CN108232295A - A kind of lithium-air battery ionic liquid base electrolyte and its lithium-air battery system - Google Patents
A kind of lithium-air battery ionic liquid base electrolyte and its lithium-air battery system Download PDFInfo
- Publication number
- CN108232295A CN108232295A CN201711395689.2A CN201711395689A CN108232295A CN 108232295 A CN108232295 A CN 108232295A CN 201711395689 A CN201711395689 A CN 201711395689A CN 108232295 A CN108232295 A CN 108232295A
- Authority
- CN
- China
- Prior art keywords
- lithium
- ionic liquid
- air battery
- electrolyte
- liquid base
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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 present invention provides a kind of lithium-air battery ionic liquid base electrolyte and the lithium-air battery system being made from it, wherein ionic liquid base electrolyte includes pyrrole ionic liquid, lithium salts, organic cosolvent and a certain amount of lithium nitrate, and thus the air cathode of the lithium-air battery of electrolyte composition is carbon nanotube In-situ reaction birnessite manganese dioxide.This kind of ionic liquid base electrolyte is to O2Reduction-state substance has excellent electrochemistry and chemical stability, and stable SEI films can be formed in the negative terminal surface containing lithium metal.The lithium-air battery system formed with carbon nanotube In-situ reaction birnessite manganese dioxide air cathode, play the advantage of the embedded growth of discharging product, reversible reaction activity improves, and it is obviously improved with stable gas-liquid-solid reaction interface and more product storage places, the cycle life and high rate performance of lithium-air battery system.
Description
Technical field
The invention belongs to technical field of chemical power, more particularly to a kind of lithium-air battery with ionic liquid base electrolyte with
And the lithium-air battery system being made from it.
Background technology
Anode is directly using the oxygen in air in lithium-air battery, have it is high it is theoretical than energy (3623Wh/kg,
By product Li2O2Calculate), far above the ratio energy of lithium ion battery, while there is advantages of environment protection.But lithium air is electric
Also there are problems for the practical application in pond.Electrolyte system is the important component of lithium-air battery, especially special at its
Chemical work environment under, electrolyte system, which becomes, ensures that lithium-air battery realizes high-energy conversion efficiency and long service live
Basis and key.It is organic liquid electrolytes system (esters, ether to be studied in the electrolyte system of lithium-air battery at present wider
Class, sulfone class etc.), it is notable that organic liquid electrolyte is volatile and O2The stability of reduction-state substance superoxide ion
Difference, leads to that battery polarization is serious, capacity declines rapidly, poor circulation.Part lithium-air battery also continue to use propene carbonate,
The electrolyte system of the lithium ion batteries such as ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, but shown by transmitted electron
Micro mirror, FTIR spectrum method and Raman spectroscopy find that main discharging product is carbonate, it was demonstrated that these electrolyte exist
Severe decomposition has occurred in lithium-air battery.The application of ethers electrolyte plays low-viscosity and improves oxygen diffusion rate, together
When high-k can enhance dissolving lithium salts ability.But Fruenberger et al. has studied n- polyvinylethers in lithium sky
Stability in pneumoelectric pond finds that its hydroperoxyl radical in discharge process in CH2 groups is reacted with superoxide radical anion,
Electrolyte is degraded.DMSO was applied in lithium-air battery by Xu et al. in 2012 for the first time, DMSO bases lithium-air battery tool
There is the advantages of high-discharge-rate, high specific discharge capacity and low charging voltage.But research shows that in the presence of having superoxide anion
DMSO is oxidized to DMSO2, therefore the cyclical stability of the lithium-air battery of application DMSO electrolyte is poor.As it can be seen that electrolyte
System develops into the key that lithium-air battery technological progress is promoted to regenerate with innovation.
