CN105899280B - Rechargeable metal nitrogen oxide gas battery system - Google Patents
Rechargeable metal nitrogen oxide gas battery system Download PDFInfo
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- CN105899280B CN105899280B CN201480072628.0A CN201480072628A CN105899280B CN 105899280 B CN105899280 B CN 105899280B CN 201480072628 A CN201480072628 A CN 201480072628A CN 105899280 B CN105899280 B CN 105899280B
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- gas
- metal
- accumulator
- anode
- cathode
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 294
- 239000007789 gas Substances 0.000 title claims abstract description 156
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002485 combustion reaction Methods 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 238000007600 charging Methods 0.000 claims abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 125000006850 spacer group Chemical group 0.000 claims abstract description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 7
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
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- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 4
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 210000000352 storage cell Anatomy 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9481—Catalyst preceded by an adsorption device without catalytic function for temporary storage of contaminants, e.g. during cold start
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
-
- 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
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
-
- 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
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
- H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
- H01M8/222—Fuel cells in which the fuel is based on compounds containing nitrogen, e.g. hydrazine, ammonia
-
- 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
- Secondary Cells (AREA)
Abstract
Charging is provided and is selected from formula N comprising nitrogen oxide (NO) and optional at least onexOyNitrogen oxides, oxygen, vapor, gaseous hydrocarbon, carbon monoxide and carbon dioxide gas metal nitrogen oxide electrochemical cell.The battery can contain spacer body, inhibit NxOy +Diffusion of the active material from cathodic compartment to anodal compartment.There is also provided the rechargeable battery containing the metal nitrogen oxide electrochemical cell.It is additional to provide the N from internal combustion engine exhaust gas whereinxOyIt feeds to metal NxOyThe Vehicular system of accumulator.
Description
The cross reference of related application
It on March 21st, 14/150,168,2014 is submitted this application claims the U.S. Application No. submitted on January 8th, 2014
The priority of U.S. Application No. 14/222,989 that U.S. Application No. is submitted on March 24th, 14/221,814 and 2014, disclosure
Content is incorporated herein through this incorporated.
Background technology
The present invention relates to metal-gas accumulator, more particularly to including nitrogen oxide (NO) or redox active
NxOyMetal-gas accumulator of the gaseous compound as the cathode of active material.
Input business uses, and be conventionally used as the power of mobile electronic device lithium-ions battery since 1991
Source.Construction and the relevant technology of composition with lithium-ions battery (LIB) are research and improved object, and ripe to existing
The LIB accumulators for having technology, which are reported, has the degree of the up to energy density of 7000Wh/L.But even if state-of-the-art LIB
Technology is also not regarded as that following commercial electric vehicle (EV) the required power source can be met.For example, it is equal to for have
It is necessary to have the energy of about 2000Wh/L by the EV of 300 mile ranges of the powertrain of existing conventional internal combustion engine vehicle
The EV accumulator groups of density.Since this energy density is close to the theoretical limit of lithium ion active material, studying can be with
The technology of the higher battery system of energy density is provided.
For multiple reasons, air-metal batteries are to replace and replace lithium as the potential progress in energy technologies
Ion accumulator in one of technology of grinding.In air-metal batteries, active positive electrode material is oxygen, conceptually
Air can be obtained from.As a result, with most of gum fraction of the relevant accumulator of cathode assembly.In metal-air electric power storage
Interest in terms of pond has also obtained the support of following concept：O2The continuous outside from the accumulator of gas, therefore, the accumulator
It will be determined in capacity and the performance in terms of the service life by metal anode.In theory, such accumulator will work until metal
Anode exhausts, therefore air-metal batteries may have than at present in the higher energy density of other battery technologies for grinding
Potentiality.
Due to the known energy potentiality of Li, Li-O2Accumulator is interested candidate high-energy density type rechargeable
Accumulator.It has illustrated based on purifying O2The Li-O in source2Accumulator.But when use environment air is as oxygen source, store
Degradation of cell performance, and the practicability as rechargeable battery is lost.This deterioration is believed to be due to depositing in air
H2O and CO2Lead to oxidate for lithium such as Li2O2And Li2O is by forming Li2CO3(it is a kind of inertia for recharging
Material) it inactivates and occurs.Therefore, Li-O2The successful significant challenge of accumulator is must to purify the O from surrounding air or air2
Gas.In general, the accumulator of consumption pure oxygen will be unpractical for traditional consumer's effectiveness.But using being currently known
Technology, H2O and CO2Presence hinder and successfully develop commercially useful accumulator.
One of method for overcoming problems is to remove H by membrane technology2O and CO2.Air administrative is to implementing gas purification
It is required.But required purification seems extremely difficult, even if using gas separation membrane technology of the prior art.In addition, have
(such as on zeolite) may be absorbed using gas to eliminate H2O and CO2, still, such gas absorption system it is excessive so that
It can not be considered as the solution of reality in most of battery applications.
In view of with metal-O2The problem of accumulator is related is making great efforts the replacement cathode of development of metallic-gas accumulator
System.
