corrosion protection film according to claim 1; It is characterized in that: add electrolytic salt in the said hydrophobicity il electrolyte; Said electrolytic salt is a kind of of hexafluorophosphoric acid, two acyl imonium lithium salts, two acyl imonium sodium salt, two acyl imonium sylvite, and the concentration of electrolytic salt is 0.1-3mol/l in the hydrophobicity il electrolyte.
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| CN2010105730888A CN102544426A (en) | 2010-12-07 | 2010-12-07 | Method for manufacturing anticorrosive protective membrane for metal lithium-ion battery |
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| CN2010105730888A CN102544426A (en) | 2010-12-07 | 2010-12-07 | Method for manufacturing anticorrosive protective membrane for metal lithium-ion battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3298646A4 (en) * | 2015-05-21 | 2018-12-12 | The University of North Carolina at Chapel Hill | Hybrid solid single-ion-conducting electrolytes for alkali batteries |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3298646A4 (en) * | 2015-05-21 | 2018-12-12 | The University of North Carolina at Chapel Hill | Hybrid solid single-ion-conducting electrolytes for alkali batteries |
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Application publication date: 20120704 |