With conventional organic solution liquid phase ratio, ionic liquid has low volatility, good hydrophobicity, electric conductivity, heat surely
Qualitative and wider electrochemical window, and it is good to the stability of superoxide ion, it is empty that current lithium can be solved to a certain extent
Pneumoelectric pond there are the problem of.But viscosity of il is big, limits the solubility of oxygen and the diffusion of superoxides, so as to limit
High rate performance is made.Moreover, solubility of the lithium salts in number of types of ionic liquid is relatively low, at the same with the table of lithium anode
Face compatibility is poor, and therefore, ionic liquid base electrolyte has the advantage and potentiality of research and development, while urgently technical prominent
Application problem broken, solution ionic liquid is in lithium-air battery, so as to as the ideal electrolyte system of lithium-air battery.
In addition, carbon material is common positive electrode in non-water system lithium-air battery.But recent studies have indicated that filling
The stability of carbon-based anode is by larger threat in discharge process.Ottakam et al. has found carbon material in below 3.5V charge and discharge
When relatively stablize, but when voltage be more than 3.5V when, can in cyclic process with Li2O2It reacts, promotes point of electrolyte
Solution generates LiCO3Or the carboxylate of lithium, cause the rapidly deterioration of cycle performance of battery.
Invention content
The object of the present invention is to provide a kind of electrolysis being made of lithium salts, ionic liquid, organic cosolvent and lithium nitrate
Liquid overcomes poor, the low lithium salts solubility of ionic liquid high viscosity, electrode wettability etc. empty in lithium while playing ionic liquid advantage
In pneumoelectric pond apply there are the problem of, lithium-air battery ionic liquid base electrolyte system is made to have high conductivity, high anti-oxidation
Property, high stability, excellent hydrophobicity.And propose the lithium-air battery system for including this ionic liquid base electrolyte, make lithium
Air cell system has high circulation service life and excellent high rate performance.
The lithium-air battery ionic liquid base electrolyte at least consisting of of the present invention：
Pyrrole ionic liquid, lithium salts, organic cosolvent and lithium nitrate.Wherein pyrrole ionic liquid have it is following sun from
Minor structure (1)：
R1 and R2 is mutual indepedent in general formula structure (1), and R1 and R2 is selected from the aliphatic group and carbon that carbon atom number is 1-4
Atomicity is the ether of 2-5.The anion of pyrrole ionic liquid is selected from at least one of following substance：BF4 -、PF6 -、
CF3SO3 -、(CF3SO2)3C-、(CF3SO2)2N-。
Wherein, pyrrole ionic liquid and the volume ratio of organic cosolvent are X：1-X, 0<X<1.Organic cosolvent is following
At least one of substance：Dimethyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether or tetraethylene glycol two
Methyl ether, dimethyl sulfoxide, sulfolane, diphenyl sulfoxide or thionyl chloride.
The molar concentration of the lithium salts in the electrolytic solution is 0.5-1.5mol/L.Wherein, lithium salts in following substance extremely
Few one kind：LiPF6、LiClO4、LiBF4、LiAsF6、LiAlCl4、LiCF3SO3、LiN(SO2CF3)2、LiBOB、LIODFB。
The molar concentration of the lithium nitrate in the electrolytic solution is 0.1-1mol/L.
A kind of lithium-air battery system, specifically includes：The above-described ionic liquid base electrolyte of the present invention, and by metal
Lithium contains the material of lithium metal as cathode, and carbon nanotube In-situ reaction birnessite manganese dioxide is as anode.
The present invention has the following advantages：
The ionic liquid base electrolyte system of the present invention, overcomes the single electrolyte system such as ionic liquid and organic solvent
The shortcomings that, play that ionic liquid high chemical stability, stable, high ionic conductivity and high hydrophobicity etc. are excellent to superoxide radical
Point；And the advantages that organic solvent low viscosity, high oxygen solubility, high lithium salts dissolution rate.
