CN104810574A - Air battery - Google Patents
Air battery Download PDFInfo
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- CN104810574A CN104810574A CN201510249641.5A CN201510249641A CN104810574A CN 104810574 A CN104810574 A CN 104810574A CN 201510249641 A CN201510249641 A CN 201510249641A CN 104810574 A CN104810574 A CN 104810574A
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- China
- Prior art keywords
- nonaqueous electrolyte
- ion
- solid electrolyte
- electrolyte layer
- lithium
- Prior art date
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-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
-
- 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 invention provides an air battery in an implementation mode. The air battery comprises a container, a positive electrode, a negative electrode, a first nonaqueous electrolyte, a second nonaqueous electrolyte, a solid electrolyte layer and a hole, wherein the positive electrode is accommodated in the container, the negative electrode is accommodated in the container, the first nonaqueous electrolyte is maintained in the positive electrode and contains ion liquid, the second nonaqueous electrolyte is maintained in the negative electrode and contains organic solvents, the solid electrolyte layer is configured between the positive electrode and the negative electrode and has the lithium ion conductivity, and the hole is formed in the container and is used for supplying oxygen to the positive electrode.
Description
The divisional application that the application is the applying date is on June 25th, 2010, Chinese application number is the patent application of 201080037651.8.
Technical field
The present invention relates to air cell.
Background technology
In recent years, the market of the portable information device such as portable phone and e-mail terminal is expanding rapidly.Along with the development of the miniaturization and of these equipment, power supply also requires small-sized and light weight.Now, the lithium rechargeable battery using high-energy-density in these portable sets more, but requirement can obtain the battery of high power capacity further.
The air cell that oxygen in air is used as positive active material is not needed positive active material in the battery built-in, thus can expect high capacity.Lithium/oxygen organic electrolyte cell is described in non-patent literature 1.This lithium/oxygen organic electrolyte cell possesses containing MnO
2and the positive pole of carbon black, the negative pole be made up of lithium, configuration barrier film between a positive electrode and a negative electrode and containing the nonaqueous electrolyte be immersed in positive pole, negative pole and barrier film.
Patent documentation 1 proposes and use hydrophobic ionic liquid in the nonaqueous electrolyte of nonaqueous electrolyte air cell.Patent documentation 2 proposes applying solid electrolyte in the nonaqueous electrolyte of nonaqueous electrolyte air cell.
On the other hand, non-patent literature 2 is pointed out: according to the lithium-air battery adopting organic bath, at product and the Li of positive pole accumulation solid
2o, the pore of blocking positive pole, thus has the problem points that exoelectrical reaction stops.In order to avoid this problem points, the air cell of non-patent literature 2 proposes and configures solid electrolyte between a positive electrode and a negative electrode as barrier film, adopts organic bath, adopt water system electrolyte at side of the positive electrode in negative side.
Prior art document
Patent documentation
Patent documentation 1: Japan Patent No. 4015916 specification
Patent documentation 2: U.S. Patent Application Publication No. 2009/317724 specification
Non-patent literature
Non-patent literature 1:Journal of The Electrochemical Society, 149 (9) A1190-A1195 (July 29,2002)
Non-patent literature 2: industrial technology comprehensive study institute, " Port ス ト リ チ ウ system イ オ Application Electricity pond-novel リ チ ウ system empty mood Electricity Chi development ", on July 15th, 2009, AT International 2009Forum (sponsoring: Nikkei Automotive Technology and Nikkei Electronics, meeting-place: the attached hall of Pacific Ocean Heng Bang)
Summary of the invention
Invent problem to be solved
Excellent durability, chargeable and improve the air cell of large current density electrical characteristics is provided.
For the means of dealing with problems
The air cell of execution mode comprises:
Container;
Be accommodated in the positive pole in described container;
Be accommodated in the negative pole in described container;
To remain in described positive pole and the 1st nonaqueous electrolyte containing ionic liquid;
To remain in described negative pole and the 2nd nonaqueous electrolyte containing organic solvent;
To be configured between described positive pole and described negative pole and there is the solid electrolyte layer of lithium-ion-conducting; With
If the hole for supplying oxygen supply to described positive pole on the container.
Invention effect
Excellent durability, chargeable and improve the air cell of large current density electrical characteristics can be provided.
Embodiment
The problem points of patent documentation 1,2 and non-patent literature 1,2 is as follows.
As described in non-patent literature 1, only adopt the nonaqueous electrolyte containing organic solvent as nonaqueous electrolyte air cell in a state of use, namely under the open state importing the airport of oxygen to positive pole, the impact by ambient temperature and humidity is larger.Under the high temperature conditions, because organic solvent makes amount of electrolyte reduce from airport volatilization, result makes shorter battery life.In addition, under high humidity conditions, moisture immerses from airport, and make negative pole deterioration, result makes shorter battery life.
As described in patent document 1, which, when only adopting ionic liquid in nonaqueous electrolyte, ionic liquid because of with cathode contact and require that reducing resistance is excellent.As the ionic liquid that reducing resistance is excellent, there will be a known the ionic liquid with ammonium cation, but high with the ionic liquid phase specific viscosity with glyoxaline cation of reducing resistance difference.Therefore, when in nonaqueous electrolyte, only employing has the ionic liquid of ammonium cation, lithium-ion-conducting deterioration, thus heavy-current discharge characteristic reduces.
When only adopting the solid electrolyte described in patent documentation 2 as nonaqueous electrolyte, current value reduces.In nonaqueous electrolyte air cell, near the positive pole when discharging, need to produce continuously the reaction of oxygen to electrolytical dissolving and the lithium ion with electrode surface.When only adopting solid electrolyte as nonaqueous electrolyte, because oxygen can not obtain sufficient current value slowly to electrolytical dissolving.
The reaction equation during electric discharge of the air cell of non-patent literature 2 as described in chemical formula 1.
[chemical formula 1]
Positive pole 1/2O
2+ H
2o+2e
-→ 2OH
-
Negative pole 2Li → 2Li
++ 2e
-
Overall reaction 2Li+1/2O
2+ H
2o → 2LiOH ↓
By adopting water system electrolyte at side of the positive electrode, as described in chemical formula 1, when the electric discharge of positive pole, product is OH
-ion.Exoelectrical reaction is limited by capacity of negative plates and water volume, becomes and does not rely on positive pole.But consume the water in electrolyte when exoelectrical reaction at positive pole, carry out electrolyte minimizing along with exoelectrical reaction, thus electrolyte is easily exhausted, can not obtain the long-life.If increase amount of electrolyte to improve the life-span, then volume energy density reduces.In addition, if as non-patent literature 2 be shown in side of the positive electrode and adopt water system electrolyte, then can not carry out battery charging.This is because the lithium that moves to side of the positive electrode is separated out so that the form of lithium hydroxide is non-reversible in water system electrolyte when discharging.