Albertus et al. (U.S.2012/0094193) describes a kind of with lithium negative electrode and oxygen/carbon dioxide activity
Electrochemical metal-gas cell of cathode material.Oxygen/the carbon dioxide mixture is based on surrounding air and including CO2.Such as
Described in Albertus, CO2/O2Special ratios --- 2:1 --- it is to realize that high-energy density institute is required as an accumulator
's.But other than the exhaust gas from factory or other large-scale fixed exhaust gas sources, it is difficult to by CO2Gas is enriched with so far class ratio,
Since in surrounding air, CO2Amount be about 0.03%.It is possible that design air control system is so as to full in fixed buildings
This requirement of foot, although keeping constant CO2The air manager system of concentration is simultaneously unconventional available.But for being used for automobile,
Such accumulator will be impracticable, because of CO2Fluctuation of concentration, and control to special ratios and will be difficult.
Takechi et al. (JP 2011-070835) describes metal-air battery, wherein anode metal can be lithium,
Sodium, potassium, magnesium, calcium, aluminium or zinc.Oxidant supplied to cathode is the combination of oxygen and carbon dioxide.
Hillhouse (U.S.2013/0216924) describes the capacitor device for generating electric power, wherein The fuel stream
Thus working electrode through the capacitor charges the capacitor.The stream then reverses, and oxidant stream is through working electrode, thus
The electric current flowing of electrode is crossed in generation.Be enumerated as may act as the fuel in electronics source material include hydrogen, carbon monoxide, NO,
NO2、SO2And volatile hydrocarbon.
It is anti-that Hiraiwa et al. (U.S.2013/0089810) describes a kind of electrochemistry that the stream containing ammonia is decomposed for liquid stream
Equipment is answered, wherein when air or oxygen are coupled as oxidant, NH3It is converted into N2And water.Due between the equipment anode and cathode
Potential difference, electric power may be generated.The equipment is membrane electrode assembly piece installing (MEA) form, and serves as fuel cell rather than serve as storage
Battery.
Lee et al. (U.S.2012/0141889) describes a kind of lithium air accumulator containing organic bath, described
Organic bath includes metal-ligand complex.The negative electrode contains lithium, and anode contains the oxygen from outside supply.The metal-
Ligand complex has the charging/discharging voltages range fallen in the range of lithium storage battery, and is being charged and discharged cyclic process
In can shift electronics via redox couple is formed.Air or oxygen are disclosed unique active material of cathode.
Huang (U.S.2010/0247981) describes the Energy Management System of composition accumulator (fuel cell).This is
System includes a series of modules, and the module is for exhaust gas of the collection from fuel cell, analysis waste gas content and then guides useless
Gas is to the position of further fuel consumption.For example, when exhaust gas contains hydrogen, it can be in internal combustion engine or hydrogen fuel cell
Consumption.
Limaye (U.S.5,976,721) describes chemical joint production process, in the special configuration with multigroup channel
It is carried out in monolithic mass.Fuel such as hydrogen sulfide, ammonia or hydrocarbon are introduced into a channel, by oxidant such as air, nitrogen oxides, dioxy
Change carbon, sulfur dioxide, sulfur trioxide or vapor and introduce second channel.The channel is by being connected to the conductive material structure of external circuit
Into.
Langer et al. (U.S.4,321,313) is described in the presence of electro catalytic electrode and electrolyte by anti-with hydrogen
Power generation reduction should be carried out to nitrogen oxide.As described, which is analogous to the electrochemical reactor of fuel cell.
Smith et al. (U.S.3,979,225) describes a kind of based on nitrogen dioxide (NO2) cathodic reduction is into nitrogen oxide
(NO) fuel cell.Subsequent NO is captured and is oxidized to nitrogen dioxide again to be circulated back to the cathode of the fuel cell.Hydrogen
Gas or reformation hydrocarbon stream are disclosed as anode reactant, and still, any other anode half-reaction can be coupled with the cathodic reduction.
Liang et al. (CN102371888) (only making a summary) describes a kind of plasma generator, effectively from gasoline
Removing nitrogen oxide is removed in the exhaust gas of engine.Although NO passes through between the electrodes, the effectiveness as accumulator is not disclosed.
Wen et al. (CN 102208653) (only making a summary) describes a kind of lithium air accumulator with air electrode, institute
It states air electrode and contains catalyst, carrier and adhesive.
Park (KR20090026589) is described for engine exhaust system based on the preprocessor for removing removing nitrogen oxide
Fuel cell.
It is safe, easy it is, thus, sought for exploitation for the replacement cathode gas of metal-gas accumulator
It is obtaining and cost-effective.Furthermore, it is necessary to commericially feasible use be easy to get replacement gas accumulator and electric power storage
Cell system.
Summary of the invention
Solving these and other objects by the present invention, the first embodiment includes a kind of electrochemical cell, comprising：
Anode comprising metal；It is supplied with the porous cathode of the gas comprising nitrogen oxide (NO)；Separation between anode and cathode
Body；And electrolyte；Wherein NO is activated cathode ingredient.
In the one side of the first embodiment, the gas comprising nitrogen oxide (NO) further includes at least one and is selected from
Formula NxOyNitrogen oxides, oxygen, vapor, gaseous hydrocarbon, carbon monoxide and carbon dioxide gas；Wherein the activated cathode into
It is NO or formula N to dividexOyCompound, the integer that x is 1 or 2, y are 1 to 4.
In the particular embodiment of the present invention, the metal of anode is included selected from lithium, sodium, potassium, magnesium, calcium, aluminum and zinc
One kind.
In a further embodiment, which is lithium, sodium or magnesium.