First, the pyrrole ionic liquid volatility in the present invention is small, its viscosity compared with other kinds of ionic liquid
Relatively low, chemical and electrochemical stability is good.Second, the introducing of lithium nitrate promotes il electrolyte and bearing containing lithium metal
The interface of pole forms stable SEI films, is effectively protected cathode, reduces interface impedance.Third, pyrrole ionic liquid,
Organic liquid cosolvent and lithium nitrate, lithium salts composition ionic liquid base electrolyte played the synergistic effect of each component, by than
Example, which has collectively constituted, not only has high chemical stability, but also the system with high electrochemical stability, not only in anode/electrolyte circle
Face is stabilized, and stable passivating film is formed at the interface of lithium anode/electrolyte, the performance ratio ionic liquid of electrolyte
It is obviously improved with the performance of organic liquid electrolyte.4th, proposing carbon nanotube In-situ reaction birnessite manganese dioxide just
Pole and the ionic liquid base electrolyte system of the present invention match, and form a lithium-air battery system, efficiently solve charging
The decomposition of carbon-based anode in the process, and increase the catalytic activity of positive electrode.It is just great with reference to birnessite manganese dioxide
There are the feature of layer structure and larger interlamellar spacing, the embedded growth of discharging product, and the wellability between electrolyte is moderate,
It constructs and stablizes effective solid-liquid-gas three-phase reaction interface and more places for accommodating discharging product, be obviously improved lithium sky
The cycle performance and high rate performance in pneumoelectric pond.
Description of the drawings
The il electrolyte that Fig. 1 is ionic liquid base electrolyte system prepared by embodiment 1 and prepared by comparative example 1
Shear viscosity-shear rate change curve.
Fig. 2 is Li//electrolyte //Li battery AC impedances that the assembling of il electrolyte system is prepared with embodiment 2
It changes with time.
Fig. 3 is Li//electrolyte //Li battery AC impedances of traditional organic liquid electrolyte assembling prepared by comparative example 2
It changes with time.
Fig. 4 is that lithium-air battery system prepared by embodiment 3 is electric with recycling when charging and discharging currents density is 100mA/g
The discharge capacity in pond keeps figure.(test condition：Discharge capacity is limited to 1000mAh/g, voltage range 2.0-4.5V).
Fig. 5 is that charge and discharge of the lithium-air battery system of the preparation of comparative example 3 when charging and discharging currents density is 100mA/g follow
Ring figure.(test condition：Discharge capacity is limited to 1000mAh/g, voltage range 2.0-4.5V).
Fig. 6 is that charge and discharge of the lithium-air battery system of the preparation of embodiment 4 when charging and discharging currents density is 200mA/g follow
Ring figure.(test condition：Discharge capacity is limited to 1000mAh/g, voltage range 2.0-4.5V).
Fig. 7 is the circulation figure of the lithium-air battery of ionic liquid base electrolyte assembling prepared by embodiment 5.(test
Condition：Discharge capacity is limited to 1000mAh/g, voltage range 2.0-4.5V).
Specific embodiment
Embodiment 1
2.4mL N- Methyl-N-propyl pyrroles's bis trifluoromethyl sulfimide salts (PYR is measured respectively1(1o2)TFSI) and
3.6mL dimethyl sulfoxide (DMSO)s (DMSO), volume ratio 0.4:0.6 (wherein x=0.4), the two mixing, adds in 0.9115g hexafluoro phosphorus
Sour lithium LiPF6(1mol/L), adds 0.0827g lithium nitrates (0.2mol/L), and magnetic agitation obtains the mixing of ionic liquid base for 24 hours
Electrolyte.Above-mentioned steps operate in the glove box of water content and oxygen content less than 0.5ppm.Wherein, ionic liquid cation
PYR1(1o2) +Structural formula be：
(wherein R1 is CH2CH2OCH3, R2 CH3),
Moreover, the anion of ionic liquid is (CF3SO2)2N-, it is abbreviated as TFSI-。
Fig. 1 is the shear viscosity of embodiment 1 with the change curve of shear rate.The shear viscosity of mixed electrolytic solution compared with
It is small, when shear rate is 100S-1When, the shear viscosity of ionic liquid base electrolyte is 6.328mPas.