In the air cell of execution mode, make the 1st nonaqueous electrolyte containing ionic liquid remain in positive pole, make the 2nd nonaqueous electrolyte containing organic solvent remain in negative pole simultaneously.Between a positive electrode and a negative electrode, configure the material containing having lithium-ion-conducting, and configure in the 1st nonaqueous electrolyte and the 2nd nonaqueous electrolyte and do not dissolve or non-swelling solid electrolyte layer.Because solid electrolyte layer does not dissolve in ion and organic solvent, therefore, it is possible to avoid generating in solid electrolyte layer the ionic liquid in the 1st nonaqueous electrolyte or the organic solvent in the 2nd nonaqueous electrolyte by through hole.Therefore, the 2nd nonaqueous electrolyte of negative side can not move to side of the positive electrode and from hole volatilization, in addition, the 1st nonaqueous electrolyte of side of the positive electrode also can not move and reduction decomposition to negative side.In addition, because solid electrolyte layer is not swelling in the 1st nonaqueous electrolyte and the 2nd nonaqueous electrolyte, thus following situation can be avoided: because ionic liquid and organic solvent invade in solid electrolyte layer, the concentration with the material of lithium-ion-conducting in solid electrolyte layer is reduced, and then lithium-ion-conducting reduces thereupon, result flash-over characteristic reduces.
Here, what is called has the material of lithium-ion-conducting, is can the material of movement by voltage difference or concentration gradient lithium ion.So-called solid electrolyte layer does not dissolve in the 1st nonaqueous electrolyte and the 2nd nonaqueous electrolyte, and be meant to when being immersed in by solid electrolyte layer in the 1st nonaqueous electrolyte or the 2nd nonaqueous electrolyte, the weight of solid electrolyte layer does not reduce.Specifically, by solid electrolyte layer being immersed in the 1st nonaqueous electrolyte or the 2nd nonaqueous electrolyte under low humidity inactive gas atmosphere, heat at 45 DEG C after 24 hours, clean with methyl ethyl carbonate, at room temperature after drying, the weight of described solid electrolyte layer is reduced to less than 3% to confirm.
In addition, so-called solid electrolyte layer is not swelling in the 1st nonaqueous electrolyte and the 2nd nonaqueous electrolyte, be meant to when making solid electrolyte layer be immersed in the 1st nonaqueous electrolyte or the 2nd nonaqueous electrolyte, the molecule forming the 1st nonaqueous electrolyte and the 2nd nonaqueous electrolyte does not enter in solid electrolyte layer.Specifically, be immersed in the 1st nonaqueous electrolyte or the 2nd nonaqueous electrolyte under low humidity inactive gas atmosphere by making solid electrolyte layer, place at 45 DEG C after 24 hours, clean with methyl ethyl carbonate, at room temperature after drying, confirm within the weight of described solid electrolyte layer increases to 3%.
The ionic liquid adopted in 1st nonaqueous electrolyte has fixedness, and it thus can be prevented from for volatilizing to the hole of positive pole for oxygen supply.In addition, negative pole can not be arrived because the 1st nonaqueous electrolyte is blocked by solid electrolyte layer, therefore can not pass through cathodic reduction decomposable ions liquid.
The organic solvent adopted in 2nd nonaqueous electrolyte is by selecting the excellent solvent of reducing resistance to suppress the reduction decomposition on negative pole.In addition, can not arrive positive pole because the 2nd nonaqueous electrolyte is blocked by solid electrolyte layer, therefore organic solvent can not volatilize from hole.
In addition, solid electrolyte layer, as previously mentioned because having imporosity, thus can prevent the mixing of the 1st nonaqueous electrolyte and the 2nd nonaqueous electrolyte, and because can not suppress the deterioration of the negative pole caused by moisture through water.
So, the 1st nonaqueous electrolyte not with cathode contact, lithium ion electrical conductance thus can be used excellent but the ionic liquid of reducing resistance difference, compared with when only adopting ionic liquid in nonaqueous electrolyte, the raising of large current density electrical characteristics.In addition, the 2nd nonaqueous electrolyte can not arrive hole, and therefore contained in the 2nd nonaqueous electrolyte organic solvent can not volatilize from hole, and compared with when only adopting organic solvent in nonaqueous electrolyte, durability improves.Consequently, the performance of both positive and negative polarity two electrode improves, and thus can improve the Li generated at positive pole
2the invertibity of O, can improve durability and large current density electrical characteristics.Thus, excellent durability, chargeable and improve the air cell of large current density electrical characteristics can be provided.
Below, the 1st nonaqueous electrolyte, the 2nd nonaqueous electrolyte, solid electrolyte layer, positive pole, negative pole and container are described.
1st nonaqueous electrolyte contains ionic liquid, therefore, it is possible to as required containing the supporting electrolyte be dissolved in ionic liquid.Ionic liquid has positively charged cation and electronegative anion, has fixedness.Therefore, by adopting ionic liquid in the 1st nonaqueous electrolyte, the volatile quantity that nonaqueous electrolyte volatilizees from hole can be reduced.
In addition, by selecting hydrophobic ionic liquid, moisture can be suppressed from the intrusion in hole.Therefore, by adopting hydrophobic ionic liquid, the life-span of air cell can be improved further.
The ionic liquid that can adapt to the reducing resistance of the negative pole of inferior current potential excellent mostly is high viscosity.On the other hand, the ionic liquid that viscosity is low has the tendency of reducing resistance deterioration, thus when requiring the vehicle-mounted power supply in more than 10 years life-spans for electric automobile, hybrid vehicle, plug-in hybrid-power automobile etc., if be mixed in negative pole, then have by the misgivings of slow reduction decomposition.According to the air cell of execution mode, the misgivings that ionic liquid is mixed in negative pole are few, thus can use the ionic liquid that viscosity is low.The ionic liquid that viscosity is low can improve the heavy-current discharge characteristic of air cell further.
As cation, such as, can list more than a kind that is selected among ammonium ion, imidazol ion, Phosphonium radical ion and the cation that obtains to importing substituting group in described each ion (ammonium ion, imidazol ion, Phosphonium radical ion).
Ammonium ion such as can have the structural formula represented by chemical formula 2.
[chemical formula 2]
R
1, R
2, R
3, R
4being be selected from the substituting group among alkyl, ester group, ether and itrile group, can be mutually identical substituting group, also can be not identical substituting group.The carbon number contained in preferred substituents is less than 8.Thus, the viscosity brought by the increase of the molecular weight of ionic liquid can be suppressed to rise, the lithium-ion-conducting of the 1st nonaqueous electrolyte can be improved.In substituting group, preferred alkyl and ether.Alkyl is compared with other substituting group, and intermolecular interaction is more weak, and the viscosity of ionic liquid thus can be made to reduce.As alkyl, alkyl, phenyl, benzyl etc. can be listed.Wherein, alkyl, because of molecular structure softness, can realize more low-viscosity ionic liquids, thus preferably.When adopting alkyl, ether, the preferred scope of carbon number is 1 ~ 4.In addition, preferred R
1, R
2, R
3, R
4in at least one substituent carbon number be 1, be methyl.By at least one substituting group is defined as methyl, the ionic liquid that viscosity is lower can be realized.In addition, substituent R
1, R
2, R
3, R
4also can combine each other by substituting group.
