CN102479940A - Method for preparing metal lithium electrode having anti-corrosion protective film - Google Patents
Method for preparing metal lithium electrode having anti-corrosion protective film Download PDFInfo
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- CN102479940A CN102479940A CN2010105695668A CN201010569566A CN102479940A CN 102479940 A CN102479940 A CN 102479940A CN 2010105695668 A CN2010105695668 A CN 2010105695668A CN 201010569566 A CN201010569566 A CN 201010569566A CN 102479940 A CN102479940 A CN 102479940A
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Abstract
The invention relates to a method for preparing a metal lithium electrode having an anti-corrosion protective film, comprising the following three steps: (1) preparing hydrophobic polymer electrolyte; (2) forming a hydrophobic polymer electrolyte film and a cationic film on the surface of an NASICON solid electrolyte sheet to preparing a metal lithium electrode anti-corrosion protective film; and (3) compacting the metal lithium electrode anti-corrosion protective film into a pocket shape, putting the pocket-shaped film in lithium metal pressed by current collector, injecting a transition electrolyte layer, and sealing the pocket to prepare the metal lithium electrode having the anti-corrosion protective film. According to the invention, by preparing the hydrophobic polymer electrolyte film on the surface of the NASICON solid electrolyte sheet and simultaneously overlaying a layer of the cationic film, the corrosion due to immersion of the NASICON solid electrolyte sheet in aqueous electrolytes for a long time and the hydrolysis into powder are avoided, the stability of the NASICON solid electrolyte sheet in aqueous electrolytes for a long time is greatly improved, the service life of the metal lithium electrode is prolonged, and the safety of the metal lithium electrode is increased.
Description
Technical field
The invention belongs to the lithium metal battery technical field, especially relate to a kind of preparation method who has the metal lithium electrode of 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; A kind of preparation method who has the metal lithium electrode of 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 preparation method who has the metal lithium electrode of anti-corrosion protection film, 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 metal lithium electrode anti-corrosion protection film.
Step (3): the metal lithium electrode anti-corrosion protection mould of preparing in (2) is processed pocket-like; Cationic membrane is at outermost layer; The NASICON solid electrolyte sheet is at internal layer; The general polymer barrier film that one deck lithium ion battery is used wraps the lithium metal 5 that pressing has collector 6, puts into above-mentioned pocket, in pocket, injects the common liq electrolyte that lithium battery is used; General polymer barrier film and common liq electrolyte constitute transition dielectric substrate 4, process the metal lithium electrode that has the anti-corrosion protection film after pocket seals.
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; The preparation method who has the metal lithium electrode 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.
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; Simultaneously can realize the transmission of lithium ion between anti-corrosion protection film and 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 the metal lithium electrode anti-corrosion protection film cross-sectional schematic that the present invention prepares;
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 2g one hexyl tributyl imidazoles 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 metal lithium electrode anti-corrosion protection film shown in Figure 1.
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 5 that pressing has collector 6, 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 transition dielectric substrate 4, seal the isolation between back solid electrolyte sheet and the lithium metal to guarantee pocket, promptly obtain the metal lithium electrode that has the anti-corrosion protection film shown in Figure 2.The metal lithium electrode that has the anti-corrosion protection film that also available aluminum plastic film will be processed carries out packaging protecting.
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 2g one hexyl tributyl imidazoles 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.
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 5 that pressing has collector 6, 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 transition dielectric substrate 4, seal the isolation between back solid electrolyte sheet and the lithium metal to guarantee pocket, promptly obtain the metal lithium electrode that has the anti-corrosion protection film shown in Figure 2.The metal lithium electrode that has the anti-corrosion protection film that also available aluminum plastic film will be processed carries out packaging protecting.
Operation principle of the present invention:
The present invention is through being covered with double-layer films on the NASICON solid electrolyte sheet; Effectively avoid the corrosion in aqueous solution electrolysis liquid for a long time of NASICON solid electrolyte sheet and be hydrolyzed into Powderedly, simultaneously can realize the transmission of lithium ion between anti-corrosion protection film and 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. preparation method who has the metal lithium electrode of anti-corrosion protection film, 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 metal lithium electrode anti-corrosion protection film.
Step (3): the metal lithium electrode anti-corrosion protection mould of preparing in (2) is processed pocket-like; Cationic membrane is at outermost layer; The NASICON solid electrolyte sheet is at internal layer; The general polymer barrier film that one deck lithium ion battery is used wraps the lithium metal 5 that pressing has collector 6, puts into above-mentioned pocket, in pocket, injects the common liq electrolyte that lithium battery is used; General polymer barrier film and common liq electrolyte constitute transition dielectric substrate 4, process the metal lithium electrode that has the anti-corrosion protection film after pocket seals.
2. the preparation method who has the metal lithium electrode of anti-corrosion protection film according to claim 1; 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. metal lithium electrode 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. metal lithium electrode 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 who has the metal lithium electrode 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016020249A1 (en) * | 2014-08-04 | 2016-02-11 | Robert Bosch Gmbh | Superhydrophobic, nanostructured protective layer for rechargeable lithium battery cells having a metal lithium anode |
| CN111490237A (en) * | 2020-04-07 | 2020-08-04 | 华中科技大学 | Lithium metal negative electrode containing cationic polymer coating and preparation and application thereof |
| CN114204102A (en) * | 2021-10-29 | 2022-03-18 | 同济大学 | Water-proof, air-proof, dendritic crystal-inhibiting all-solid-state lithium metal protective film and construction strategy thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1680482A (en) * | 2005-02-04 | 2005-10-12 | 武汉大学 | Non-aqueous/aqueous two-phase gel electrolyte, preparation and battery thereof |
| CN101702444A (en) * | 2004-02-06 | 2010-05-05 | 波利普拉斯电池有限公司 | Protected active metal electrode and battery cell structures with non-aqueous interplayer architecture |
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2010
- 2010-11-29 CN CN2010105695668A patent/CN102479940A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101702444A (en) * | 2004-02-06 | 2010-05-05 | 波利普拉斯电池有限公司 | Protected active metal electrode and battery cell structures with non-aqueous interplayer architecture |
| CN1680482A (en) * | 2005-02-04 | 2005-10-12 | 武汉大学 | Non-aqueous/aqueous two-phase gel electrolyte, preparation and battery thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016020249A1 (en) * | 2014-08-04 | 2016-02-11 | Robert Bosch Gmbh | Superhydrophobic, nanostructured protective layer for rechargeable lithium battery cells having a metal lithium anode |
| CN106537645A (en) * | 2014-08-04 | 2017-03-22 | 罗伯特·博世有限公司 | Superhydrophobic, nanostructured protective layer for rechargeable lithium battery cells having a metal lithium anode |
| CN111490237A (en) * | 2020-04-07 | 2020-08-04 | 华中科技大学 | Lithium metal negative electrode containing cationic polymer coating and preparation and application thereof |
| CN114204102A (en) * | 2021-10-29 | 2022-03-18 | 同济大学 | Water-proof, air-proof, dendritic crystal-inhibiting all-solid-state lithium metal protective film and construction strategy thereof |
| CN114204102B (en) * | 2021-10-29 | 2023-11-14 | 同济大学 | Waterproof, air-insulating and dendrite-inhibiting all-solid-state lithium metal protection film and construction strategy thereof |
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Application publication date: 20120530 |