CN108352556A - Gas analysis unit and gas analysis system - Google Patents
Gas analysis unit and gas analysis system Download PDFInfo
- Publication number
- CN108352556A CN108352556A CN201680064835.0A CN201680064835A CN108352556A CN 108352556 A CN108352556 A CN 108352556A CN 201680064835 A CN201680064835 A CN 201680064835A CN 108352556 A CN108352556 A CN 108352556A
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- gas analysis
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- 238000004868 gas analysis Methods 0.000 title claims abstract description 230
- 239000007789 gas Substances 0.000 claims description 345
- 239000012159 carrier gas Substances 0.000 claims description 113
- 238000005192 partition Methods 0.000 claims description 56
- 239000012528 membrane Substances 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004458 analytical method Methods 0.000 description 51
- 239000000203 mixture Substances 0.000 description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000001307 helium Substances 0.000 description 16
- 229910052734 helium Inorganic materials 0.000 description 16
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 238000001514 detection method Methods 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000873 masking effect Effects 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
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- 230000005611 electricity Effects 0.000 description 5
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229960004424 carbon dioxide Drugs 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000009931 harmful effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
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- 238000007789 sealing Methods 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
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- 238000009835 boiling Methods 0.000 description 3
- 229920005549 butyl rubber Polymers 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- 229920001155 polypropylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229910018095 Ni-MH Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910018477 Ni—MH Inorganic materials 0.000 description 2
- 229920006169 Perfluoroelastomer Polymers 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
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- 229920002530 polyetherether ketone Polymers 0.000 description 2
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- 239000007784 solid electrolyte Substances 0.000 description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 239000001996 bearing alloy Substances 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- VUFYPLUHTVSSGR-UHFFFAOYSA-M hydroxy(oxo)nickel Chemical compound O[Ni]=O VUFYPLUHTVSSGR-UHFFFAOYSA-M 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The gas analysis unit and gas analysis system that can be more precisely analyzed are provided.Measuring chamber (6) configuration positive (7) in unit main body (2) and cathode (8).Separator (9) is configured between 1 pair of electrode (7), (8).The gas generated in positive (7) side relative to separator (9) and the gas generated in cathode (8) side relative to separator (9), are detached and are captured respectively by 1 pair of capture portion (21), capture portion (22).Since the gas that can be captured to each capture portion (21), capture portion (22) is individually analyzed, so compared with the case where being analyzed with not making the gas generated in positive (7) side and cathode (8) side reciprocally detach, can more precisely be analyzed.
Description
Technical field
The present invention relates to gas analysis unit and gas analysis system, the gas analysis unit is arranged in inside
There is a pair of electrodes being made of anode and cathode and is configured at the pair of interelectrode separation membrane.
Background technology
In the various batteries such as lithium ion battery (secondary cell), generated from anode and cathode in electric discharge or when charging
Gas, the gas make electrode or electrolyte aging or make the reduction of the efficiency of electric discharge or charging sometimes.Therefore, grinding in battery
In studying carefully or developing, sometimes analyze positive electrode and negative electrode between voltage variation with the variation and from anode and cathode
Relationship between the ingredient or amount of the gas of generation.
In this case, using with the material of material identical used in actual battery and the anode that is formed and negative
Pole utilizes gas-chromatography by being discharged or being charged with these positive and cathode in unit to being configured at gas analysis
The analytical equipment of instrument etc. analyzes (referring for example to following non-patent literatures the gas generated in gas analysis unit
1)。
Existing technical literature
Non-patent literature
Non-patent literature 1：《Electro-chemical test unit ECC-DEMS user's manuals (Electrochemical Test Cell
ECC-DEMS User Manual)》, German EL-CELL companies, [online], on 2 11st, 2015, [on October 28th, 2015
Retrieval], network address ＜ URL：http://el-cell.com/wp-content/uploads/manuals/ECC_DEMS_
manual.pdf〉
Invention content
Technical problems to be solved by the inivention
It is made of respectively different ingredients in the gas that the side of the positive electrode and negative side of battery generate, in side of the positive electrode and cathode
The amount for the gas that side generates is also different.But in existing gas analysis unit, generated in side of the positive electrode and negative side
Gas is sent to gas chromatograph and is analyzed in a manner of mutually unseparated.Therefore, it is impossible to distinguish the gas generated in side of the positive electrode
The ingredient of body and amount and the ingredient of gas and amount that are generated in negative side and be accurately proceed analysis.