As the ammonium ion shown in chemical formula 2, such as, N-butyl-N can be listed, N, N-trimethyl ammonium ion, N-ethyl-N, N-dimethyl-N-propyl ammonium ion, N-butyl-N-ethyl-N, N-Dimethyl Ammonium ion, N-butyl-N, N-dimethyl-N-propyl ammonium ion, N-propyl group-N-crassitude ion, N-butyl-N-crassitude ion etc., but be also not limited to these.
Imidazol ion such as can be defined as the imidazol ion represented with the structural formula shown in chemical formula 3.
[chemical formula 3]
R
5, R
6, R
7for being selected from the substituting group among alkyl, ester group, ether and itrile group, can be mutually identical substituting group, also can be not identical substituting group.Carbon number contained in preferred substituents is less than 8.Thus, the viscosity caused by the increase of the molecular weight of ionic liquid can be suppressed to rise, the lithium-ion-conducting of the 1st nonaqueous electrolyte can be improved.In substituting group, preferred alkyl.Alkyl is compared with other substituting group, and intermolecular interaction is more weak, and the viscosity of ionic liquid thus can be made to reduce.As alkyl, such as, alkyl, phenyl, benzyl etc. can be listed.Wherein, alkyl, because of molecular structure softness, can realize the ionic liquid that viscosity is lower, thus preferably.When adopting alkyl, the preferred scope of carbon number is: R
5, R
7in be 1 ~ 5, R
6in be 0 ~ 2.Further, so-called R
6middle carbon number represents hydrogen when being 0.In addition, at R
5, R
7in, be preferably mutually different substituting groups.If R
5, R
7structure different, then the symmetry of molecule reduces, and can realize more low-viscosity ionic liquids.At R
5, R
7in, more preferably the carbon number of at least one party is 1, is methyl.
As the imidazol ion shown in chemical formula 3, specifically, 1-ethyl-3-methylimidazole ion, 1-butyl-3-methylimidazole ion, 1-ethyl-2,3-methylimidazole ion, 1-ethyl-3 can be listed, 4-methylimidazole ion etc., but be also not limited to these.
Phosphonium radical ion such as can have the structural formula represented by chemical formula 4.
[chemical formula 4]
R
8, R
9, R
10, R
11for being selected from the substituting group among alkyl, ester group and ether, can be mutually identical substituting group, also can be not identical substituting group.In either case, the carbon number contained by substituting group is all preferably less than 8.In substituting group, preferred alkyl, ether.As alkyl, can list alkyl, phenyl, benzyl etc., wherein, alkyl, because of molecular structure softness, can realize more low-viscosity ionic liquids, thus preferably.When adopting alkyl, the preferred scope of carbon number is 1 ~ 4.In addition, substituent R
8, R
9, R
10, R
11also can combine each other by substituting group.
As the radical ion of Phosphonium shown in chemical formula 4, specifically, tributyl (2-methoxy ethyl) Phosphonium radical ion, tributyl Jia Ji Phosphonium radical ion etc., but be also not limited to these can be listed.
As anion, such as, can list and be selected from PF
6 -, BF
4 -, CF
3sO
3 -, C
4f
9sO
3 -, [B (OOC-COO)
2]
-, [(CN)
2n]
-, [(CF
3sO
2)
2n]
-, [(C
2f
5sO
2)
2n]
-, BF
3(CF
3)
-and at above-mentioned each ion (PF
6 -, BF
4 -, CF
3sO
3 -, C
4f
9sO
3 -, [B (OOC-COO)
2]
-, [(CN)
2n]
-, [(CF
3sO
2)
2n]
-, [(C
2f
5sO
2)
2n]
-, BF
3(CF
3)
-) in import substituting group and among the anion that obtains more than a kind.As anion, at employing BF
3(CF
3)
-, there is the [(CF of sulfimide structure
3sO
2)
2n]
-or [(C
2f
5sO
2)
2n]
-when, because ionic liquid is hydrophobicity, thus more preferably.Particularly preferred is [(CF
3sO
2)
2n]
-, more low-viscosity ionic liquids can be realized.
As supporting electrolyte, if can be used for lithium rechargeable battery just without particular limitation of, such as, can LiPF be listed
6, LiBF
4, Li (CF
3sO
3), Li (C
4f
9sO
3), Li [B (OOC-COO)
2], Li [(CN)
2n], Li [(CF
3sO
2)
2n], Li [(C
2f
5sO
2)
2n] and at above-mentioned each compound (LiPF
6, LiBF
4, Li (CF
3sO
3), Li (C
4f
9sO
3), Li [B (OOC-COO)
2], Li [(CN)
2n], Li [(CF
3sO
2)
2n], Li [(C
2f
5sO
2)
2n]) in import substituting group and the compound etc. that obtains.The kind of the supporting electrolyte used can be one kind or two or more.
Form ionic liquid anion and formation supporting electrolyte anion can identical also can not be identical.Wherein, the anion of ionic liquid, the anion of supporting electrolyte are all preferably the PF obtained by a part for fluoro-alkyl replacement fluorine atom
6 -, BF
4 -, or there is the anion of sulfimide base.Particularly preferably ionic liquid and supporting electrolyte all have BF
3(CF
3)
-or [(CF
3sO
2)
2n]
-as anion.
The concentration of supporting electrolyte is preferably defined as 0.1 ~ 4 mole/L.By making the concentration of supporting electrolyte at 0.1 mole/more than L, the ionic conductance of the 1st nonaqueous electrolyte can be improved, thus can obtain high flash-over characteristic.In addition, by making the concentration of supporting electrolyte at 4 moles/below L, the viscosity of the 1st nonaqueous electrolyte can be suppressed to rise, thus can improve the ionic conductance of the 1st nonaqueous electrolyte.Preferred concentration is 0.3 ~ 2 mole/L.
2nd nonaqueous electrolyte can containing organic solvent and the supporting electrolyte be dissolved in organic solvent.As long as the 2nd nonaqueous electrolyte can be used for lithium rechargeable battery, just do not limit especially.
Organic solvent is preferably containing more than a kind that is selected among ester class, carbonates, ethers, nitrile and the compound that imported substituting group and obtain in above-mentioned each compound (ester class, carbonates, ethers, nitrile).Preferably be selected from ester class, carbonates.In ester class, the ester class of preferred circulus, the particularly preferably gamma butyrolactone (γ BL) of 5 rings.
As carbonates, ring-type, chain structure can adopt.The carbonates of preferred 5 ring structures of cyclic carbonates, particularly preferably ethylene carbonate (EC), vinylene carbonate (VC), propylene carbonate (PC).The carbonates of the preferred carbon number less than 7 of linear carbonate class, particularly preferably dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC).
As ethers, ring-type, chain structure can adopt.As ring-type ethers, the preferably ethers of 5 rings and 6 ring structures, wherein preferably not double bond containing.As chain ethers, preferably containing more than 5 carbon atoms.Such as, oxinane, dioxane, oxolane, 2-methyltetrahydrofuran, butyl ether, isoamyl ether etc. can be listed.
As nitrile, such as, acetonitrile, propionitrile etc. can be listed.
Organic solvent can be used alone, but the preferably multiple use of mixing.Particularly preferably containing carbonates, the carbonates wherein preferably containing 5 ring structures, particularly preferably containing EC or PC.