In the respective aspect of these embodiments, which includes：Anodal compartment comprising working electrode, institute
It states working electrode and includes metal；Cathodic compartment comprising porous cathode, the porous cathode be supplied with comprising nitrogen oxide (NO) and
Redox active NxOyAt least one gas of gaseous compound；Between anodal compartment and cathodic compartment and separate two
The separator of person；And mobility ionophore；The wherein NO and redox active NxOyIt is activated cathode ingredient, and
The spacer body conducts the mobility ionophore and non-conducting NxOy +Ion.
In the one side of the embodiment, which is comprising gel, polymer, ceramic material and polymer and pottery
The film of at least one of the composite material of ceramic material.In the further special aspects of the embodiment, which is packet
Film containing ceramic material, and the ceramic material is dense ceramic membrane.
The present invention further comprises rechargeable battery, the electrochemical cell containing foregoing embodiments.
In the embodiment further embodied, the present invention include NO supply systems, be connected to the accumulator and to
The cathode feeds NO.
In the particular aspects of the embodiment, the present invention includes NxOySupply system is connected to the accumulator and to the moon
Pole feeds NxOy。
In another embodiment, the present invention includes having rechargeable battery and NxOyThe vehicle of supply system, wherein
The NxOySupply system obtains N by the exhaust gas of vehicle internal combustion enginexOy。
The paragraph of front is provided by way of generally introducing, and is not intended to limit the range of following claims.
Currently preferred embodiment and further advantage obtain best reason as detailed below by what is carried out with reference to attached drawing
Solution.
Summary of drawings
Fig. 1, which is shown, uses Li-O2The comparison of cyclic voltammogram that battery and the battery of the present invention obtain.
Fig. 2 shows the charge-discharge curves of the NO gases in 0.2 mol/kg of PP13TFSI-LiTFSI solution.
Fig. 3 shows the schematic diagram of the NO electrochemical cells of one embodiment of the invention.
Fig. 4 is shownIn the test for the NO for being mixed with waste gas componentIn bis- (the trifluoro methylsulfonyls of N- Methyl-N-propyl piperidines
Base) cyclic voltammogram of embodiment 2 and embodiment 3 in acid imide (PP13TFSI) base electrolyte solution.
Fig. 5 is shownIn the test for the NO for being mixed with waste gas componentIn bis- (the trifluoro methylsulfonyls of N- Methyl-N-propyl piperidines
Base) cyclic voltammogram of embodiment 4-1 and embodiment 4-2 in acid imide (PP13TFSI) base electrolyte solution.
Fig. 6 shows the metal N of one embodiment of the inventionxOyThe schematic diagram of accumulator.
Fig. 7 shows the metal N of the embodiment schematically shown in Fig. 6xOyThe charge-discharge curves of gas accumulator.
Fig. 8 shows the schematic diagram of the battery system of the vehicle of one embodiment of the invention.
The description of the preferred embodiments of the invention
The present inventor to the material that may be used as the active material of cathode of metal-gas accumulator grind on a large scale
Study carefully and assess.The purpose of the research is to find to work in the metal with high power capacity and high operating potential-gas accumulator
Cathode activity gas, and without the described problem to oxygen above.The cathode gas should be easy to get, is safe, easily
In operation and obtain and it is cost-effective.
Throughout this manual, all ranges of description include all values therein and subrange, unless otherwise stated.
In addition, that, unless otherwise stated, indefinite article "one" or " one kind " containing with " one or more " throughout this manual
Justice.
According to the present invention, term " vehicle " refers to any power drive unit designed for transport, including automobile, box
Lorry, bus, golf cart and other transport effectiveness forms.
In the research and evaluation process of potential gaseous cathode material, present inventors have surprisingly discovered that, oxidation
Nitrogen (NO) can serve as the cathode gas of metal-gas eletrochemistry battery.Experiment described in embodiment is shown, with O2Gas phase
Than NO gases have higher operating voltage and higher invertibity (rechargeablility).In addition, the research is also shown that
When NO is used as cathode gas, charging and discharging state will be kept on cathode, thus shows redox property.It in addition, can
With the operating voltage and voltage hysteresis for significantly improving the battery by introducing NO gases into the metal-gas accumulator.
As shown in embodiment and Fig. 1, present inventor have determined that, NO gases are showed during oxidation/reduction and are provided
There is the redox reaction of narrow peak separation.With other gas phase ratios, NO gases show improved rechargeablility.
About operating voltage, NO also has high operation voltage.Its operating voltage is estimated as 4.2V vs.Li/Li+, such as Fig. 1
Shown in, it is high when this is compared with the redox reaction (ORR) (2.2-2.7V) of oxygen.
Therefore, first embodiment of the invention is a kind of electrochemical cell, comprising：Anode comprising metal；It is supplied with
The porous cathode of gas comprising nitrogen oxide (NO)；Spacer body between anode and cathode；And electrolyte；The wherein NO
It is activated cathode ingredient.
In embodiments of the invention, which can include oxidation reduction catalyst, conductive material and bonding
The porous battery structure of agent.The cathode can pass through mixed oxidization reducing catalyst, conductive material and optional adhesive and general
Mixture is applied to the collector of suitable shape to construct.The oxidation reduction catalyst can promote NO redox reactions
Any material.NO absorbing catalysts can contain any material that NO is promoted to absorb as its active component.Suitable catalyst
The example of active component includes but not limited to its oxide (Li2O、Na2O、K2O, MgO, CaO, SrO, BaO), hydroxide
(LiOH、NaOH、KOH、Mg(OH)2、Ca(OH)2、Sr(OH)2、Ba(OH)2), carbonate (Li2CO3、Na2CO3、K2CO3、MgCO3、
CaCO3、SrCO3、BaCO3) or its form arbitrarily combined alkali or alkaline earth metal.The active component is usually immersed in height
Surface area oxide support such as Al2O3、ZrO2、TiO2、CeO2Or on its arbitrary mixed oxide.The rate that NO absorbs can lead to
Addition noble metal such as Pt, Pd, Rh or its arbitrary combination are crossed to improve.