The present invention proposes that its purpose is to provide the gases that can be more precisely analyzed point in view of the above circumstances
Analysis unit and gas analysis system.
Scheme for solving above-mentioned technical problem
(1) gas analysis of the invention has with unit：Unit main body, 1 pair of electrode, separation membrane, 1 pair of capture portion.It is described
Unit main body has measuring chamber in inside.1 pair of electrode is made of the anode and cathode for being configured at the measuring chamber.It is described
Separation membrane is configured between 1 pair of electrode.1 pair of capture portion will be generated relative to the separation membrane in the side of the positive electrode
Gas and the gas generated in the negative side relative to the separation membrane are detached and are captured respectively.
According to such composition, the gas that is generated in side of the positive electrode relative to separation membrane and relative to separation membrane in negative side
The gas of generation is detached and is captured in 1 pair of capture portion respectively, thus can to gas that each capture portion is captured individually into
Row analysis.Therefore, compared with the case where being analyzed with not making the gas generated in side of the positive electrode and negative side reciprocally detach
Compared with can more precisely be analyzed.
(2) can also be that the gas analysis is also equipped with 1 pair of partition for closing off 1 pair of capture portion with unit.
According to such composition, syringe is inserted into each capture portion via 1 pair of partition, it can be independent by the syringe
Ground suction is analyzed by the gas that each capture portion is separated and captures.Therefore, it is possible to more precisely carry out interim analysis.
Can also be that the gas analysis is also equipped with the 1 pair of partition for respectively pressing 1 pair of partition and installing with unit
Holder.In this case, space that can also be into partition holder supplies masking gas.
According to such composition, syringe is inserted into each capture portion via 1 pair of partition, is individually taken out by the syringe
Inhale by each capture portion it is separated and capture gas after, when syringe is extracted from partition, can prevent outside air into
Enter in syringe.That is, even if in the state of in syringe being decompression, since the masking of the space supply into partition holder is used
Gas enters instead of extraneous air in syringe, so can prevent external air from entering in syringe.
(3) can also be, 1 pair of capture portion be respectively formed with make carrier gas flow into the inflow entrance in the capture portion with
The outflux for making carrier gas be flowed out out of this capture portion.
According to such composition, the gas captured in capture portion is flowed into from inflow entrance together with the carrier gas in capture portion
It flows out from outflux, therefore by analyzing the gas, more precisely can continuously be analyzed.
Can also be to configure the outflux on the extended line of the inflow direction of the carrier gas flowed into from the inflow entrance.
According to such composition, since inflow entrance and outflux are configured in straight line along the inflow direction of carrier gas
On, therefore flow path composition can be simplified.
(4) can also be that the gas analysis unit makes the carrier gas flowed into from the inflow entrance generate stirring stream.
According to such composition, stirring stream is generated by the carrier gas for making to flow into from inflow entrance, capture portion can be captured
Gas equably stirred, therefore stable analysis result can be obtained.
Can also be that the gas analysis is also equipped with resistance elements with unit, which becomes and pass through the capture
The resistance of carrier gas in portion and generate stirring stream.
According to such composition, the carrier gas flowed into from inflow entrance is due to by the resistance from resistance elements and in capture portion
Inside it is stirred.It is equably stirred thereby, it is possible to the gas captured to capture portion and it is made to be flowed out from outflux, it can be right
The gas is analyzed, therefore can obtain stable analysis result.
