CN102655250A - Solid electrolyte for lithium air cells and preparation method thereof - Google Patents
Solid electrolyte for lithium air cells and preparation method thereof Download PDFInfo
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- CN102655250A CN102655250A CN2012101100173A CN201210110017A CN102655250A CN 102655250 A CN102655250 A CN 102655250A CN 2012101100173 A CN2012101100173 A CN 2012101100173A CN 201210110017 A CN201210110017 A CN 201210110017A CN 102655250 A CN102655250 A CN 102655250A
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Abstract
The invention discloses a solid electrolyte for lithium air cells. The solid electrolyte comprises a thin film prepared from a mixture of Al2O3, Li2O, GeO2 and P2O5, wherein the molar ratio of Al2O3 to Li2O to GeO2 to P2O5 is 1: (2.5-3.5): (5.5-6.5): (5.5-6.5). According to the invention, because a solid electrolyte is adopted, and no organic solvent is used, an air positive electrode is not flooded by the electrolyte, thereby solving the problem that in the process of discharge, the oxygen supply is insufficient and the cycle performance of the cell is reduced; and the solid electrolyte is environment-friendly, so that the harms that an electrolyte for traditional lithium ion cells is toxic and volatile are avoided.
Description
Technical field
The present invention relates to solid electrolyte of a kind of lithium-air battery and preparation method thereof.
Background technology
Along with day by day consuming and energy demand growing of fossil energy, extremely urgent to the research and development of novel energy material.Electric energy is as far back as the eighties of last century popularization and application, and battery is to use one of common tool of electric energy, and studying now and using is lithium ion battery more widely.Because the lithium ion battery energy density is high, long service life, self-discharge rate low with advantage such as memory-less effect, lithium ion battery is just receiving World Science man's concern.But present business-like lithium ion battery mainly also is based on LiCoO
2Deng the rocking chair mechanism of lithium ion inlay compound, positive electrode becomes the restriction of lithium ion battery energy density, and end-point energy density can only reach 400Wh/Kg, so, the unbearable important task of lithium ion battery, it is imperative to seek new electrochemical power source approach.
The research of lithium-air battery is arisen at the historic moment, and it is negative pole with the lithium metal, and the porous electrode of being made up of carbon-based material is anodal; In the discharge process; Lithium metal loses battery at negative pole becomes lithium ion, and it is anodal that electronics arrives porous through external circuit, with airborne oxygen reduction; This reaction continues to carry out, and battery just can provide energy to load.Charging process is just in time opposite, and under the effect of charging voltage, the discharging product that produces in the discharge process is at first oxidized at the porous positive pole; Again emit oxygen; Lithium ion then is reduced into lithium metal at negative pole, treats that this process carries out fully, and then battery can provide energy to load again again.This shows that lithium-air battery can not produce environmentally harmful material in the whole charging and discharging process, is the green process of zero pollution fully.
Another significant advantage of lithium-air battery be exactly anodal active material oxygen be to be directed to surrounding air; Thereby be inexhaustible; And need not be stored in inside battery; So not only reduced cost but also alleviated the weight of battery, so the energy density of battery depends on lithium metal one side fully.Can draw through Theoretical Calculation, the energy density of lithium-air battery can reach the superelevation theoretical energy density of 13200Wh/Kg, and this energy density is enough to compare favourably with gasoline, thereby is expected to complete gasoline replacing, really realizes pure electric automobile.
Lithium-air battery has huge application potential, but study prematurity still at present, still has the solution that requires study of many key technology points.For example, as positive active material, the inevitable requirement positive electrode can help the oxygen molecule rapid diffusion with airborne oxygen, with the electronics fast reaction of battery.And for example, traditional lithium ion battery adopts organic electrolyte, and surface tension can make oil loving air electrode flooded by electrolyte, is unfavorable for forming diffusion electrode, and oxygen supply is not enough during guiding discharge, reduces cycle performance of battery.
Summary of the invention
The purpose of this invention is to provide solid electrolyte of a kind of lithium-air battery and preparation method thereof.
The technical scheme that the present invention taked is:
A kind of solid electrolyte of lithium-air battery comprises that by mol ratio be 1: (2.5-3.5): (5.5-6.5): Al (5.5-6.5)
2O
3, Li
2O, GeO
2, P
2O
5The film processed of mixture.
Also comprising the film of being processed by the mixture of polyethylene glycol oxide, lithium salts electrolyte, boron nitride, is 100% calculating with three's quality sum, and the lithium salts electrolyte is 18-25wt%, and boron nitride is 8-16wt%, and surplus is a polyethylene glycol oxide.
Also comprise by polyethylene glycol oxide, lithium salts electrolyte, Li
2The film that the mixture of O is processed is 100% calculating with three's quality sum, and the lithium salts electrolyte is 18-25wt%, Li
2O is 8-16wt%, and surplus is a polyethylene glycol oxide.
Described lithium salts electrolyte is LiPF
6, LiClO
4, LiAsF
6, LiBF
4, LiN (SO
2CF
2CF
3)
2In a kind of.