Organic solvent preferably consist of EC/PC, EC/ γ BL, EC/EMC, EC/PC/EMC, EC/EMC/DEC, EC/PC/ γ BL.
As supporting electrolyte, as long as can be used for lithium rechargeable battery, just without particular limitation of.Such as, the electrolyte with the identical type illustrated in the 1st nonaqueous electrolyte can be used.Particularly preferred is LiPF
6, LiBF
4, Li (CF
3sO
3), Li [(CF
3sO
2)
2n].
Solid electrolyte layer contains and does not dissolve and non-swelling material with lithium-ion-conducting in the 1st nonaqueous electrolyte and the 2nd nonaqueous electrolyte.Solid electrolyte layer preferably has imporosity and optionally through lithium ion.
As the material with lithium-ion-conducting, be preferably selected from more than a kind among organic polymer, oxide and sulfide.Which kind of material all demonstrates lithium-ion-conducting in the solid state, thus can realize having imporosity and optionally through the solid electrolyte layer of lithium ion.
Organic polymer and supporting electrolyte together use.As organic polymer, specifically, the macromolecule containing polyethylene glycol oxide and the macromolecule containing polyvinyl can be listed.Macromolecule containing polyethylene glycol oxide contains polyethylene glycol oxide as main chain, and a part also can branch.The end of polyethylene glycol oxide is preferably by ehter bond or ester bond protection hydroxyl.Macromolecule containing polyvinyl contains Polyethylene Chain as main chain, is preferably containing the functional group comprising ester bond or carbonic acid ester bond from the side chain of main chain branch.Particularly, containing polyethylene glycol oxide macromolecule because of the jump conductibility of lithium ion excellent, thus preferably.Also can containing a small amount of softening agent such as dibutyl phthalate in organic polymer.
As long as the supporting electrolyte together used with organic polymer can be used for lithium rechargeable battery, just without particular limitation of.Such as, the electrolyte with the identical kind illustrated in the 1st nonaqueous electrolyte can be used.Particularly preferably be LiPF
6, LiBF
4, Li (CF
3sO
3), Li [(CF
3sO
2)
2n] and the lithium salts that imports substituting group and obtain in above-mentioned each compound.
As oxide, such as, oxide glass, oxide crystallization can be listed.All in constitution element, contain lithium, different from containing organic macromolecule solid electrolyte layer, do not need supporting electrolyte.As oxide glass, the oxide containing more than the a kind element be selected among B, Si and P and Li can be listed, specifically, can Li be listed
4siO
4-Li
3bO
3it is oxide.In addition, as oxide crystallization, the oxide containing more than the a kind element be selected among Al, Ti, P, La, N, Si, In and Nb and Li can be listed.Specifically, Na can be listed
3zr
2si
2pO
12, LiTi (PO
4)
3, LiAlTi (PO
4)
3, Li
7la
3zr
2o
12, La
0.5li
0.5tiO
3deng.
As sulfide, such as, chalcogenide glass, sulfide crystallization can be listed.All in constitution element, contain lithium, different from containing organic macromolecule solid electrolyte layer, do not need supporting electrolyte.Specifically, Li can be listed
3pS
4, Li
4siS
4, LiGeS
4-Li
3pS
4, LiS-SiS
2system, SiS-P
2s
5system, LiS-B
2s
3system, Li
2s-SiS
2-Li
4siO
4system etc.Wherein, Li
2s-P
2s
5, Li
3.25ge
0.25p
0.75s
4deng preferred because conductance is high.
When the reducing resistance difference of the oxide contained in solid electrolyte layer and/or sulfide, preferably between solid electrolyte layer and negative pole, configure multiple aperture plasma membrane, nonwoven fabrics or metal oxide layer.By configuring multiple aperture plasma membrane, nonwoven fabrics or metal oxide layer between solid electrolyte layer and negative pole, solid electrolyte layer not with cathode contact, thus can to avoid in solid electrolyte layer contained oxide and/or sulfide because of with cathode contact and be reduced decomposition, make solid electrolyte layer deterioration.As multiple aperture plasma membrane or nonwoven fabrics, polyethylene multiple aperture plasma membrane, polypropylene (PP) multiple aperture plasma membrane processed, cellulose nonwoven fabrics etc. can be used to can be used as multiple aperture plasma membrane or the nonwoven fabrics of the barrier film of lithium rechargeable battery.As described metal oxide layer, as long as the metal oxide that aluminium oxide, silica, zinc oxide etc. are insoluble in the nonaqueous electrolyte of negative side, just without particular limitation of.In addition, oxide contained in solid electrolyte layer and/or the reducing resistance of sulfide excellent, because can volume energy density be improved, therefore preferred multiple aperture plasma membrane, nonwoven fabrics or metal oxide layer to be omitted.
1st nonaqueous electrolyte, the 2nd nonaqueous electrolyte, solid electrolyte layer be preferably combined as following combination.
Under solid electrolyte layer contains organic macromolecule situation, preferably contained in the 1st nonaqueous electrolyte, the 2nd nonaqueous electrolyte and solid electrolyte layer supporting electrolyte is identical.Wherein, the LiPF preferably obtained by a part for fluoro-alkyl replacement fluorine atom
6, LiBF
4, or there is the lithium salts of anion of sulfimide base, particularly preferably Li [(CF
3sO
2)
2n].A part containing supporting electrolyte contained in organic macromolecule solid electrolyte layer has the possibility exchanged with the supporting electrolyte in the 1st nonaqueous electrolyte or the 2nd nonaqueous electrolyte.Therefore, by being defined as identical by supporting electrolyte contained in the 1st nonaqueous electrolyte, the 2nd nonaqueous electrolyte and solid electrolyte layer, the change of battery behavior can be suppressed.Preferably the 1st nonaqueous electrolyte is hydrophobicity, thus preferably by instead of the part of fluorine element with fluoro-alkyl and the PF obtained
6 -, BF
4 -or the anion with sulfimide base is unified, the [(CF particularly preferably had excellent water-resistance
3sO
2)
2n]
-.
Anion used in ionic liquid for the 1st nonaqueous electrolyte, as previously mentioned preferred [(CF
3sO
2)
2n]
-.As cation, preferred N-butyl-N, N, N-trimethyl ammonium ion, N-ethyl-N, N-dimethyl-N-propyl ammonium ion, N-butyl-N-ethyl-N, N-Dimethyl Ammonium ion, N-butyl-N, N-dimethyl-N-propyl ammonium ion, N-propyl group-N-crassitude ion, N-butyl-N-crassitude ion, 1-ethyl-3-methylimidazole ion, 1-butyl-3-methylimidazole ion, 1-ethyl-2,3-methylimidazole ion, 1-ethyl-3,4-methylimidazole ion.Particularly preferably N-propyl group-N-crassitude ion, N-butyl-N-crassitude ion, 1-ethyl-3-methylimidazole ion.Most preferably can realize the 1-ethyl-3-methylimidazole ion of low-viscosity ionic liquids.