The positive electrode can contain conductive material, be chemically stable in the potential window used of the battery.It is excellent
The conductive material is selected to be porous and there is big specific surface area to provide height output.The example of such material can be included but not
It is limited to carbonaceous material such as Ketjen black, acetylene black, gas-phase growth of carbon fibre, graphene, native graphite, Delanium and activated carbon.
Other suitable conductive materials can be conductive fiber, such as metallic fiber, metal powder, such as nickel and aluminium and organic conductive material
Material, such as polyphenylene derivatives.In some embodiments, a mixture of these materials can be used.Other suitable conductions
Material can be conductivity ceramics such as titanium nitride and titanium carbide.
The known chemically stable proper adhesive in the potential window used of the battery of those of ordinary skill in the art
It can include thermoplasticity and thermosetting resin.For example, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) (PTFE), polyvinylidene fluoride
(PVDF), styrene butadiene ribber, tetrafluoroethene hexafluoroethylene analog copolymer, tetrafluoroethene hexafluoropropylene copolymer (FEP),
Tetrafluoroethene perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE resins), polychlorostyrene trifluoro second
Olefine resin (PCTFE), vinylidene fluoride-pentafluoropropylenecopolymer copolymer, ethylene-chlorotrifluoro-ethylene copolymer (ECTFE) and ethylene-acrylic acid are total to
Polymers.These adhesives can be used independently or can use mixture.
The component wet method can be blended or be set using mortar or other conventionally known mixing in the presence of suitable solvent
Standby dry method blends.The mixture then can be applied to charge collector by conventionally known method.It is any suitable to use
Charge collector.Preferred charge collector can be any one of carbon, stainless steel, nickel, aluminium and copper.In order to assist NO's
Diffusion, the preferable collector is porous body, such as net.In certain embodiments, which can include resistance to oxidation
The protective coating of metal or alloy with protect the collector from oxidation.
In the particular embodiment of the present invention, the metal of the negative electrode is included selected from lithium, sodium, potassium, magnesium, calcium, aluminium
With one kind of zinc, in one particular embodiment, the metal of the negative electrode is one kind of lithium and magnesium.
LiPF can be included by being inserted in the electrolyte ion transmitting medium between positive electrode and anode6、LiClO4、LiAsF6、
LiBF4、Li(CF3SO2)2N、Li(CF3SO3) and LiN (C2F5SO2)2It is one or more be used as electrolyte.Non-aqueous solvent is
Preferably, and organic solvent can be selected from, including cyclic carbonate ester, chain carbonic acid ester, cyclic ester, cyclic ethers and chain ether.The reality of cyclic carbonate ester
Example includes ethylene carbonate, propylene carbonate, butylene carbonate and vinylene carbonate.The example of chain carbonic acid ester includes carbonic acid two
Methyl esters, diethyl carbonate and methyl ethyl carbonate.The example of cyclic ester carbonic ester includes gamma-butyrolacton and gamma-valerolactone.The reality of cyclic ethers
Example includes tetrahydrofuran and 2- methyltetrahydrofurans.The example of chain ether includes dimethoxy-ethane and glycol dimethyl ether.One
In a little preferred embodiments, which can be nitrile series solvent such as acetonitrile or ionic liquid.Ionic liquid include it is arbitrary sun from
Son such as glyoxaline cation, piperidines cation, pyrrolidines cation and ammonium cation and arbitrary anion such as bis- (three
Fluorine mesyl) imide anion, bis- (fluorosulfonyl) imide anions, tetrafluoroborate anion and hexafluorophosphoric acid
Root anion.In a preferred embodiment, which is ionic liquid, such as the bis- (trifluoros of N- Methyl-N-propyl piperidines
Methyl sulphonyl) acid imide (PP13TFSI).
One example of the electrochemical cell of the present invention is shown in figure 3.The negative electrode 25 is placed in shell 21, and put
Positive electrode is put with opposite via spacer body 27 and negative electrode 25.Electrolyte 28 is between anode 23 and cathode 25.Porous plate 22 exists
On positive electrode 23, NO supply inlets 29 are connected across the porous plate with the positive electrode.
In addition, the it has been found by the present inventors that gas of component containing NO and usually found in internal combustion engine exhaust gas
It can effectively function as and wait to feed to the source of the active material of the cathode.Such unexpected discovery allows exploitation by gold
Belong to the energy resource system in the car that NO gases accumulator is formed, wherein internal combustion engine exhaust gas is fed to the moon of the accumulator
The source of the gas of pole.
Even if the present inventor further shows as NO and nitrogen oxide such as NO in figures 4 and 52During mixing, still
Observe NxOyGas redox reacts, and the redox property is quite similar to the redox of pure NO gas reactions
Performance.Even if under exhaust gas conditions, N is also observedxOyGas redox reacts, and then it is quite similar in aspect of performance
The performance of pure NO gas reactions.Other materials such as hydro carbons and carbon monoxide are not shown to NxOyAny shadow of redox reaction
It rings.