Comparative example 1
By the lithium hexafluoro phosphate LiPF of 0.9115g6(1mol/L) is dissolved in the double trifluoros of N- Methyl-N-propyls pyrroles of 6mL
Sulfonyloxy methyl inferior amine salt (PYR13TFSI in), magnetic agitation obtains pure il electrolyte for 24 hours.Above-mentioned steps are in water content
It is operated in glove box of the oxygen content less than 0.5ppm.It will be seen from figure 1 that when shear rate is 100S-1When, pure ionic liquid
The shear viscosity of electrolyte is 176.7mPas, is approximately 28 times of 1 electrolyte of embodiment.
Embodiment 2
1.8mL N- methyl-N- butyl pyrroles's fluoroform sulphonates (PYR is measured respectively14CF3SO3) and 4.2mL tetrems two
Diethylene glycol dimethyl ether (TEGDME), volume ratio 0.3:0.7 (wherein x=0.3), the two mixing, by 1.3781g bis trifluoromethyl sulphonyl
Imine lithium LiTFSI (0.8mol/L) dissolves wherein, adds 0.2069g lithium nitrates LiNO3(0.5mol/L) is to mixed solvent
In, magnetic agitation for 24 hours, obtains ionic liquid base mixed electrolytic solution.Above-mentioned steps are less than 0.5ppm in water content and oxygen content
Glove box in operate.Wherein, ionic liquid cation PYR14 +Structural formula be：
(wherein, R1 CH2CH2CH2CH3, R2 CH3),
Moreover, the anion of ionic liquid is CF3SO3 -。
Fig. 2 is Li//electrolyte //Li batteries that electrolyte and metal lithium sheet prepared by embodiment 2 is assembled into, test with
The AC impedance variation of time battery.Interface impedance of the ionic liquid base electrolyte between lithium metal is smaller, and with when
Between transforming impedance increase it is also smaller, illustrate to contact stabilization between electrolyte and lithium anode.
Comparative example 2
1.7226g bis trifluoromethyl sulfimide lithium LiTFSI (1mol/L) are dissolved in 6mL organic solvents ethylene glycol two
In methyl ether (DME), magnetic agitation obtains organic liquid electrolyte for 24 hours.Above-mentioned steps are less than in water content and oxygen content
It is operated in the glove box of 0.5ppm.Fig. 4 is the interfacial contact impedance between electrolyte and lithium metal prepared by comparative example 1.With reality
It applies example 2 to compare, the interface between electrolyte and lithium metal is larger, and with the increase of standing time, and impedance increased dramatically, most
Reach 3200 Ω eventually.It is poor with the direct interface stability of lithium anode when comparative example 2 is applied in lithium-air battery, gold
Belong to the dusting of lithium, directly affect the cycle life of battery.And the ionic liquid mixed electrolytic solution used in this patent, with cathode of lithium
Between form one layer of stable SEI film so that contact interface stablize, protect cathode of lithium.