Supporting electrolyte used in 2nd nonaqueous electrolyte is preferred Li [(CF as previously mentioned
3sO
2)
2n].Organic solvent preference as formed by high boiling organic solvent EC/PC, EC/ γ BL, EC/PC/ γ BL, PC/ γ BL.Soft containing organic macromolecule solid electrolyte layer, if thus under the high temperature conditions the vapour pressure of organic solvent rise, then have the possibility of distortion.Therefore, as organic solvent, preferred boiling point is high.Wherein, the mixed solvent system containing EC and PC because of excellent in stability preferably.
Containing the supporting electrolyte adopted in organic macromolecule solid electrolyte layer preferred Li [(CF as previously mentioned
3sO
2)
2n].As organic polymer, preferably containing the macromolecule of polyethylene glycol oxide.Polyethylene glycol oxide is because the Oxyerhylene of main chain can embody lithium-ion-conducting.
Adopt containing to be most preferredly combined as during organic macromolecule solid electrolyte layer: the 1st nonaqueous electrolyte contains [(CF
3sO
2)
2n]-1-ethyl-3-methylimidazole [(CF
3sO
2)
2n], solid electrolyte layer contains Li [(CF
3sO
2)
2n]-polyethylene glycol oxide, the 2nd nonaqueous electrolyte contains Li [(CF
3sO
2)
2n] combination of-EC/PC.According to this combination, can use and there is hydrophobicity and the low ionic liquid of viscosity, and can suppress and electrolytical decomposition reaction when air or contact with moisture, thus can improve durability and the heavy-current discharge characteristic of air cell further.
When adopting the solid electrolyte layer containing oxide and/or sulfide, in the 1st nonaqueous electrolyte and the 2nd nonaqueous electrolyte, contained supporting electrolyte does not need identical.Solid electrolyte layer containing oxide and/or sulfide, not containing supporting electrolyte, therefore can not produce the exchange with contained supporting electrolyte in the 1st, the 2nd nonaqueous electrolyte.
As ionic liquid used in the 1st nonaqueous electrolyte, high, the hydrophobic ionic liquid of preferred lithium ionic conductivity.As anion, preferably instead of the part of fluorine element and the PF obtained with fluoro-alkyl
6 -, BF
4 -or there is the anion of sulfimide base.Wherein, preferred BF
3(CF
3)
-or [(CF
3sO
2)
2n]
-, particularly preferably [(CF
3sO
2)
2n]
-.
As cation, such as, preferred N-butyl-N, N, N-trimethyl ammonium ion, N-ethyl-N, N-dimethyl-N-propyl ammonium ion, N-butyl-N-ethyl-N, N-Dimethyl Ammonium ion, N-butyl-N, N-dimethyl-N-propyl ammonium ion, N-propyl group-N-crassitude ion, N-butyl-N-crassitude ion, 1-ethyl-3-methylimidazole ion, 1-butyl-3-methylimidazole ion, 1-ethyl-2,3-methylimidazole ion, 1-ethyl-3,4-methylimidazole ion.Particularly preferably N-propyl group-N-crassitude ion, N-butyl-N-crassitude ion, 1-ethyl-3-methylimidazole ion.Most preferably can realize the 1-ethyl-3-methylimidazole ion of low-viscosity ionic liquids.
As the organic solvent adopted in the 2nd nonaqueous electrolyte, EC/PC, EC/ γ BL, the EC/PC/ γ BL that form preferably by the organic solvent excellent by the dissolubility of carbon dioxide, PC/ γ BL.Solid electrolyte layer containing oxide and/or sulfide is inorganic electrolyte layer, is therefore upright and outspoken, if there is the gases such as carbon dioxide because of decomposition of nonaqueous electrolyte etc. in negative pole, makes volumetric expansion, then has the possibility that dielectric substrate ruptures.Therefore, organic solvent is preferably high to the dissolubility of carbon dioxide.Wherein EC/ γ BL, EC/PC/ γ BL because of carbon dioxide solubility and reducing resistance excellent and preferred.Supporting electrolyte preferred lithium ionic conductivity is excellent, specifically, and preferred LiPF
6, LiBF
4.Particularly LiBF
4because of excellent in stability preferably.
In oxide and sulfide, more preferably contain the solid electrolyte layer of the excellent sulfide of lithium-ion-conducting.More preferably chalcogenide glass.As chalcogenide glass, specifically, Li can be listed
3pS
4, Li
4siS
4, LiGeS
4-Li
3pS
4, LiS-SiS
2system, SiS-P
2s
5system, LiS-B
2s
3system etc.Wherein, Li
2s-SiS
2-LiSiO
4system and Li
2s-SiS
2-Li
3pO
4be because conductance is high and reducing resistance is excellent and preferred.
Thus, most preferred when adopting the solid electrolyte layer containing oxide and/or sulfide is combined as: the 1st nonaqueous electrolyte contains Li [(CF
3sO
2)
2n]-1-ethyl-3-methylimidazole [(CF
3sO
2)
2n], solid electrolyte layer contains Li
2s-SiS
2-Li
3pO
4system, and the 2nd nonaqueous electrolyte contains LiBF
4the combination of-EC/PC/ γ BL.According to this combination, can use and there is hydrophobicity and the low ionic liquid of viscosity, and suppress, with the decomposition reaction of the 1st nonaqueous electrolyte when air or contact with moisture, durability and the heavy-current discharge characteristic of air cell to be improved further.
Then, positive pole, negative pole, container are described.
Positive pole contains positive electrode collector and is supported on the anode layer on this positive electrode collector.
As positive electrode collector, in order to carry out rapidly the diffusion of oxygen, such as grid, punch metal plate, expanded metal etc. are preferably adopted to have the conductive board of through hole.About the material of conductive board, such as, can list stainless steel, nickel, aluminium, iron, titanium etc.Further, the surface of collector body is in order to suppress oxidation, also can be coated to the metal or alloy of oxidative resistance.
Anode layer is such as by mixing Carbonaceous matter and binding agent, and this mixture is rolled into film-form and is filmed, then drying is formed.Or, such as, can, by mixing Carbonaceous matter and binding agent in a solvent, being coated with on the current collector, then carrying out drying and rolling being formed.
As Carbonaceous matter, such as, can list Ketjen black, acetylene black, carbon black, furnace black, active carbon, activated carbon fiber, charcoal class etc.By having the particulate of the function making oxygen generation overvoltage reduce at the surface of this Carbonaceous matter load supported cobalt phthalocyanine etc., the efficiency of the reduction reaction of oxygen can be improved.In addition, by adding the contour conductive carbon pledge of acetylene black in Carbonaceous matter, the conductivity of anode layer can also be improved.
In order to maintain the layer shape of the layer containing Carbonaceous matter, and Carbonaceous matter being adhered on the current collector, also can add binding agent in anode layer.As binding agent, such as, can use polytetrafluoroethylene (PTFE), Kynoar (PVdF), ethylene-propylene-diene rubber (EPBR), butadiene-styrene rubber (SBR) etc.
Carbonaceous matter in anode layer and the mixing ratio of binding agent are preferably the scope of Carbonaceous matter 70 ~ 98 % by weight, binding agent 2 ~ 30 % by weight.