The preparation method of the solid electrolyte of lithium-air battery may further comprise the steps:
1) with mixture melt, abrasive dust flattens, and sintering obtains the first film;
2) mixture is mixed, ball milling, hot pressing obtains second film to 200-400 μ m;
3) mixture is mixed, ball milling, hot pressing obtains the 3rd film to 200-400 μ m;
4) the first film is clipped between B and the C, is depressed into 800-1000 μ m, obtain solid electrolyte.
In the step 1), fusion temperature is 1200-1400 ℃.
In the step 1), sintering temperature is 800-1000 ℃.
In the step 1), sintering time is 1-2h.
The invention has the beneficial effects as follows: the present invention adopts solid electrolyte, does not have organic solvent, and the air positive pole can not flooded by electrolyte, and oxygen supply is not enough when solving discharge, reduces the problem of cycle performance of battery.And environmentally friendly, the harm that solves the electrolyte toxic and volatile of traditional lithium ion battery.
Description of drawings
Fig. 1 is the battery structure sketch map.
Fig. 2 is the specific capacity-cycle-index curve chart that contains the battery of solid electrolyte of the present invention.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explanation:
The step 2 that below relates to hot pressing), 3) in, hot pressing pressure is 25-30MPa, hot pressing time is 0.5-1h.
Embodiment 1:
1) with Al
2O
3, Li
2O, GeO
2, P
2O
5Press the mixed in molar ratio of 1:3:6:6,1400 ℃ of fusings down, abrasive dust flattens then, at 1000 ℃ of following sintering 1h, obtains the first film, and the thickness of film is 400 μ m;
2) with the polyethylene glycol oxide of 60wt%, the LiPF of 25wt%
6Mix with the BN of 15wt%, ball milling, 1000 ℃ of following hot pressing to 400 μ m obtain second film;
3) with the polyethylene glycol oxide of 60wt%, the LiPF of 25wt%
6Li with 15wt%
2O mixes, ball milling, and 1000 ℃ of following hot pressing to 400 μ m obtain the 3rd film;
4) the first film is clipped in respectively between second film and the 3rd film, 1000 ℃ of following hot pressing to 1000 μ m obtain solid electrolyte.
Embodiment 2:
1) with Al
2O
3, Li
2O, GeO
2, P
2O
5Press the mixed in molar ratio of 1:2.5:5.5:5.5,1200 ℃ of fusings down, abrasive dust flattens then, at 800 ℃ of following sintering 2h, obtains the first film, and the thickness of film is 400 μ m;
2) with the polyethylene glycol oxide of 70wt%, the LiClO of 18wt%
4Mix with the BN of 12wt%, ball milling, 1000 ℃ of following hot pressing to 400 μ m obtain second film;
3) with the polyethylene glycol oxide of 70wt%, the LiClO of 18wt%
4Li with 12wt%
2O mixes, ball milling, and 1000 ℃ of following hot pressing to 400 μ m obtain the 3rd film;
4) the first film is clipped in respectively between second film and the 3rd film, 1000 ℃ of following hot pressing to 1000 μ m obtain solid electrolyte.
With LiFePO4, acetylene black, PVDF, be that the mass ratio of 7:2:1 is dissolved among the NMP with the mass ratio, process slurry; Be coated on again on the aluminium foil, oven dry, compacting, be cut to the disk of 1 cm, process positive electrode layer; With the metallic lithium foil is negative electrode layer, and electrolyte adopts the solid electrolyte of embodiment 1, forms battery; Further, in conjunction with Fig. 1 battery structure of the present invention is described, this lithium-air battery has anode coat 4 (plastic housing); On the inside bottom surface of anode coat 4, form aluminium foil 6 as negative current collector, be connected with cathode conductor 2 (1mm diameter steel bar); On negative current collector, form metallic lithium foil 5 as negative electrode layer; Positive electrode layer 9 is connected with positive wire 1 (copper bar of 1mm diameter); Three layers of solid electrolyte of configuration between negative electrode layer and positive electrode layer; Metallic lithium foil 5 and the 3rd film 7 are fitted; The positive electrode layer 9 and second film 13 are fitted; The first film 8 is between second film 13 and the 3rd film 7; Also be provided with anodal shell 3 (steel casing) outside the anode coat 4 of this battery, be provided with sealing ring 12 (sealing ring material is the M-11 lithium ion battery fluid sealant that Harbin Jingcheng Battery Sealant Co., Ltd produces) between anode coat 4 and the anodal shell 3.
(MBRAUN, LabMater100 carry out in Germany) the anhydrous glove box of the anaerobic that is full of argon gas that is assembled in of battery.
With electrochemical workstation above-mentioned sample is carried out the constant current charge-discharge test, current density is 40mA/cm
2, voltage range is controlled between the 2.0-4.8 V, circulates the specific capacity that obtains-cycle-index curve such as Fig. 2 50 times.As can be seen from Figure 2, of the present invention is that the battery of part has good cycle charge discharge electrical property with the solid electrolyte.