Embodiment 3
1.2mL N- methyl-N- butyl pyrroles's fluoroform sulphonates (PYR is measured respectively13CF3SO3) and 4.8mL sulfolane
(SL), volume ratio 0.2:0.8 (wherein x=0.2), the two mixing, by 0.9361g trifluoromethanesulfonic acid lithiums LiCF3SO3(1mol/
L it) is dissolved in mixed liquor, adds 0.2482g lithium nitrates LiNO3In (0.6mol/L) to mixed liquor, magnetic agitation for 24 hours, obtains
To ionic liquid base electrolyte.Above-mentioned steps operate in the glove box of water content and oxygen content less than 0.5ppm.Wherein, from
Sub- liquid cation PYR13 +Structural formula be：
(wherein, R1 CH2CH2CH3, R2 CH3),
Moreover, the anion of ionic liquid is CF3SO3 -。
Lithium-air battery is assembled, while positive electrode is carbon nanotube In-situ reaction using more than ionic liquid base electrolyte
Birnessite manganese dioxide, cathode use lithium metal.Fig. 4 is the CR2032 button lithium-air batteries for assembling embodiment 3
Charge and discharge cycles figure.Charge-discharge mechanism is set as：Discharge capacity is limited to 1000mAh/gcarbon, charging/discharging voltage is ranging from
2.0-4.5V charging and discharging currents density is 100mA/g.Battery stabilization has recycled 138 circles, still charge/discharge capacity is kept to be maintained at
100%, and the charge and discharge overpotential of battery is relatively low, and the cycle life of battery is obviously improved.
Comparative example 3
1.7226g bis trifluoromethyl sulfimide lithium LiTFSI (1mol/L) are dissolved in 6mL organic solvents dimethyl Asia
In sulfone (DMSO), magnetic agitation obtains sulfuryl organic liquid electrolyte for 24 hours.Above-mentioned steps are less than in water content and oxygen content
It is operated in the glove box of 0.5ppm.
Organic liquid electrolyte assembling lithium-air battery more than, while positive electrode is multi-walled carbon nanotube, is born
Pole uses lithium metal.Fig. 5 is the charge and discharge cycles figure of CR2032 button lithium-air batteries for assembling comparative example 3.Charge-discharge machine
It sets up and is set to：Discharge capacity is limited to 1000mAh/gcarbon, charging/discharging voltage ranging from 2.0-4.5V, charging and discharging currents density
For 100mA/g.
From test result as can be seen that using sulfuryl organic liquid electrolyte, the charge and discharge overpotential in battery first week is
1.48V, the discharge voltage of the second circle electric discharge latter stage battery further decline, and the discharge capacity of battery is also begun to down from third circle
Drop, polarization are more serious.Organic electrolyte is poor to the stability of superoxide ion, is easily decomposed in battery charge and discharge process, and
And organic liquid water imbibition is strong, corrodes cathode of lithium, causes interface impedance big, the poor circulation of battery.Comparison is found, of the invention
In ionic liquid base electrolyte system, significantly improve the cycle performance of lithium-air battery.
Embodiment 4
1.2mL N- methyl-N- butyl pyrroles's bis trifluoromethyl sulfimide salts (PYR is measured respectively14) and 4.8mL TFSI
Dimethyl sulfoxide (DMSO) (DMSO), volume ratio 0.2:0.8 (wherein x=0.2), the two mixing, by 1.3781g bis trifluoromethyl sulphonyl
Imine lithium LiTFSI (0.8mol/L) is dissolved in mixed liquor, adds 0.2069g lithium nitrates LiNO3(0.5mol/L) is to mixing
In liquid, magnetic agitation for 24 hours, obtains ionic liquid base mixed electrolytic solution.Above-mentioned steps are less than in water content and oxygen content
It is operated in the glove box of 0.5ppm.Wherein, ionic liquid cation PYR14 +Structural formula be：
(wherein, R1 CH2CH2CH2CH3, R2 CH3)
Lithium-air battery is assembled, while positive electrode is carbon nanotube In-situ reaction using more than ionic liquid base electrolyte
Birnessite manganese dioxide, cathode use lithium metal.
Fig. 6 is the charge and discharge cycles figure for the CR2032 button lithium-air batteries that embodiment 4 assembles.Charge-discharge mechanism is set
For：Discharge capacity is limited to 1000mAh/gcarbon, charging/discharging voltage ranging from 2.0-4.5V, charging and discharging currents density is
200mA/g.As can be seen that under larger multiplying power 0.2C, battery, which is still stablized, has recycled 78 circles, and first circle charge and discharge overpotential is only
1.14V, hence it is evident that better than cycle performance of the lithium-air battery in 100mA/g charging and discharging currents density of comparative example 3, and charge and discharge
Electric overpotential also substantially reduces.