Negative pole contain negative electrode collector and be supported on negative electrode collector containing negative electrode active material layer.
Negative electrode active material such as can use the material that can embed deintercalate lithium ions.
There is no particular limitation can to embed the material of deintercalate lithium ions, can use the material that can use in lithium ion battery or lithium battery.Wherein, preferably use be selected from metal oxide, metal sulfide, metal nitride, lithium metal, lithium alloy, lithium composite xoide, maybe can embed deintercalate lithium ions Carbonaceous matter among at least a kind of material as negative electrode active material.
As the Carbonaceous matter that can embed deintercalate lithium ions, such as, can list the graphite materials such as graphite, coke, carbon fiber, Spherical Carbon or carbonaceous material, heat-curing resin, isotropic pitch, mesophase pitch, mesophase pitch based carbon fiber, mesophasespherule etc. by implementing the available graphite material of heat treatment or carbonaceous material at 500 ~ 3000 DEG C.
As metal oxide, such as, can list tin-oxide, Si oxide, Li-Ti oxide, niobium oxide, tungsten oxide etc.
As metal sulfide, such as, can list tin sulfide, titanium sulfide etc.
As metal nitride, such as, can list lithium cobalt nitride, lithium iron-nitride, lithium manganese nitride etc.
As lithium alloy, such as, can list lithium-aluminium alloy, lithium-tin alloy, Li-Pb alloy, Li-Si alloy etc.
As negative electrode collector, such as, can use and there is the conductive board of through hole or the conductive board of atresia.These conductive boards such as can be formed by copper, stainless steel or nickel.As the conductive board of porous structure, grid, punch metal plate, expanded metal etc. can be adopted, or adopt using supporting on metal foil containing the layer of negative electrode active material, the substrate of perforate in above-mentioned metal forming is as the conductive board of porous structure.
Negative pole containing the such negative electrode active material of Carbonaceous matter such as makes by following method: when there is solvent, anticathode active material and binding agent carry out mixing, by the suspended matter coating that obtains on the current collector, 1 pressurization is carried out with desired pressure after drying or the pressurization of 2 ~ 5 multistages makes.
As binding agent, such as, polytetrafluoroethylene (PTFE), Kynoar (PVdF), ethylene-propylene-diene rubber (EPBR), butadiene-styrene rubber (SBR), carboxymethyl cellulose (CMC) etc. can be adopted.
The mixing ratio of Carbonaceous matter and binding agent is preferably: the scope that Carbonaceous matter is 80 ~ 98 % by weight, binding agent is 2 ~ 20 % by weight.
In addition, as negative electrode active material, if use the metal material such as lithium metal or lithium alloy, even if these metal materials also can be processed into sheet form individually, therefore, it is possible to formed containing negative electrode active material layer when not using binding agent.In addition, what formed by these metal materials can also directly be connected with negative terminal containing negative electrode active material layer.
As container, such as, can be formed by metallic plate, the sheet material etc. with resin bed.
As metallic plate, such as, can be formed by iron, stainless steel, aluminium.
Preferred sheet material contains the resin bed of metal level and coated metal layer.Preferred metal layers is formed by aluminium foil.On the other hand, resin bed can be formed by the thermoplastic resin such as polyethylene, polypropylene.Resin bed can make single or multiple lift structure.
One example of the air cell of execution mode shown in Fig. 1.Shown in Fig. 1 is nonaqueous electrolyte air cell.Nonaqueous electrolyte air cell possesses the container 1 of the laminate film that inner surface is formed by thermoplastic resin.Container 1 is such as sealed by three limits overlapped by inner surface by heat seal the laminate film obtained and forms.Solid electrolyte layer 2 is configured in container 1, is clipped between laminate film on three limits.Space in container 1 with solid electrolyte layer 2 for boundary is divided into two spaces.Positive pole 3 is received in the space (upside of Fig. 1) of one side, is called as the 1st space 4.The space storage negative pole 5 of the opposing party, is called as the 2nd space 6.Hole (such as airport) 7, by opening, is communicated with the 1st space 4 to make the wall of container 1.Airport 7 is for supplying oxygen supply to positive pole 3.
Positive pole 3 comprises and solid electrolyte layer 2 anode layer that face contacts 8 and the positive electrode collector 9 be such as made up of porous conductive substrate supporting anode layer 8.One end of positive terminal 10 is electrically connected with positive electrode collector 9, and the other end is externally stretched out by the thermal seal of container 1 part of hot melt adhesive (between the laminate film).Air diffusion layer 11 is configured on positive electrode collector 9.As long as air diffusion layer 11 can supply to positive pole 3 air introduced from airport 7, just without particular limitation of, such as, the synthetic resin nonwoven fabrics, glass fibre non-woven etc. of the porous film containing fluororesin such as polyethylene, polypropylene or PTFE, polypropylene or PTFE etc. can be listed.1st nonaqueous electrolyte (not shown) is maintained in positive pole 3, also can be housed in the 1st space 4 as required.
Negative pole 5 comprises the negative electrode collector 13 be such as made up of porous conductive substrate containing negative electrode active material layer 12 and support containing negative electrode active material layer 12 contacted with the face of the opposition side of solid electrolyte layer 2.One end of negative terminal 14 is electrically connected with negative electrode collector 13, and the other end is externally stretched out by the thermal seal of container 1 part of hot melt adhesive (between the laminate film).The direction of stretching out of stretching out direction and positive terminal 10 of negative terminal 14 is rightabout.2nd nonaqueous electrolyte (not shown) is maintained in negative pole 5, also can be housed in the 2nd space 6 as required.
At the outer surface of container 1, be releasably configured with the sealant tape 15 for dead air hole 7.When battery uses, by taking off sealing adhesive tape 15, can to anode layer 8 air supply.
As illustrated in Figure 1, by coming the 1st space 4 in spacing container 1 and the 2nd space 6 with solid electrolyte layer 2, the effect that prevention the 1st nonaqueous electrolyte spreads to positive pole to negative pole diffusion and prevention the 2nd nonaqueous electrolyte can be improved, thus can expect the durability of air cell and the further improvement of large current density electrical characteristics.
Embodiment
Below, with reference to accompanying drawing, embodiment is described in detail.
(embodiment 1)
By the polytetrafluoroethylene dry type of the Ketjen black of 90 % by weight and 10 % by weight is mixed, and roll, obtain the anode layer that length and width are 20mm, thickness is the film-form of 200 μm.This anode layer is crimped on positive electrode collector and stainless steel grid, has made positive pole.And then the part to be exposed by the positive electrode collector of the positive pole obtained is connected with one end of positive terminal.
Metallic lithium foil is crimped on nickel grid, obtains negative pole.Further, nickel grid is connected with one end of negative terminal.In addition, the air diffusion layer that is laminated by polypropylene-made nonwoven cloth and PTFE multiple aperture plasma membrane and polypropylene multiple aperture plasma membrane is got out.
By will by Li
2s-SiS
2-Li
3pO
4form chalcogenide glass be shaped as 100 μm thick, have adjusted solid electrolyte layer.