Claims (8)
1. the solid electrolyte of a lithium-air battery is characterized in that: comprise that by mol ratio be 1: (2.5-3.5): (5.5-6.5): Al (5.5-6.5)
2O
3, Li
2O, GeO
2, P
2O
5The film processed of mixture.
2. the solid electrolyte of a kind of lithium-air battery according to claim 1; It is characterized in that: also comprise the film of processing by the mixture of polyethylene glycol oxide, lithium salts electrolyte, boron nitride; With three's quality sum is 100% calculating; The lithium salts electrolyte is 18-25wt%, and boron nitride is 8-16wt%, and surplus is a polyethylene glycol oxide.
3. the solid electrolyte of a kind of lithium-air battery according to claim 1 is characterized in that: also comprise by polyethylene glycol oxide, lithium salts electrolyte, Li
2The film that the mixture of O is processed is 100% calculating with three's quality sum, and the lithium salts electrolyte is 18-25wt%, Li
2O is 8-16wt%, and surplus is a polyethylene glycol oxide.
4. according to the solid electrolyte of a described a kind of lithium-air battery in claim 2 or 3, it is characterized in that: described lithium salts electrolyte is LiPF
6, LiClO
4, LiAsF
6, LiBF
4, LiN (SO
2CF
2CF
3)
2In a kind of.
5. the preparation method of the solid electrolyte of each the described lithium-air battery among the claim 1-3 is characterized in that: may further comprise the steps:
1) with the described mixture melt of claim 1, abrasive dust flattens, and sintering obtains the first film;
2) the described mixture of claim 2 is mixed, ball milling, hot pressing obtains second film to 200-400 μ m;
3) the described mixture of claim 3 is mixed, ball milling, hot pressing obtains the 3rd film to 200-400 μ m;
4) the first film is clipped between B and the C, is depressed into 800-1000 μ m, obtain solid electrolyte.
6. the preparation method of the solid electrolyte of a kind of lithium-air battery according to claim 5, it is characterized in that: in the step 1), fusion temperature is 1200-1400 ℃.
7. the preparation method of the solid electrolyte of a kind of lithium-air battery according to claim 5, it is characterized in that: in the step 1), sintering temperature is 800-1000 ℃.
8. the preparation method of the solid electrolyte of a kind of lithium-air battery according to claim 5, it is characterized in that: in the step 1), sintering time is 1-2h.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108011078A (en) * | 2016-11-01 | 2018-05-08 | 中山大学 | Electrode assemblie based on flexible substrate, lithia hull cell and preparation method |
| CN108023145A (en) * | 2016-11-01 | 2018-05-11 | 中山大学 | Electrode assemblie, lithia hull cell and preparation method |
| CN111446490A (en) * | 2019-04-10 | 2020-07-24 | 西安瑞智材料科技有限公司 | Single-layer boron nitride modified PEO polymer electrolyte and preparation method thereof |
| CN114478328A (en) * | 2020-10-27 | 2022-05-13 | 上海漫关越水处理有限公司 | Ionic membrane compound of lithium air battery tert-aryl ether diene difluoromethyl sulfonate |
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| CN1726608A (en) * | 2002-10-15 | 2006-01-25 | 波利普拉斯电池有限公司 | Ionically conductive membranes for protection of active metal anodes |
| CN1925203A (en) * | 2005-08-31 | 2007-03-07 | 株式会社小原 | Lithium ion secondary battery and solid electrolyte therefor |
| CN1938895A (en) * | 2004-02-06 | 2007-03-28 | 波利普拉斯电池有限公司 | Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture |
-
2012
- 2012-04-16 CN CN201210110017.3A patent/CN102655250B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1726608A (en) * | 2002-10-15 | 2006-01-25 | 波利普拉斯电池有限公司 | Ionically conductive membranes for protection of active metal anodes |
| CN1938895A (en) * | 2004-02-06 | 2007-03-28 | 波利普拉斯电池有限公司 | Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture |
| CN1925203A (en) * | 2005-08-31 | 2007-03-07 | 株式会社小原 | Lithium ion secondary battery and solid electrolyte therefor |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108011078A (en) * | 2016-11-01 | 2018-05-08 | 中山大学 | Electrode assemblie based on flexible substrate, lithia hull cell and preparation method |
| CN108023145A (en) * | 2016-11-01 | 2018-05-11 | 中山大学 | Electrode assemblie, lithia hull cell and preparation method |
| CN108023145B (en) * | 2016-11-01 | 2019-11-19 | 中山大学 | Electrode assembly, lithia hull cell and preparation method |
| CN108011078B (en) * | 2016-11-01 | 2020-02-14 | 中山大学 | Flexible substrate-based electrode assembly and preparation method of lithium-oxygen thin film battery |
| CN111446490A (en) * | 2019-04-10 | 2020-07-24 | 西安瑞智材料科技有限公司 | Single-layer boron nitride modified PEO polymer electrolyte and preparation method thereof |
| CN114478328A (en) * | 2020-10-27 | 2022-05-13 | 上海漫关越水处理有限公司 | Ionic membrane compound of lithium air battery tert-aryl ether diene difluoromethyl sulfonate |
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| CN102655250B (en) | 2014-09-17 |
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