Embodiment 5
1.8mL N- Methyl-N-propyl pyrroles's bis trifluoromethyl sulfimide salts (PYR is measured respectively13) and 4.2mL TFSI
Dimethyl sulfoxide (DMSO) (DMSO), volume ratio 0.3:0.7 (wherein x=0.3), the two mixing, by 1.7226g bis trifluoromethyl sulphonyl
Imine lithium LiTFSI (1mol/L) is dissolved in mixed liquor, adds 0.2069g lithium nitrates LiNO3(0.5mol/L) is to mixed liquor
In, magnetic agitation for 24 hours, obtains ionic liquid base mixed electrolytic solution.Above-mentioned steps are less than 0.5ppm in water content and oxygen content
Glove box in operate.Wherein, ionic liquid cation PYR13 +Structural formula be：
(wherein, R1 CH2CH2CH3, R2 CH3),
Lithium-air battery is assembled, while positive electrode is carbon nanotube In-situ reaction using more than ionic liquid base electrolyte
Birnessite manganese dioxide, cathode use lithium metal.
Fig. 7 is charge and discharge cycles figure of the CR2032 buttons lithium-air battery of the assembling of embodiment 5 under different discharge-rates.
Charge-discharge mechanism is set as：Discharge capacity is limited to 1000mAh/gcarbon, charging/discharging voltage ranging from 2.0-4.5V exists respectively
Charge-discharge magnification is respectively to recycle 6 circles under 0.1C, 0.2C, 0.5C, 1C, 2C and 5C, continues cycling through 6 under the multiplying power of 0.1C later
Circle.From experiment as can be seen that the lithium-air battery system of the present invention shows excellent high rate performance.It is prepared using the present invention
Ionic liquid base mixed electrolytic solution system and the lithium-air battery of multi-walled carbon nanotube dioxide composite manganese material assembling are starting
Charge and discharge process in, electrolyte forms one layer of stable SEI film on cathode of lithium surface.And positive electrode has Gao Bibiao
Area and pore volume, high catalytic performance so that anode can accommodate more discharging products and oxygen transmission in discharge process
Channel, high catalytic performance contribute to product Li in charging process2O2Decomposition.Significantly improve the cyclicity of lithium-air battery
Energy and high rate performance.
Claims (5)
1. a kind of lithium-air battery ionic liquid base electrolyte, it is characterised in that：At least consisting of：Pyroles ionic liquid
Body, lithium salts, organic cosolvent and lithium nitrate, wherein pyrrole ionic liquid contain cationic structural (1)：
R1 and R2 is mutual indepedent in its general structure (1), and R1 and R2 is selected from the aliphatic group and carbon that carbon atom number is 1-4
Atomicity is the ether of 2-5, and the anion of pyrrole ionic liquid is selected from at least one of following substance：BF4 -、PF6 -、
CF3SO3 -、(CF3SO2)3C-、(CF3SO2)2N-。
2. lithium-air battery according to claim 1 ionic liquid base electrolyte, it is characterised in that：The pyroles from
The volume ratio of sub- liquid and organic cosolvent is X：1-X, 0<X<1, wherein organic cosolvent is at least one of following substance：
Dimethyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether, dimethyl sulfoxide, ring
Fourth sulfone, diphenyl sulfoxide or thionyl chloride.
3. lithium-air battery according to claim 1 ionic liquid base electrolyte, it is characterised in that：The lithium salts is in electricity
It is 0.5-1.5mol/L to solve the molar concentration in liquid, and wherein lithium salts is at least one of following substance：LiPF6、LiClO4、
LiBF4、LiAsF6、LiAlCl4、LiCF3SO3、LiN(SO2CF3)2、LiBOB、LIODFB。
4. lithium-air battery according to claim 1 ionic liquid base electrolyte, it is characterised in that：The lithium nitrate exists
Molar concentration in electrolyte is 0.1-1mol/L.