By in the hydrophobic ionic liquid containing the two trifluoromethanesulfonamide of 1-ethyl-3-methylimidazole, in the ratio of 0.8 mole/L, dissolve by two trifluoromethanesulfonamide lithium (Li [(CF
3sO
2)
2n]) supporting electrolyte that forms, modulate the 1st liquid nonaqueous electrolyte.
By in the solvent of by volume ratio 1: 1: 4 mixed carbonic acid ethyl (EC), propylene carbonate (PC) and gamma-butyrolacton (γ BL), dissolve by LiBF in the ratio of 1.5 moles/L
4the supporting electrolyte formed, has modulated the 2nd liquid nonaqueous electrolyte.
Stack gradually negative pole, polypropylene multiple aperture plasma membrane, solid electrolyte layer, positive pole and air diffusion layer.Air diffusion layer using polypropylene-made nonwoven cloth side as side of the positive electrode, using PTFE multiple aperture plasma membrane side as outside.Be ready to there is aluminium-PE/PP layer at a mask of aluminium lamination, have the laminate film of aluminium-PE/PP-PET layer at another mask.The softening point of pet layer is lower than PE/PP layer, by adding thermo-compressed between pet layer, shows cementability, and the one side with pet layer is the inner surface of housing material.Be positioned at the mode of inner side with the pet layer of laminate film (thermoplastic resin) face, be coated to this sandwich with laminate film.When making the inner surface of laminate film overlap each other, clip three limits of solid electrolyte layer in-between.In addition, the airport be located on laminate film is configured in air diffusion layer.In addition, make it inaccessible at this airport adhesive seal adhesive tape.In addition, stretch out between the laminate film that the other end of positive terminal and negative terminal overlaps each other from inner surface.
For between the laminate film that inner surface overlaps each other, except liquid injection port, carry out hot melt adhesive by heat seal.Now, the scope heat seal of the end of solid electrolyte layer will be covered, with solid electrolyte layer isolation the 1st space and the 2nd space.Then, inject the 1st nonaqueous electrolyte from liquid injection port to the 1st space, inject the 2nd nonaqueous electrolyte to the 2nd space simultaneously.Finally by heat seal, liquid injection port is sealed, thus made the nonaqueous electrolyte air cell of the structure shown in Fig. 1.Now, will the scope heat seal of the end of solid electrolyte layer be covered, close the 1st space and the 2nd space respectively.
(embodiment 2)
Be after the polyethylene glycol oxide heating of 10000 by mean molecule quantity at 100 DEG C, make the Li [(CF containing 5 % by weight
3sO
2)
2n] supporting electrolyte dissolve and in teflon plate upper, cooling, made containing organic macromolecule solid electrolyte layer.
In addition, by the solvent of by volume ratio 1: 1 mixed carbonic acid ethyl and propylene carbonate, the Li [(CF as supporting electrolyte is dissolved in the ratio of 1.0 moles/L
3sO
2)
2n], modulate the 2nd liquid nonaqueous electrolyte.
Except making solid electrolyte layer and the 2nd nonaqueous electrolyte as stated above, by method similarly to Example 1, make nonaqueous electrolyte air cell.
(embodiment 3)
Except adopting Li
2o-Al
2o
3-TiO
2-P
2o
5glass as solid electrolyte layer, and is beyond the Porous PP film of 25 μm at the negative side configuration thickness of solid electrolyte layer, by method similarly to Example 1, has made nonaqueous electrolyte air cell.
(embodiment 4)
Except adopting La
0.5li
0.5tiO
3crystallization as solid electrolyte, and is beyond the Porous PP film of 25 μm at the negative side configuration thickness of solid electrolyte layer, by method similarly to Example 1, has made nonaqueous electrolyte air cell.
(embodiment 5)
Except adopting Li
3pS
4crystallization as solid electrolyte, and is beyond the Porous PP film of 25 μm at the negative side configuration thickness of solid electrolyte layer, by method similarly to Example 1, has made nonaqueous electrolyte air cell.
(embodiment 6)
Except as the 1st nonaqueous electrolyte, adopt containing N-ethyl-N, in the hydrophobic ionic liquid of the two trifluoromethanesulfonamide of N-dimethyl-N-propyl ammonium, dissolve by two tetrafluoromethane sulfonamide lithium (Li [(CF in the ratio of 0.5 mole/L
3sO
2)
2n]) supporting electrolyte that forms and beyond the nonaqueous electrolyte obtained, by method similarly to Example 1, made nonaqueous electrolyte air cell.
(embodiment 7)
Except as the 1st nonaqueous electrolyte, adopt and (in the hydrophobic ionic liquid of the two trifluoromethanesulfonamide of methoxy ethyl) Phosphonium root, dissolving by two tetrafluoromethane sulfonamide lithium (Li [(CF in the ratio of 1 mole/L containing triethyl group
3sO
2)
2n]) beyond the nonaqueous electrolyte of supporting electrolyte that forms, by method similarly to Example 1, make nonaqueous electrolyte air cell.
(embodiment 8)
Except as the 2nd nonaqueous electrolyte, adopt in 1: 1: 1: 1 ratio mixed carbonic acid ethyl, propylene carbonate, propionitrile, butyl ether solvent in, dissolve by LiBF in the ratio of 1 mole/L
4beyond the nonaqueous electrolyte of the supporting electrolyte formed, by method similarly to Example 1, make nonaqueous electrolyte air cell.
(comparative example 1)
Except as the 1st, the 2nd nonaqueous electrolyte, adopt respectively and dissolve by two trifluoromethanesulfonamide lithium (Li [(CF in the ratio of 0.8 mole/L in the two trifluoromethanesulfonamide of 1-ethyl-3-methylimidazole
3sO
2)
2n]) beyond the nonaqueous electrolyte of supporting electrolyte that forms, by method similarly to Example 1, make nonaqueous electrolyte air cell.
(comparative example 2)
Except as the 1st, the 2nd nonaqueous electrolyte, adopt respectively with in the solvent of volume ratio by 1: 1: 4 mixed carbonic acid ethyl, propylene carbonate and gamma-butyrolacton, dissolve by LiBF in the ratio of 1.5 moles/L
4beyond the nonaqueous electrolyte of the supporting electrolyte formed, by method similarly to Example 1, make nonaqueous electrolyte air cell.
(comparative example 3)
In the two trifluoromethanesulfonamide of 1-ethyl-3-methylimidazole, dissolve by two trifluoromethanesulfonamide lithium (Li [(CF in the ratio of 0.8 mole/L
3sO
2)
2n]) electrolyte that forms, modulate the 1st solution.In the solvent of by volume ratio 1: 1: 4 mixed carbonic acid ethyl, propylene carbonate and gamma butyrolactone, dissolve by LiBF in the ratio of 1.5 moles/L
4the electrolyte formed, has modulated the 2nd solution.Except being used separately as except the 1st, the 2nd nonaqueous electrolyte by the solution obtained in volume ratio 1: 1 mixing the 1st solution and the 2nd solution, by method similarly to Example 1, make nonaqueous electrolyte air cell.