(5) can also be that the gas analysis unit can also have：Gas supply line, gas discharge duct, side
Through-flow road, bypass switching part.The gas supply line supplies carrier gas to the inflow entrance.The gas discharge duct makes load
Gas is discharged from the outflux.The bypass flow path connects the gas supply line and described not via the capture portion
Gas discharge duct.The bypass switching part switches over so that the gas supply line and the capture portion or the bypass
Any of flow path is connected to.
According to such composition, can be made in gas supply line and capture portion or bypass flow path by bypassing switching part
Any one connection.Therefore, by making gas supply line be connected to bypass flow path, gas can supplied via bypass flow path
After air discharge in flow path, gas supply line is made to be connected to capture portion and supply carrier gas to capture portion.Thereby, it is possible to anti-
Only the air in gas supply line flows into capture portion and causes harmful effect to analysis, therefore can more precisely carry out
Analysis.
(6) can also be that the gas analysis is also equipped with to be impregnated in unit and be filled to the electrolyte of the measuring chamber
Reference electrode.
According to such composition, using the voltage measured by reference electrode as reference voltage, reference electrode 20 can be carried out
The analysis of the current potential between current potential and reference electrode 20 and cathode 8 between anode 7.
(7) can also be that the gas analysis is also equipped with electrode guides with unit, the electrode guides are accommodated in
In the measuring chamber, the side in 1 pair of electrode is held in the inside of electrode guides.In this case, can also be,
The electrode guides are formed with the opening being connected to the side in 1 pair of capture portion.
According to such composition, the side in 1 pair of electrode is kept by electrode guides, and is produced in the electrode guides
Raw gas is directed to the side in 1 pair of capture portion via opening.The gas generated as a result, in the electrode side of a side is from electrode
It is captured well to the capture portion of a side, therefore can be more precisely analyzed via opening in guide part.
(8) can also be that another party in 1 pair of electrode is configured at the survey on the outside of the electrode guides
Amount is indoor.In this case, can also be to be formed with path of navigation in the unit main body, it will be in the electrode of described another party
The gas that side generates is guided to another party in 1 pair of capture portion.
According to such composition, the gas that the electrode side of another party on the outside of electrode guides generates is via in unit master
Path of navigation that body is formed and captured well to the capture portion of another party, therefore can more precisely be analyzed.
(9) gas analysis system of the invention have the gas analysis unit with to 1 pair of capture portion at least
The gas analysis portion that the gas that one side is captured is analyzed.
According to such composition, the gas generated in gas analysis unit is divided by using gas analysis portion
Analysis, can more precisely analyze the ingredient in gas.
(10) it can also be that the gas analysis system is also equipped with supply switching part, gas supply state be switched to the 1st
Any one of supply state or the 2nd supply state, the 1st supply state are will to be produced in gas analysis unit
Raw gas supplies together with carrier gas to the gas analysis portion, and the 2nd supply state will not be contained in the gas point
The carrier gas of the gas generated in analysis unit is supplied to the gas analysis portion.
According to such composition, in the 1st supply state, pass through the gas and load that will be generated in gas analysis unit
Gas is directly supplied to gas analysis portion together, can continuously be analyzed.Therefore, with use syringe single in gas analysis
The gas generated in first is injected into such constitute in gas analysis portion and compares, and external air is difficult to be mixed into the flow path of gas
It is interior.Thereby, it is possible to prevent being mixed into for air from being impacted to analysis result, therefore more precisely can continuously be analyzed.
In addition, each interval between supply switching part switching, can supply the gas generated in gas analysis unit
To gas analysis portion and being analyzed, therefore quantitative analysis can be correctly carried out to the gas generated at each interval.