5. a kind of lithium-air battery system, the lithium-air battery system includes anode, electrolyte and cathode, it is characterised in that：
Lithium-air battery ionic liquid base electrolyte described in claim 1-4 is used, by lithium metal or material containing lithium metal
Material is as cathode, and carbon nanotube In-situ reaction birnessite manganese dioxide material is as anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711395689.2A CN108232295B (en) | 2017-12-21 | 2017-12-21 | Ionic liquid-based electrolyte for lithium-air battery and lithium-air battery system thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711395689.2A CN108232295B (en) | 2017-12-21 | 2017-12-21 | Ionic liquid-based electrolyte for lithium-air battery and lithium-air battery system thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108232295A true CN108232295A (en) | 2018-06-29 |
| CN108232295B CN108232295B (en) | 2020-11-17 |
Family
ID=62648358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711395689.2A Active CN108232295B (en) | 2017-12-21 | 2017-12-21 | Ionic liquid-based electrolyte for lithium-air battery and lithium-air battery system thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108232295B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101916869A (en) * | 2010-08-16 | 2010-12-15 | 广州市鹏辉电池有限公司 | Lithium nitrate non-aqueous solvent electrolyte, preparation method and lithium/iron disulfide battery thereof |
| US20120141889A1 (en) * | 2010-12-07 | 2012-06-07 | National University Corporation Mie | Lithium air battery |
| CN103069626A (en) * | 2010-08-17 | 2013-04-24 | 丰田自动车株式会社 | Liquid air electrode for metal-air battery and metal-air battery provided with same |
| CN103208668A (en) * | 2013-04-08 | 2013-07-17 | 中国科学院长春应用化学研究所 | Sulfone electrolyte for lithium-air battery |
| CN103250297A (en) * | 2010-10-12 | 2013-08-14 | 丰田自动车株式会社 | Ionic liquid, lithium secondary battery electrolyte comprising ionic liquid, and lithium secondary battery comprising electrolyte |
| CN103996892A (en) * | 2014-06-17 | 2014-08-20 | 常州盈华高科储能材料科技有限公司 | Ether electrolyte and lithium air battery |
| CN103996891A (en) * | 2013-02-19 | 2014-08-20 | 中国科学院宁波材料技术与工程研究所 | Lithium-air cell electrolyte solution system |
| CN105161759A (en) * | 2015-08-21 | 2015-12-16 | 北京科技大学 | Composite electrolyte of lithium-air battery and preparation method of composite electrolyte |
| CN107004908A (en) * | 2014-10-10 | 2017-08-01 | 株式会社半导体能源研究所 | Electrical storage device and electronic equipment |
| CN107039680A (en) * | 2016-02-03 | 2017-08-11 | 三星电子株式会社 | Solid electrolyte and the lithium battery for including the solid electrolyte |
| CN107112592A (en) * | 2014-12-22 | 2017-08-29 | 日清纺控股株式会社 | Secondary cell electrolyte and secondary cell |
-
2017
- 2017-12-21 CN CN201711395689.2A patent/CN108232295B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101916869A (en) * | 2010-08-16 | 2010-12-15 | 广州市鹏辉电池有限公司 | Lithium nitrate non-aqueous solvent electrolyte, preparation method and lithium/iron disulfide battery thereof |
| CN103069626A (en) * | 2010-08-17 | 2013-04-24 | 丰田自动车株式会社 | Liquid air electrode for metal-air battery and metal-air battery provided with same |
| CN103250297A (en) * | 2010-10-12 | 2013-08-14 | 丰田自动车株式会社 | Ionic liquid, lithium secondary battery electrolyte comprising ionic liquid, and lithium secondary battery comprising electrolyte |
| US20120141889A1 (en) * | 2010-12-07 | 2012-06-07 | National University Corporation Mie | Lithium air battery |
| CN103996891A (en) * | 2013-02-19 | 2014-08-20 | 中国科学院宁波材料技术与工程研究所 | Lithium-air cell electrolyte solution system |