Therefore, further embodiment of the invention is a kind of electrochemical cell, comprising：Anode comprising metal；For
Should have comprising nitrogen oxide (NO) and at least one selected from formula NxOyNitrogen oxides, oxygen, vapor, gaseous hydrocarbon, carbon monoxide and
The porous cathode of the gas of gas in carbon dioxide；Spacer body between anode and cathode；And electrolyte；It is wherein active
Cathode composition is NO or formula NxOyCompound, wherein x be 1 or 2 and y be 1 to 4 integer.
Without being limited by theory, it is believed that the element of the present invention includes the N with unpaired electronxOyGas is made
For reactant gas, i.e. active cathode material, the wherein NxOyGas defines NO, NO2And N2O4.This NxOyGas is included in
In exhaust gas.
But in the model battery described in front, discharge capacity is generally only about the 33% of charging capacity.The present inventor
Think, in model battery, the NO of charged state+Anode can be easily diffused in electrolyte medium, it will be also there
Original is into NO, even if in charging process so.Due to this migration and reduction, the after charging electrification near working electrode
The concentration of lotus substance significantly exhausts, therefore, in electric discharge, NO+Concentration it is at a fairly low compared with charging capacity, thus coulombic efficiency
Also it is very low.
Therefore, in a further embodiment, the present invention includes a kind of electrochemical cell, it includes：Include work electricity
The anodal compartment of pole, the working electrode include metal；Cathodic compartment comprising porous cathode, the porous cathode are supplied with packet
Containing NxOyGas；Between anodal compartment and cathodic compartment and the separator that both separates；And mobility ionophore；
The wherein NxOyIt is activated cathode ingredient, and the separator conducts the mobility ionophore and non-conducting NxOy +Ion.
Present inventor have determined that do not allow N by being inserted between the anode and the cathodexOy +Substance by separator,
Electrically charged substance is merely retained near cathode.The purpose of the separator is that electrically charged substance is hindered to spread Zhiyang by cathode
Pole, and finally cut off the diffusion.The separator must be allowed for mobility carrier to pass through in entire battery system.Therefore, should
The structure of separator must be changed to meet ionic conduction property according to mobility carrier.For example, in Li electro-chemical systems
In, use the separator for effectively conducting Li ions.Equally, in Mg electro-chemical systems, the separator of conduction magnesium ion is used.
The separator can be the form of film, by polymer, ceramics or its composite material structure.In order to reduce gas to anode performance
Any adverse effect, effective separator will to gas completely it is impermeable or substantially impermeable, thus prevent gas by cathode
Compartment enters anodal compartment.Preferred separator is dense ceramic membrane.For example, the separator can be in Li systems lithium-from
Sub- conductive ceramic plate, more specifically, Li-La-Ti-O based perovskites, Li-Al-Ti-P-O bases NASICON, Li-La-Zr-O
Foundation stone garnet, Li-P-S based solid electrolytes and Li-Ge-P-S based solid electrolytes are the examples of lithium-ion-conducting ceramics.
Since there are separator, which is divided into anodal compartment and cathodic compartment.Select the electrolyte ion
Or mobility ionophore is so as to the metals compatible with electrode.Such material is conventionally known to those skilled in the art.Example
Such as, when anode includes lithium, which can include LiPF6、LiClO4、LiAsF6、LiBF4、LiN(CF3SO2)2、Li
(CF3SO3) and LiN (C2F5SO2)2It is one or more.
One example of the lithium electrochemical cells of the embodiment is illustrated schematically in Fig. 6.In figure 6, the separator
Labeled as ceramic electrolyte, and the cathodic compartment contains the 2nd liquid electrolyte and carbon cathode, and the anodal compartment contains the 1st
Electrolyte and lithium anode.The battery is contained in container, and the container is filled with including cathode activity gas (NO or the equilibrium oxygen compound
NO2And/or N2O4) gas.The gas enters the cathode by the opening of poly- (ether ether ketone) (PEEK) resin containing cathode line
Compartment.
The present inventor further shows in figures 4 and 5, even if as NO and nitrogen oxides such as NO2During mixing, still observe
NxOyGas redox reacts, and redox property is quite similar to pure NO gas reactions.Even if under exhaust gas conditions,
Also N is observedxOyGas redox reacts, and it is quite similar to pure NO gas reactions in aspect of performance.Other materials are such as
Hydro carbons and carbon monoxide are not shown to NxOyAny influence of redox reaction.
Present inventors have surprisingly discovered that even if the NO gases are exposed to surrounding air, NO is generated2Gas, still
Observe almost the same redox active (Fig. 4).The NxOyAdmixture of gas is as the moon in metal-gas accumulator
Pole active material provides the highly reactive property gas group of excellent properties.
As a result, in a further embodiment, the present invention provides the rechargeable electric power storages equipped with NO gas feeds
Pond, in one particular embodiment, the gas feed are a components of system, and the wherein NO is obtained from the useless of internal combustion engine
Gas.One example of such system is illustrated schematically in Fig. 8, wherein by using such as NO gas absorbers from leaving internal combustion
The NO gases are collected in the main flow of gas of engine.Then, the NO gases of collection are discharged into from absorber in accumulator, described
It is produced electricl energy in accumulator.After cycling, the NO gases for accumulator reaction can be discharged from the accumulator, and then will
New NO gases from absorber are introduced into the accumulator.Release can pass through vacuum suction or other routines from accumulator
Method is realized.The gas of release can be mixed with fresh exhaust gas and be guided into for processed conventionally catalytic reactor, with
After be discharged into environment.Certainly, as shown in Figure 8, the normal stream of engine exhaust can march to 15 by 11 through 12.Other
In embodiment, feed to the NO of the metal-NO accumulators and can be enriched in feed system.
In order to protect the accumulator, NO chargings can cool down before the accumulator is entered.NO chargings can be continuous
Stream or intermittent flow.
Due to NOxGas is the component of internal combustion engine exhaust gas, therefore this is had found that it is likely that with significant environment and energy
Source is as a result, because as shown in Figure 8, can build wherein NO obtained from the exhaust gas of internal combustion engine and feed to metal-NO electric power storages
The system in pond.Such system will eliminate at least NO from exhaust gas, and be translated into electric energy.
In the other aspects of the embodiment, the present invention provides equipped with NO or NxOyThe rechargeable of gas feed
Accumulator, and the gas feed is the component of wherein system of the internal combustion engine exhaust gas as active material feed source.
In another embodiment, feed to the metal-NxOyExhaust gas in accumulator can be enriched in the feed system together with NO.
In order to protect the accumulator, exhaust gas charging can be cooled before the accumulator is entered.The charging of the gas can be continuous
Stream or intermittent flow.
The present invention has been generally described, can be further understood from reference to certain specific embodiments, unless separately
Professional etiquette is determined, and the embodiment is only to illustrate purpose and provide herein, is not intended to limit.
Embodiment
It builds containing working electrode, to the test battery of electrode and reference electrode to compare the O as active material of cathode2
And NO.
Test gas is obtained by corresponding high-grade gas bomb.The working electrode is respectively to electrode and reference electrode
Rodlike vitreous carbon, Pt and containing tetrabutylammonium perchlorate (TBAP) and as support salt AgNO3Acetonitrile solution in
Ag.Sweep speed is 50 mv s, and operation temperature is room temperature.
Fig. 1 is shown in bis- (trifyl) acid imide (PP13TFSI) the base electrolysis of N- Methyl-N-propyl piperidines
Cyclic voltammogram in matter solution；
Comparative example 1
In pure O2Under gas in 0.2 mol/kg of PP13TFSI-LiTFSI solution
Embodiment 1
In 0.2 mol/kg of PP13TFSI- under NO/Ar/He mixed gas (l volume %/l volumes %/98 volume %)
In LiTFSI solution
Embodiment 2
In 0.l mols/kg of PP13TFSI- under NO/Ar/He mixed gas (l volume %/l volumes %/98 volume %)
Mg(TFSI)2In solution
As can be seen, in about -1.0V (vs.Ag/Ag+) at observe because of O2Cathode peak caused by reduction, and
1.0V(vs.Ag/Ag+) at observe and be attributed to NO+The peak of reduction.In addition, in O2It is observed under atmosphere big between reduction and oxidation
Peak separation (1.2V), and small separation is observed under NO atmosphere.Should the result shows that, with O2Gas phase ratio, NO gases have
Higher operating voltage and higher invertibity (rechargeablility).
With NO gases as cathode material and 0.2 mol/kg of PP13TFSI-LiTFSI solution as electrolyte with
The identical battery of above-mentioned construction is maintained at 700nA/cm2Current density under, the charge-discharge curves measured are as shown in Figure 2.
Respectively charging and discharging platform is observed in about 1.05 volts and 0.95 Fu Chu.In addition, when battery is maintained under open circuit potential, point
The flat current potential after being charged and discharged is observed at 1.0V not at slightly above 1.0V and slightly below.It is kept on cathode as a result,
Charging and discharging state, and the evidence of NO redox reactions is provided.By introducing NO gases into metal-gas accumulator,
Significantly improve operating voltage and voltage hysteresis.
Test the NO mixed with waste gas component
It builds containing working electrode, to the test battery of electrode and reference electrode to compare as active material of cathode not
Same gas containing NO.Then obtain cyclic voltammogram.Fig. 4 is shown in bis- (the trifluoro methylsulfonyls of N- Methyl-N-propyl piperidines
Base) cyclic voltammogram in acid imide (PP13TFSI) base electrolyte solution：
Embodiment 2 is under pure NO/Ar/He (l%/l%/98%) gas condition in 0.1 mol/kg of PP13TFSI-Mg
(TFSI)2It is carried out in solution.The color of the gas atmosphere of the battery is always transparent.
Embodiment 3 in the case where being exposed to surrounding air the NO/Ar/He of 5 minutes (l%/l%/98%) gas 0.1 mole/
Kilogram PP13TFSI-Mg (TFSI)2It is carried out in solution.The color of the gas atmosphere is slightly moderate brown.
Fig. 5 is shown in bis- (trifyl) acid imide (PP13TFSI) the base electrolysis of N- Methyl-N-propyl piperidines
Cyclic voltammogram in matter solution：
Embodiment 4-1 and 4-2 is in pure O2/NO/CO/C3H6/ Ar/He (2%/0.4%/0.1%/0.13%/97.5%) gas
In 0.1 mol/kg of PP13TFSI-Mg (TFSI) under concrete conditions in the establishment of a specific crime2It is run in solution with different scanning range.The face of gas atmosphere
Color is slightly moderate brown.