In the constant temperature and humidity cabinet of temperature 45 C, humidity 65%, determine the flash-over characteristic of the air cell of making by following condition.In test 1, determine the discharge capacity (mAh/g) of unit positive pole carbon weight when discharging into 2.0V with discharging current 0.04mA.In test 2, determine the discharge capacity (mAh/g) of unit positive pole carbon weight when discharging into 2.0V with discharging current 0.4mA.In test 3, to carrying out after discharging into 2.0V with discharging current 0.4mA, the period that discharge capacity when being charged to the charge and discharge cycles of 4.0 with charging current 0.4mA is reduced to 80% of initial capacity measures.The result of test 1 ~ 3 is shown in following table 1.
Table 1
Learn from table 1: the air cell of embodiment 1 ~ 8 is compared with the battery of comparative example 1 ~ 3, and the discharge capacity when 0.04mA, 0.4mA is all large, heavy-current discharge characteristic good, and the cycle characteristics becoming durability index is also excellent.
About the battery of comparative example 1, the discharge capacity when 0.04mA, 0.4mA is all little than embodiment 1 ~ 8.If point electrolytic cell after test 1 ~ 3, the 2nd nonaqueous electrolyte is coloured to yellow, and negative terminal surface changes color to yellowish-brown.Think because ionic liquid makes battery behavior reduce in negative pole current potential reduction decomposition.
About the battery of comparative example 2,3, although the discharge capacity when 0.4mA and embodiment are equal, the discharge capacity when 0.04mA and cycle characteristics be remarkable decline compared with embodiment, not talkatively has both heavy-current discharge characteristic and durability.In addition, about the battery of comparative example 2,3, if disintegrated by the battery after test 1, test 3, the 1st non-aqueous solution electrolysis quality all reduces, and particularly in comparative example 2, solid is separated out.Think if the electric discharge under repeating low current or discharge and recharge etc., use battery for a long time, then contained in the 1st nonaqueous electrolyte organic solvent volatilizees from airport, and battery behavior is reduced.
Symbol description
1 container, 2 solid electrolyte layers, 3 positive poles, 4 the 1st spaces, 5 negative poles, 6 the 2nd spaces, 7 airports, 8 anode layer, 9 positive electrode collectors, 10 positive terminals, 11 air diffusion layer, 12 are containing negative electrode active material layer, 13 negative electrode collectors, 14 negative terminals, 15 sealant tapes.
Accompanying drawing explanation
Fig. 1 is the cutaway view blocked along thickness direction by the air cell of execution mode.
Claims (6)
1. an air cell, is characterized in that, it comprises:
The container that inner surface is formed by thermoplastic resin;
Be accommodated in the positive pole in described container;
Be accommodated in the negative pole in described container;
To remain in described positive pole and the 1st nonaqueous electrolyte containing ionic liquid;
To remain in described negative pole and the 2nd nonaqueous electrolyte containing organic solvent;
To be configured between described positive pole and described negative pole and there is the solid electrolyte layer of lithium-ion-conducting; With
If the hole for supplying oxygen supply to described positive pole on the container,
That described solid electrolyte layer is mixing for preventing described 1st nonaqueous electrolyte and described 2nd nonaqueous electrolyte, that not there is through hole solid electrolyte layer,
Be fixed in the inner surface of described container by heat seal between the inner surface that the end of described solid electrolyte layer is sandwiched in described container, described positive pole and described negative pole are isolated by described solid electrolyte layer thus.
2. air cell according to claim 1, it is characterized in that, described in there is lithium-ion-conducting solid electrolyte layer contain and do not dissolve and non-swelling oxide, sulfide or organic polymer in described 1st nonaqueous electrolyte and described 2nd nonaqueous electrolyte.
3. air cell according to claim 1, it is characterized in that, described in there is lithium-ion-conducting solid electrolyte layer contain and be selected from oxide glass, oxide crystallization, chalcogenide glass, sulfide crystallization and containing more than a kind among the macromolecule of polyethylene glycol oxide.
4. air cell according to claim 3, is characterized in that, described ionic liquid contains:
Be selected from ammonium ion, imidazol ion Ji the cation of more than a kind among Phosphonium radical ion; With
Be selected from PF
6 -, BF
4 -, CF
3sO
3 -, C
4f
9sO
3 -, [B (OOC-COO)
2]
-, [(CN)
2n]
-, [(CF
3sO
2)
2n]
-, [(C
2f
5sO
2)
2n]
-and BF
3(CF
3)
-among the anion of more than a kind.
5. air cell according to claim 4, is characterized in that, described ionic liquid has hydrophobicity.
6. air cell according to claim 5, is characterized in that, described organic solvent contains more than a kind that is selected among ester class, carbonates, ethers and nitrile.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201080037651.8A CN102511107B (en) | 2010-06-25 | 2010-06-25 | Air cell |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080037651.8A Division CN102511107B (en) | 2010-06-25 | 2010-06-25 | Air cell |
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|---|---|
| CN104810574A true CN104810574A (en) | 2015-07-29 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107394316A (en) * | 2017-06-21 | 2017-11-24 | 昆明理工大学 | A kind of sodium air cell based on ionic liquid gel positive pole and preparation method thereof |
| CN109686944A (en) * | 2018-12-21 | 2019-04-26 | 福建翔丰华新能源材料有限公司 | A kind of carbon coating lithium alloy combination electrode material and preparation method thereof |
| CN111480256A (en) * | 2018-04-20 | 2020-07-31 | 株式会社Lg化学 | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
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| US20060078790A1 (en) * | 2004-10-05 | 2006-04-13 | Polyplus Battery Company | Solid electrolytes based on lithium hafnium phosphate for active metal anode protection |
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| US5827602A (en) * | 1995-06-30 | 1998-10-27 | Covalent Associates Incorporated | Hydrophobic ionic liquids |
| US20060078790A1 (en) * | 2004-10-05 | 2006-04-13 | Polyplus Battery Company | Solid electrolytes based on lithium hafnium phosphate for active metal anode protection |
| US20070117007A1 (en) * | 2005-11-23 | 2007-05-24 | Polyplus Battery Company | Li/air non-aqueous batteries |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107394316A (en) * | 2017-06-21 | 2017-11-24 | 昆明理工大学 | A kind of sodium air cell based on ionic liquid gel positive pole and preparation method thereof |
| CN107394316B (en) * | 2017-06-21 | 2020-01-10 | 昆明理工大学 | Sodium-air battery based on ionic liquid gel anode and preparation method thereof |
| CN111480256A (en) * | 2018-04-20 | 2020-07-31 | 株式会社Lg化学 | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
| US11646442B2 (en) | 2018-04-20 | 2023-05-09 | Lg Energy Solution, Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery including same |
| CN111480256B (en) * | 2018-04-20 | 2023-10-10 | 株式会社Lg新能源 | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
| CN109686944A (en) * | 2018-12-21 | 2019-04-26 | 福建翔丰华新能源材料有限公司 | A kind of carbon coating lithium alloy combination electrode material and preparation method thereof |
| CN109686944B (en) * | 2018-12-21 | 2022-05-31 | 四川翔丰华新能源材料有限公司 | Carbon-coated lithium alloy composite electrode material and preparation method thereof |
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