| CN103208668A (en) * | 2013-04-08 | 2013-07-17 | 中国科学院长春应用化学研究所 | Sulfone electrolyte for lithium-air battery |
| CN103996892A (en) * | 2014-06-17 | 2014-08-20 | 常州盈华高科储能材料科技有限公司 | Ether electrolyte and lithium air battery |
| CN107004908A (en) * | 2014-10-10 | 2017-08-01 | 株式会社半导体能源研究所 | Electrical storage device and electronic equipment |
| CN107112592A (en) * | 2014-12-22 | 2017-08-29 | 日清纺控股株式会社 | Secondary cell electrolyte and secondary cell |
| CN105161759A (en) * | 2015-08-21 | 2015-12-16 | 北京科技大学 | Composite electrolyte of lithium-air battery and preparation method of composite electrolyte |
| CN107039680A (en) * | 2016-02-03 | 2017-08-11 | 三星电子株式会社 | Solid electrolyte and the lithium battery for including the solid electrolyte |
Non-Patent Citations (1)
| Title |
|---|
| 张治安等: "锂空气电池用碳纳米管/钴锰氧化物复合电极材料的制备及电化学性能", 《无机材料学报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108232295B (en) | 2020-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101373849B (en) | Electrolytes, cells and methods of forming passivation layers | |
| CN110911752A (en) | Low-internal-resistance lithium secondary battery electrolyte and lithium secondary battery | |
| CN105552430A (en) | Electrolyte and lithium ion battery | |
| CN106797051A (en) | For the solution of the prelithiation of lithium-ions battery | |
| CN104022310B (en) | Lithium rechargeable battery and the lithium ion battery containing this electrolyte | |
| CN107293792A (en) | A kind of nonaqueous electrolytic solution and nickelic tertiary cathode material battery | |
| CN105870501B (en) | A kind of high voltage functionality electrolyte and preparation method and application | |
| CN104659416B (en) | A kind of electrolyte and preparation method thereof, lithium rechargeable battery | |
| CN109088099A (en) | A kind of sulphonyl class electrolysis additive for taking into account high temperature performance and the electrolyte containing the additive | |
| KR20070085575A (en) | Electrolyte for lithium-sulphur batteries and lithium-sulphur batteries using the same | |
| CN1333933A (en) | Non-aqueous electrolytes for electrochemical cells | |
| CN102760906B (en) | Electrolyte additive, electrolyte comprising additive and lithium ion battery | |
| CN107230800A (en) | Electrolyte for lithium ion battery and lithium ion battery | |
| CN107293793A (en) | Electrolyte and electrochemical cell | |
| CN106486696A (en) | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery | |
| CN105140558A (en) | High-pressure electrolyte of lithium ion battery and preparation method thereof | |
| CN106684447A (en) | 5V high-voltage electrolyte for lithium ion battery | |
| CN110400968A (en) | A kind of nonaqueous electrolytic solution, the power battery containing the nonaqueous electrolytic solution and the vehicle containing the power battery | |
| CN107799823A (en) | A kind of electrolysis additive and electrolyte and lithium secondary battery containing the additive | |
| CN108270034A (en) | A kind of lithium-ion battery electrolytes | |
| CN108258317A (en) | A kind of lithium-sulfur cell | |
| CN109524716A (en) | Electrolyte and preparation method thereof with include its secondary cell and electrical equipment | |
| CN105789701A (en) | Electrolyte and lithium ion battery comprising same | |
| CN106450449A (en) | Electrolyte for over 4.2V high-voltage system battery | |
| CN109273765A (en) | A kind of battery electrolyte, preparation method and the silicium cathode battery containing the electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |