CN102637863A - Positive electrode material of lithium air battery and preparation method thereof - Google Patents
Positive electrode material of lithium air battery and preparation method thereof Download PDFInfo
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- CN102637863A CN102637863A CN2012101100296A CN201210110029A CN102637863A CN 102637863 A CN102637863 A CN 102637863A CN 2012101100296 A CN2012101100296 A CN 2012101100296A CN 201210110029 A CN201210110029 A CN 201210110029A CN 102637863 A CN102637863 A CN 102637863A
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- positive electrode
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- sintering
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- 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 discloses a positive electrode material of a lithium air battery. The positive electrode material comprises a mixture of Al2O3, Li2O, GeO2 and P2O5 at the weight ratio of 1:(2.5-3.5):(5.5-6.5):(5.5-6.5). A positive electrode of the battery, disclosed by the invention, is of an air material with a catalytic reduction role against oxygen, and the external oxygen can be used for participating in the reaction of the electrode. Compared with a traditional lithium ion battery, the positive electrode material does not use lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate and the like, so that the consumption of valuable metals is low and the cost is further reduced. The cyclic performance of the air battery containing the air positive electrode disclosed by the invention is better.
Description
Technical field
The present invention relates to a kind of positive active material and the anodal preparation method of air of lithium-air battery.
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.The air of prior art for preparing is anodal, and oxygen molecule can not rapid diffusion, and the cycle performance of battery is relatively poor.
Summary of the invention
The present invention relates to a kind of positive electrode and the anodal preparation method of air of lithium-air battery.
The technical scheme that the present invention taked is:
A kind of positive electrode of lithium-air battery, it comprises that mol ratio is 1: (2.5-3.5): (5.5-6.5): Al (5.5-6.5)
2O
3, Li
2O, GeO
2, P
2O
5Mixture.
Also comprise acetylene black, polymeric media.
In mixture, acetylene black, polymeric media three quality be 100%, mixture quality percentage is 50-75%, and acetylene black is 25-50%, and surplus is a polymeric media.
Described polymeric media is a kind of in PEO, PPOX, polytetrafluoroethylene, polymethylacrylic acid, polyacrylamide, Merlon, the polysulfones.
The preparation method that a kind of air is anodal may further comprise the steps:
1) with described mixture melt, abrasive dust, sintering, obtains powders A;
2) acetylene black of 25-50wt%, powders A and the polymeric media of 50-75wt% are mixed in the water, stir, be applied to the two sides of Ni-based material, and Ni-based material is clipped between two corrosion resistant plates, flatten, drying, sintering under the protective atmosphere obtains the air positive pole.
In the step 1), described fusion temperature is 1200-1400 ℃.
In the step 1), the temperature of sintering is 800-1000 ℃.
In the step 1), the time of sintering is 1-2h.
Step 2) in, described protective atmosphere is a kind of among He, Ne, the Ar.
Step 2) in, described sintering temperature is 200-300 ℃, and described sintering time is 20-30min.
The invention has the beneficial effects as follows: anode of the present invention can be participated in electrode reaction with extraneous oxygen for oxygen there being the air material of catalytic reduction effect.Compare with traditional lithium ion battery, positive electrode is not cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4 etc., so the consumption of valuable metal is few, thereby has reduced cost.The cycle performance that contains the anodal air cell of air of the present invention is better.
Description of drawings
Fig. 1 is the structural section sketch map of battery of the present invention.
Fig. 2 be contain the anodal battery of air of the present invention specific capacity-cycle-index curve chart.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explanation:
Embodiment 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 at 1000 ℃ of following sintering 1h, obtains powders A.The polytetrafluoroethylene of the powders A of the acetylene black of 45wt%, 50wt% and 5% is mixed in the water (consumption of water be acetylene black, powders A, polytetrafluoroethylene three quality and 3 times), stir, be applied to the two sides of nickel screen; And nickel screen is clipped between two 1mm corrosion resistant plates; Flatten, dry 8h under 100 ℃ is at 200 ℃; Sintering 20min under the Ar gas shiled obtains the air positive pole.
Embodiment 2:
With Al
2O
3, Li
2O, GeO
2, P
2O
5Press the mixed in molar ratio of 1:2.5:5.5:5.5,1400 ℃ of fusings down, abrasive dust at 1000 ℃ of following sintering 1h, obtains powders A.The polytetrafluoroethylene of the powders A of the acetylene black of 25wt%, 70wt% and 5% is mixed in the water (consumption of water be acetylene black, powders A, polytetrafluoroethylene three quality and 3 times), stir, be applied to the two sides of nickel screen; And nickel screen is clipped between two 1mm corrosion resistant plates; Flatten, dry 10h under 100 ℃ is at 300 ℃; Sintering 30min under the He gas shiled obtains the air positive pole.
Embodiment 3:
With Al
2O
3, Li
2O, GeO
2, P
2O
5Press the mixed in molar ratio of 1:3.5:6.5:6.5,1200 ℃ of fusings down, abrasive dust at 800 ℃ of following sintering 2h, obtains powders A.The PPOX of the powders A of the acetylene black of 50wt%, 45wt% and 5% is mixed in the water (consumption of water be acetylene black, powders A, PPOX three quality and 3 times), stir, be applied to the two sides of nickel screen; And nickel screen is clipped between two 1mm corrosion resistant plates; Flatten, dry 8h under 100 ℃ is at 250 ℃; Sintering 25min under the Ar gas shiled obtains the air positive pole.