It in turn, can be in the gas if gas analysis is installed on supply switching part with unit in the 2nd supply state
Analysis carries out the connection of pipeline in the state of not being connected to gas analysis portion with unit.As a result, since be not necessarily in a great rush will be with gas
The pipeline of body analysis portion connection is connected to gas analysis unit, so installation exercise becomes easy.
(11) can also be, in the 1st supply state, via the gas analysis unit to the gas analysis
Portion supplies carrier gas, in the 2nd supply state, supplies and carries to the gas analysis portion not via the gas analysis unit
Gas.
According to such composition, in the 1st supply state, the gas generated in gas analysis unit divides from the gas
It is directly supplied to gas analysis portion in analysis unit.Therefore, it is possible to more precisely be analyzed with simply being constituted.
(12) can also be that the gas analysis system is also equipped with the gas to being generated in gas analysis unit
The trap portion accommodated.In this case, can also be, in the 1st supply state, via the trap portion to the gas
Analysis portion supplies carrier gas, and in the 2nd supply state, carrier gas is supplied to the gas analysis portion not via the trap portion,
The gas generated in gas analysis unit is accommodated in the trap portion.
According to such composition, if in the 2nd supply state, the gas generated in gas analysis unit is contained in trap
Then portion switches to the 1st supply state from the 2nd supply state, then can will be contained in the gas in trap portion together with carrier gas to gas
Body analysis portion supplies.Therefore, if it is the composition that can be accommodated in trap portion than more gases in gas analysis unit, then
More gases can be supplied from trap portion to gas analysis portion, therefore the detection sensitivity in gas analysis portion can be improved,
And then it can more precisely be analyzed.
(13) other gas analyses of the invention have with unit：Unit main body, 1 pair of electrode, separation membrane, cover,
Multiple seal members, the 1st gas supply line.The unit main body has measuring chamber in inside.1 pair of electrode is by being configured at
The anode and cathode of the measuring chamber are constituted.The separation membrane is configured between 1 pair of electrode.The cover is installed on
The unit main body closes the measuring chamber.The multiple seal member be set to the unit main body and the cover it
Between, seal the measuring chamber.1st gas flow path supplies gas to the space being formed between the multiple seal member
It gives.
According to such composition, it due to being provided with multiple seal members between unit main body and cover, can carry
The air-tightness of high measurement room makes external air hardly enter in unit main body.In turn, due to from the 1st gas supply line to
The space supply gas being formed between multiple seal members, thus even if external air flows into, because air is more thin, institute
Air can be driven out of to outside.It is entered in unit main body therefore, it is possible to effectively inhibit extraneous air.
(14) can also be that the gas analysis is also equipped with supply carrier gas into the unit main body the 2nd with unit
Gas supply line.In this case, can also be that the 1st gas supply line is described more to being formed in by the carrier gas
Space supply between a seal member.
According to such composition, the carrier gas supplied into unit main body, also to the sky being formed between multiple seal members
Between supply.It therefore, will not be to the gas even entering the situation in unit main body in the gas supplied into above-mentioned space
Analysis cause harmful effect, therefore can more precisely be analyzed.Further, since without preparing the gas different from carrier gas
Body, therefore device composition can be simplified.
(15) can also be that the unit main body is also equipped with 1 pair of capture portion, to relative to the separation membrane in the anode
The gas of side generation and the gas generated in the negative side relative to the separation membrane are detached and are captured respectively.At this
In the case of, can also be that at least one party of the 2nd gas supply line into 1 pair of capture portion supplies carrier gas.
According to such composition, to the gas that is generated in side of the positive electrode relative to separation membrane and relative to separation membrane in cathode
The gas that side generates respectively 1 pair of capture portion from and capture, therefore can to gas that each capture portion is captured individually into
Row analysis.Therefore, compared with the case where being analyzed with not making the gas that side of the positive electrode and negative side generate be separated from each other, energy
It is enough more precisely to be analyzed.