Embodiment 5
Lithium/N is built according to the structure schematically shown in Fig. 6xOyGas accumulator.Supplied to the N of cathodexOyReaction gas
Body is the mixture of NO/Ar/He (l%/l%/98%) gas, and surrounding air is had been exposed to before entering in accumulator
Lower 5 minutes.The cathode is two panels carbon paper (Toray, TGP-H-120), and catholyte (the 2nd electrolyte) is rubbed containing 0.35
Bis- (trifyl) acid imides of the N of that/kilogram LiTFSI (3M), N- diethyl-N- methyl-N- (2- methoxy ethyls) ammonium
(DEMETFSI, Kanto company), glass fibre are used as spacer body (Whattman), and ceramic separator (electrolyte) is OHARA
The Li-Al-Ti-P-O bases NASICON ceramics of Inc manufactures.Anodolyte is：In propylene carbonate (PC, Kishida
Chemical bis- (trifyl) the imide li LiTFSI (3M) of 1M in).
Fig. 7 show schematically shown in Fig. 6 and paragraph in front described in Li/NxOyGas accumulator it is initial
Charge-discharge curves.It is used as separator by introducing Li ionic conductivity ceramic membranes between cathode and anode, such as institute of the present invention
It states, the NxOyThe invertibity (coulombic efficiency) of redox reaction is almost 100% and high reversible.Discharge voltage is maintained at more
Under high voltage.As a result, as shown in Figure 7, the voltage hysteresis difference during charge and discharge is also narrow.
It is possible to many modifications and variations of the present invention in view of above description and embodiment.It is therefore understood that
, within the scope of following claims, the present invention can by be different from it is specifically described herein in a manner of implement.It is any
Such embodiment is intended within the scope of the invention.
Claims (22)
1. a kind of metal-gas accumulator, comprising：
Anode, it includes metal as active anode ingredient；
Porous cathode is contacted with the gas comprising nitrogen oxide (NO) so that NO is activated cathode ingredient；
Spacer body between anode and cathode；And
Non-aqueous electrolyte；
Wherein the accumulator is rechargeable.
2. metal as described in claim 1-gas accumulator, wherein the metal of the anode include selected from lithium, sodium, potassium, magnesium,
One kind in calcium, aluminum and zinc.
3. metal as claimed in claim 2-gas accumulator, wherein the metal includes lithium.
4. metal as claimed in claim 2-gas accumulator, wherein the metal includes magnesium.
5. metal as described in claim 1-gas accumulator, wherein the accumulator also includes to introduce the gas for including NO
The gas access of body charging.
6. a kind of vehicle, comprising：
Internal combustion engine with the exhaust gas comprising NO；
Accumulator as described in any one of claim 1-5；With
It is connected to the NO absorbers of the waste gas system of the engine；
Wherein described NO absorbers are connected with the gas access of the accumulator, and the NO from the exhaust gas enters via the gas
Mouth is fed in the accumulator.
7. a kind of metal-gas accumulator, comprising：
Anode, comprising metal as active anode ingredient；
Porous cathode, with including formula NxOyNitrogen oxides and selected from oxygen, vapor, gaseous hydrocarbon, carbon monoxide and titanium dioxide
At least one gas contact of carbon；
Spacer body between anode and cathode；With
Non-aqueous electrolyte；
Wherein activated cathode ingredient is formula NxOyCompound, wherein x be 1 or 2, and y be 1 to 4 integer and
Wherein the accumulator is rechargeable.
8. metal as claimed in claim 7-gas accumulator, wherein the metal of the anode include selected from lithium, sodium, potassium, magnesium,
One kind in calcium, aluminum and zinc.
9. metal as claimed in claim 8-gas accumulator, wherein the metal includes lithium.
10. metal as claimed in claim 8-gas accumulator, wherein the metal includes magnesium.
11. metal as claimed in claim 7-gas accumulator, wherein the accumulator also includes to introduce comprising NxOy's
The gas access of gas feed, the gas feed are the exhaust gas streams from internal combustion engine.
12. metal-gas accumulator as described in claim 7 or 11, wherein the formula NxOyNitrogen oxides be NO.
13. a kind of vehicle, comprising：
Internal combustion engine with exhaust gas, the exhaust gas are included selected from formula NxOyNitrogen oxides, oxygen, vapor, gaseous hydrocarbon, one
At least one gas of carbonoxide and carbon dioxide；With
Metal-gas accumulator as described in any one of claim 7-12.
14. vehicle as claimed in claim 13, wherein formula NxOyNitrogen oxides be NO.
15. a kind of electrochemical cell, comprising：
Anodal compartment comprising working electrode, the working electrode include metal；
Cathodic compartment comprising porous cathode, the cathodic compartment are supplied with comprising redox active NxOyGaseous compound
Gas；
Between anodal compartment and cathodic compartment and the separator that both separates；And
Mobility ionophore；
Wherein
X is 1 or 2, y are 1,2 or 4,
The NxOyIt is activated cathode ingredient, and
The separator conducts the mobility ionophore and non-conducting NxOy +Ion.
16. electrochemical cell as claimed in claim 15, wherein
The separator be in the composite material comprising gel, polymer, ceramic material and polymer and ceramic material extremely
A kind of few film.
17. electrochemical cell as claimed in claim 16, wherein
The separator is the film for including ceramic material, and the ceramic material is dense ceramic membrane.
18. electrochemical cell as claimed in claim 15, wherein the metal of the anode is included selected from lithium, sodium, magnesium, aluminium, silver
With a kind of metal in copper.