Air with embodiment 1 is just very anodal, is negative pole with the metallic lithium foil, and barrier film adopts microporous barrier, and electrolyte adopts 1 mol/L LiPF
6/ EC: DEC: EMC=3:3:4 (volume ratio) solution is formed battery.
Concrete battery structure is seen Fig. 1.This battery has anode coat 4 (plastic housing), and the aluminium foil 5 that on the inside bottom surface of anode coat 4 (plastic housing), is provided with is connected with cathode conductor 2 (1mm diameter steel bar) as negative current collector; The metallic lithium foil 6 of on aluminium foil 5, fitting is as negative electrode layer; , and be connected as positive electrode layer by air electrode 9 with positive wire 1 (1mm diameter copper bar); Setting battery barrier film 8 between negative electrode layer and positive electrode layer (model: celgard, specification: 20 μ m), and inject electrolyte 7; This battery also comprises the anodal shell 3 (steel casing) that is arranged on outside the anode coat 4, and the top of battery is provided with waterproof ventilated membrane 10 (Donaldson Company, Inc produces, and this film adheres to steel casing mutually); 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 with air just very the battery of part have good cycle charge discharge performance.
Claims (10)
1. the positive electrode of a lithium-air battery, it is characterized in that: it comprises that mol ratio is 1: (2.5-3.5): (5.5-6.5): Al (5.5-6.5)
2O
3, Li
2O, GeO
2, P
2O
5Mixture.
2. the positive electrode of a kind of lithium-air battery according to claim 1 is characterized in that: also comprise acetylene black, polymeric media.
3. the positive electrode of a kind of lithium-air battery according to claim 1 and 2; It is characterized in that: in mixture, acetylene black, polymeric media three quality be 100%; Mixture quality percentage is 50-75%, and acetylene black is 25-50%, and surplus is a polymeric media.
4. the positive electrode of a kind of lithium-air battery according to claim 2 is characterized in that: described polymeric media is a kind of in PEO, PPOX, polytetrafluoroethylene, polymethylacrylic acid, polyacrylamide, Merlon, the polysulfones.
5. the anodal preparation method of an air is characterized in that: may further comprise the steps:
1) with the described mixture melt of claim 1, abrasive dust, sintering, obtains powders A;
2) acetylene black of 25-50wt%, powders A and the described polymeric media of claim 4 of 50-75wt% are mixed in the water, stir, be applied to the two sides of Ni-based material; And Ni-based material is clipped between two corrosion resistant plates, flatten drying; Sintering under the protective atmosphere obtains the air positive pole.
6. the anodal preparation method of a kind of air according to claim 5, it is characterized in that: in the step 1), described fusion temperature is 1200-1400 ℃.
7. the anodal preparation method of a kind of air according to claim 5, it is characterized in that: in the step 1), the temperature of sintering is 800-1000 ℃.
8. the anodal preparation method of a kind of air according to claim 5, it is characterized in that: in the step 1), the time of sintering is 1-2h.
9. the preparation method that a kind of air according to claim 5 is anodal is characterized in that: step 2) in, described protective atmosphere is a kind of among He, Ne, the Ar.
10. the anodal preparation method of a kind of air according to claim 5 is characterized in that: step 2) in, described sintering temperature is 200-300 ℃, described sintering time is 20-30min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101100296A CN102637863A (en) | 2012-04-16 | 2012-04-16 | Positive electrode material of lithium air battery and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101100296A CN102637863A (en) | 2012-04-16 | 2012-04-16 | Positive electrode material of lithium air battery and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111244427A (en) * | 2020-01-21 | 2020-06-05 | 浙江理工大学 | Inorganic GeO applied to lithium metal battery2-Li composite negative electrode and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006286414A (en) * | 2005-03-31 | 2006-10-19 | Toshiba Corp | Nonaqueous electrolyte air cell |
| CN102210042A (en) * | 2008-09-08 | 2011-10-05 | 新加坡南洋理工大学 | Electrode materials for metal-air batteries, fuel cells and supercapacitors |
-
2012
- 2012-04-16 CN CN2012101100296A patent/CN102637863A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006286414A (en) * | 2005-03-31 | 2006-10-19 | Toshiba Corp | Nonaqueous electrolyte air cell |
| CN102210042A (en) * | 2008-09-08 | 2011-10-05 | 新加坡南洋理工大学 | Electrode materials for metal-air batteries, fuel cells and supercapacitors |
Non-Patent Citations (2)
| Title |
|---|
| 《Journal of The Electrochemical Society》 20091113 Binod Kumar 等 "A Solid-State, Rechargeable, Long Cycle Life Lithium-Air Battery" 第157卷, 第1期 * |
| BINOD KUMAR 等: ""A Solid-State, Rechargeable, Long Cycle Life Lithium–Air Battery"", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111244427A (en) * | 2020-01-21 | 2020-06-05 | 浙江理工大学 | Inorganic GeO applied to lithium metal battery2-Li composite negative electrode and preparation method thereof |
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Application publication date: 20120815 |