(16) other gas analysis systems of the invention have the gas analysis unit and in the unit masters
The gas analysis portion that the gas generated in vivo is analyzed.
According to such composition, the gas generated in gas analysis unit is divided by using gas analysis portion
Analysis, can more precisely analyze the ingredient in gas.
(17) it can also be that the gas analysis system is also equipped with supply switching part, gas supply state be switched to the 1st
Any one of supply state or the 2nd supply state, the 1st supply state are will to be produced in gas analysis unit
Raw gas supplies together with carrier gas to the gas analysis portion, and the 2nd supply state will not be contained in the gas point
The carrier gas of the gas generated in analysis unit is supplied to the gas analysis portion.
According to such composition, in the 1st supply state, pass through the gas and load that will be generated in gas analysis unit
Gas is directly supplied to gas analysis portion together, can continuously be analyzed.Therefore, with use syringe single in gas analysis
The gas generated in first is injected into such constitute in gas analysis portion and compares, and external air is difficult to be mixed into the flow path of gas
It is interior.Thereby, it is possible to prevent being mixed into for air from being impacted to analysis result, more precisely can continuously be analyzed.
In addition, each interval between supply switching part switching, can supply the gas generated in gas analysis unit
To gas analysis portion and being analyzed, therefore quantitative analysis can be correctly carried out to the gas generated at each interval.
It in turn, can be in the gas point if gas analysis is installed on supply switching part with unit in the 2nd supply state
Analysis carries out the connection of pipeline in the state of not being connected to gas analysis portion with unit.As a result, since be not necessarily in a great rush will be with gas
The pipeline of analysis portion connection is connected to gas analysis unit, so installation exercise becomes easy.
(18) can also be, in the 1st supply state, via the gas analysis unit to the gas analysis
Portion supplies carrier gas, in the 2nd supply state, supplies and carries to the gas analysis portion not via the gas analysis unit
Gas.
According to such composition, in the 1st supply state, the gas generated in gas analysis unit divides from the gas
It is directly supplied to gas analysis portion in analysis unit.Therefore, it is possible to more precisely be analyzed with simply being constituted.
(19) can also be that the gas analysis system is also equipped with the gas for being housed in and being generated in gas analysis unit
The trap portion of body.In this case, can also be, in the 1st supply state, via the trap portion to the gas analysis portion
Carrier gas is supplied, in the 2nd supply state, carrier gas is supplied to the gas analysis portion not via the trap portion, in the gas
The gas generated in body analysis unit is accommodated in the trap portion.
According to such composition, the gas generated in gas analysis unit can be accommodated in the 2nd supply state
In trap portion, the 1st supply state then is switched to from the 2nd supply state, then will be contained in the gas in trap portion together with carrier gas to gas
Body analysis portion supplies.Therefore, if it is can be accommodated in trap portion than structure as more gases in gas analysis unit
At, then it can be by more gases from trap portion to the supply of gas analysis portion, therefore the spirit of the detection in gas analysis portion can be improved
Sensitivity, and then can more precisely be analyzed.
Invention effect
In accordance with the invention it is possible to the gas that each capture portion is captured individually is analyzed, thus with do not make side of the positive electrode
And gas the case where reciprocally detaching and being analyzed that negative side generates, compares, and can more precisely be analyzed.
Description of the drawings
Fig. 1 is the stereogram of the configuration example for the gas analysis unit for showing one embodiment of the present invention.
Fig. 2 is the stereogram from the gas analysis unit of opposite side observation chart 1.
Fig. 3 is the exploded perspective view of the gas analysis unit of Fig. 1.
Fig. 4 is sectional view when cutting off the gas analysis of Fig. 1 in the horizontal direction with unit.
Fig. 5 A are sectional views when vertically cutting off the gas analysis of Fig. 1 with unit.
Fig. 5 B are sectional views when vertically cutting off the gas analysis of Fig. 1 with unit, show the feelings with Fig. 5 A
The section of condition different location.
Fig. 6 is the approximate vertical view for being illustrated to the action of triple valve.
Fig. 7 A are the detections that hydrogen is generated when showing in capture portion without continuously being analyzed in the state of resistance elements
The case where figure of an example of the variation of voltage, the flow velocity for showing to flow into the carrier gas in capture portion from inflow entrance is 5ml/min.
Fig. 7 B are the detections that hydrogen is generated when showing in capture portion without continuously being analyzed in the state of resistance elements
The figure of an example of the variation of voltage shows the case where flow velocity for the carrier gas being flowed into from inflow entrance in capture portion is 10ml/min.
Fig. 8 A are to show that there are the inspections of generation hydrogen when continuously being analyzed in the state of resistance elements in capture portion
The figure for surveying an example of the variation of voltage shows the case where flow velocity for the carrier gas being flowed into from inflow entrance in capture portion is 5ml/min.
Fig. 8 B are to show that there are the inspections of generation hydrogen when continuously being analyzed in the state of resistance elements in capture portion
The figure for surveying an example of the variation of voltage shows that the flow velocity for the carrier gas being flowed into from inflow entrance in capture portion is the feelings of 10ml/min
Condition.
Fig. 9 is to show that the current potential relative to reference electrode makes the potential change (i.e., cyclic voltammetry) of anode and filled
The figure of an example of the variation of electric current when electricity and electric discharge.
Figure 10 A are to show charge and discharge not to be repeated to the space supply gas being formed between multiple seal members
In the case of charge/discharge capacity variation figure.
Figure 10 B are to show that charge and discharge is repeated while to the space supply gas being formed between multiple seal members
The figure of the variation of charge/discharge capacity in the case of electricity shows the case where flow velocity of gas is 10ml/min.
Figure 10 C are to show that charge and discharge is repeated while to the space supply gas being formed between multiple seal members
The figure of the variation of charge/discharge capacity in the case of electricity shows the case where flow velocity of gas is 50ml/min.
Figure 11 is the figure for showing the oxygen concentration that the gas in unit main body is included and changing over time.
Whether Figure 12 is for illustrating influx of the oxygen into syringe because making masking be flowed into gas via connector
Partition holder and different figures.
Figure 13 A are the flow circuit diagrams of the configuration example for the gas analysis system for showing the 1st embodiment of the present invention.
Figure 13 B are the flow circuit diagrams of the configuration example for the gas analysis system for showing the 1st embodiment of the present invention.
Figure 14 A are the flow circuit diagrams of the configuration example for the gas analysis system for showing the 2nd embodiment of the present invention.
Figure 14 B are the flow circuit diagrams of the configuration example for the gas analysis system for showing the 2nd embodiment of the present invention.
Specific implementation mode
1. the composition of gas analysis unit
Fig. 1 is the stereogram of the configuration example for the gas analysis unit 1 for showing one embodiment of the present invention.Fig. 2 be from
The stereogram of the gas analysis of opposite side observation chart 1 unit 1.Fig. 3 is the exploded perspective view of the gas analysis unit 1 of Fig. 1.
Fig. 4 is sectional view when cutting off the gas analysis of Fig. 1 in the horizontal direction with unit 1.Fig. 5 A are that the gas analysis of Fig. 1 is single
Sectional view when member 1 is vertically cut off.Fig. 5 B are cuing open when vertically cutting off the gas analysis unit 1 of Fig. 1
View shows the section with different location the case where Fig. 5 A.
It is for being carried out to the gas generated from the lithium ion battery of an example as secondary cell that unit 1 is used in gas analysis
The device of analysis.In the gas analysis in unit 1, by reproducing structure identical with lithium ion battery in inside, can produce
Raw gas identical with lithium ion battery, and the gas is analyzed using gas chromatograph etc..
The gas analysis unit 1 has：Unit main body 2, multiple covers 3, the cover for being installed on the unit main body 2
4, cover 5.By these unit main bodies 2 and cover 3, cover 4, cover 5 closed survey is formed in unit main body 2
Room 6 is measured, is contained in the measuring chamber 6 by anode 7, cathode 8, separator (separation membrane) 9, electrode guides 10, the 1st curren-collecting part
11, the 2nd curren-collecting part 12, separator are with gasket 13 and spring 14 etc. (with reference to Fig. 3).In addition, in Fig. 4, Fig. 5 A and Fig. 5 B
The diagram of anode 7, cathode 8 and separator 9 etc. is omitted.
Unit main body 2 and electrode guides 10 are for example by peak (PEEK:Polyether-ether-ketone), polyphenylene sulfide (PPS), fluorine
Resin or polypropylene (PP) formation.From preventing the aging as caused by the generation of moisture or analyze essence as caused by the passing through of gas
From the perspective of reduction of degree etc., as unit main body 2 and the material of electrode guides 10, be preferably difficult to absorb moisture and
The relatively low low material of passing through property of gas.The 3,4,5, the 1st curren-collecting part 11 of each cover, the 2nd curren-collecting part 12 and spring 14 for example by
Stainless steel (SUS) formation.In unit main body 2, be equipped with each cover 3,4, the surface vertical of component 5 be provided with multiple spiral shells
Line axis 16 is anchored on these thread spindles 16 by making the thread spindle 16 be inserted through each cover 3,4,5, and by nut 17, to
Each cover 3,4,5 is fixed on unit main body 2.
At this point, the 1st curren-collecting part 11 is pressed via 14 partes tegmentalis part 3 of spring to 12 side of the 2nd curren-collecting part, the 2nd curren-collecting part 12
Partes tegmentalis part 4 is pressed to 11 side of the 1st curren-collecting part.Anode 7, cathode 8 and separator 9 are clamped in the 1st curren-collecting part 11 as a result,
Between the 2nd curren-collecting part 12.The current collecting bar 18,19 for example formed by stainless steel (SUS) is fixed on cover 3,4.As a result,
Current collecting bar 18 is electrically connected to anode 7 via cover 3, spring 14 and the 1st curren-collecting part 11, and current collecting bar 19 is via cap
Part 4 and the 2nd curren-collecting part 12 are electrically connected to cathode 8.
Anode 7 is for example formed by cobalt acid lithium.Cathode 8 is for example formed by graphite.Have such anode 7 and cathode 8
Gas analysis unit 1 is referred to as " full battery ".It is the disk-shaped of 34mm that anode 7 and cathode 8, which are, for example, outer diameter, is formed as comparing
The outer diameter of actual lithium ion battery is big.Separator 9 is that the outer diameter formed by such as polypropylene is the porous film of 41mm, thickness
Degree is, for example, 24 μm.But the separation membrane being arranged between 1 pair of electrode 7, electrode 8 is not limited to separator 9.Anode 7 and negative
Pole 8 needs access to, and distance is determined by the thickness of separation membrane.The above-mentioned thickness of separator 9 only as an example of, be not limited to
The value.The thickness of separation membrane is preferably such as 100 μm or less.But the material of anode 7 and cathode 8 is not limited to above-mentioned material,
Such as anode 7 can be by LiMn2O4 (spinel structure), LiFePO4 (olivine structural), ternary system (NMC systems), nickel system (NCA
System) etc. other materials formed, cathode 8 can also be formed by other materials such as hard carbon, titanate, silicon, germanium.In anode 7 or cathode 8
The gas analysis that is formed by lithium of a side be referred to as " half-cell " with unit, the present invention can also be applied to such gas analysis
Use unit.As the electrolyte in lithium ion battery, may be exemplified explanation has aqueous electrolyte, inorganic solid electrolyte, organic
Solid electrolyte, organic system electrolyte (EC-EMC systems), organic system electrolyte (EC-PC systems), ionic liquid system electrolyte, gel
Polymer dielectric etc..In addition, it is not limited to the gas analysis unit analyzed the gas generated by lithium ion battery, this
Invention can also be applied to by lead accumulator, Ni-MH battery, NAS batteries, redox flow batteries, sodium-ion battery, gold
The gas analysis that the gas of the generations such as category-air cell, lithium-sulfur cell, metal negative electrode battery (calcium, magnesium, aluminium etc.) is analyzed is used
Unit.As the component parts of Ni-MH battery, such as hydroxy nickel oxide can be illustrated as anode, hydrogen bearing alloy and hydrogen as negative
Pole, potassium hydroxide is as electrolyte.