19. electrochemical cell as claimed in claim 15, wherein
The metal of the anode includes lithium,
The separator be dense ceramic membrane and
The dense ceramic membrane is lithium-ion-conducting film, comprising selected from Li-La-Ti-O perovskites, Li-Al-Ti-P-O
At least one of NASICON, Li-La-Zr-O garnet, Li-P-S solid electrolytes and Li-Ge-P-S solid electrolytes pottery
Porcelain.
20. rechargeable battery includes electrochemical cell as claimed in claim 15.
21. rechargeable battery as claimed in claim 20, wherein the accumulator includes to introduce comprising oxidation also
Former activity NxOyThe gas access of the gas feed of gaseous compound.
22. a kind of vehicle, comprising：
Internal combustion engine with exhaust gas, the exhaust gas include redox active NxOyGaseous compound；
Accumulator as described in claim 20 or 21；With
It is connected to the N of the waste gas system of the enginexOyAbsorber；
Wherein described NxOyAbsorber is connected with the gas access of the accumulator, and pass through the gas access will come from it is described
The N of exhaust gasxOyIt is fed in the accumulator.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/150,168 US9331369B2 (en) | 2014-01-08 | 2014-01-08 | Rechargeable metal nitric oxide gas battery |
| US14/150,168 | 2014-01-08 | ||
| US14/221,814 US9461349B2 (en) | 2014-01-08 | 2014-03-21 | Rechargeable metal NxOy gas battery system |
| US14/221,814 | 2014-03-21 | ||
| US14/222,989 | 2014-03-24 | ||
| US14/222,989 US9368847B2 (en) | 2014-01-08 | 2014-03-24 | Rechargeable metal nitric oxide gas battery |
| PCT/IB2014/002809 WO2015104574A1 (en) | 2014-01-08 | 2014-09-29 | Rechargeable metal nitric oxide gas battery system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105899280A CN105899280A (en) | 2016-08-24 |
| CN105899280B true CN105899280B (en) | 2018-07-06 |
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| CN201480072628.0A Active CN105899280B (en) | 2014-01-08 | 2014-09-29 | Rechargeable metal nitrogen oxide gas battery system |
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| Country | Link |
|---|---|
| JP (1) | JP6373389B2 (en) |
| CN (1) | CN105899280B (en) |
| WO (1) | WO2015104574A1 (en) |
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| US3979225A (en) * | 1974-12-13 | 1976-09-07 | United Technologies Corporation | Nitrogen dioxide regenerative fuel cell |
| CN1349903A (en) * | 2000-10-25 | 2002-05-22 | 丰田自动车株式会社 | Mixed vehicle to reduce emission of NCx and method of operating said vehicle |
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| CN103154323A (en) * | 2010-10-15 | 2013-06-12 | 能源及环境研究中心基金会 | Electrochemical process for the preparation of nitrogen fertilizers |
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| US4390602A (en) * | 1981-09-21 | 1983-06-28 | Struthers Ralph C | Fuel cell |
| US5084144A (en) * | 1990-07-31 | 1992-01-28 | Physical Sciences Inc. | High utilization supported catalytic metal-containing gas-diffusion electrode, process for making it, and cells utilizing it |
| LU88021A1 (en) * | 1991-10-21 | 1993-05-17 | Euratom | Process for the preparation of hydroxylamine from NOx-containing exhaust gases |
| US5447610A (en) * | 1994-06-23 | 1995-09-05 | Sachem, Inc. | Electrolytic conversion of nitrogen oxides to hydroxylamine and hydroxylammonium salts |
| US6593023B2 (en) * | 2001-04-27 | 2003-07-15 | The Gillette Company | Battery and method of making the same |
| CN100344019C (en) * | 2004-06-16 | 2007-10-17 | 松下电器产业株式会社 | Active material, manufacturing method thereof and nonaqueous electrolyte secondary battery containing the material |
| JP5614521B2 (en) * | 2005-01-24 | 2014-10-29 | 独立行政法人産業技術総合研究所 | Solid carbon decomposition type ceramic chemical reactor |
| JP2007292010A (en) * | 2006-04-27 | 2007-11-08 | Toyota Motor Corp | Purification of exhaust gas exhausted from internal combustion engine and including nitrogen oxides |
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2014
- 2014-09-29 WO PCT/IB2014/002809 patent/WO2015104574A1/en active Application Filing
- 2014-09-29 JP JP2016545355A patent/JP6373389B2/en active Active
- 2014-09-29 CN CN201480072628.0A patent/CN105899280B/en active Active
Patent Citations (4)
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|---|---|---|---|---|
| US3979225A (en) * | 1974-12-13 | 1976-09-07 | United Technologies Corporation | Nitrogen dioxide regenerative fuel cell |
| CN1349903A (en) * | 2000-10-25 | 2002-05-22 | 丰田自动车株式会社 | Mixed vehicle to reduce emission of NCx and method of operating said vehicle |
| CN103140437A (en) * | 2010-09-30 | 2013-06-05 | 巴斯夫欧洲公司 | Process for working up an exhaust gas from a system for producing hydroxylamine or hydroxylammonium salts |
| CN103154323A (en) * | 2010-10-15 | 2013-06-12 | 能源及环境研究中心基金会 | Electrochemical process for the preparation of nitrogen fertilizers |
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| WO2015104574A1 (en) | 2015-07-16 |
| JP6373389B2 (en) | 2018-08-15 |
| JP2017504163A (en) | 2017-02-02 |
| CN105899280A (en) | 2016-08-24 |
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