Filled with the electrolyte being for example made of organic solvent in measuring chamber 6, it is impregnated with anode 7 in the electrolyte, bears
Pole 8 and separator 9.Lithium ion is generated by anode 7 when charging, which is moved to 8 side of cathode across separator 9.Separately
On the one hand, lithium ion when electric discharge positioned at 8 side of cathode is moved to positive 7 sides across separator 9.
In the state that 1 pair of electrode 7, electrode 8 are powered, in the case where generating gas by each electrode 7,8, these gas quilts
It is formed in 1 pair of capture portion 21 of unit main body 2, capture portion 22 captures.Specifically, being produced in positive 7 sides relative to separator 9
The captured portion 21 of raw gas captures, and the captured portion 22 of gas generated in 8 side of cathode relative to separator 9 captures.At this
In embodiment, as described above, while with very short distance configuration anode 7 and cathode 8, it can be by the gas of generation
It is detached respectively to different capture portion 21, capture portion 22.
The voltage applied to anode 7 and cathode 8, by charge and discharge device control (not shown).As shown in dotted line in Fig. 5 B,
Reference electrode 20 can also be set in unit main body 2.Reference electrode 20 for example by being formed with the lithium of positive 7 identical materials, leads to
It crosses and is inserted into capture portion 21, be impregnated in filling to the electrolyte of measuring chamber 6.But the material of reference electrode 20 is not limited to lithium,
Can also be other materials.If using reference electrode 20, using the voltage measured by reference electrode 20 as reference voltage, into
The analysis of current potential between current potential and reference electrode 20 and cathode 8 of the row between reference electrode 20 and anode 7.
1st curren-collecting part 11 is formed as cylindric.The end face of 7 side of anode in 1st curren-collecting part 11 is flat surface, this is flat
Face is whole to abut with anode 7.On the other hand, the end face of the side opposite with positive 7 sides in the 1st curren-collecting part 11 is formed with
Recess portion 111 for accommodating spring 14, in the state of containing spring 14 in the recess portion 111, the 1st curren-collecting part 11 is via the bullet
14 partes tegmentalis part 3 of spring presses.
Electrode guides 10 are formed as cylindric.The outer diameter substantially one of the internal diameter of electrode guides 10 and the 1st curren-collecting part 11
It causes, the 1st curren-collecting part 11 is configured at being inserted into the state of the inside of electrode guides 10 in measuring chamber 6.Anode 7 is to be configured at electricity
The state of the inside of pole guide part 10 is kept.The circumferential surface of electrode guides 10 be formed with it is multiple opening 15, these opening 15 with
Capture portion 21 is connected to.The gas generated in positive 7 sides accordingly, with respect to separator 9 is directed to capture portion via opening 15
21.The gas generated as a result, in positive 7 sides is captured out of electrode guides 10 via 15 captured portions 21 of opening well.
2nd curren-collecting part 12 is by being respectively formed as columned small diameter portion 121 and large-diameter portion 122 one on the same axis
Ground is formed and is constituted.The end face of the side opposite with 122 side of large-diameter portion of small diameter portion 121 is flat surface, and the flat surface is whole
It is abutted with the cathode 8 being configured in measuring chamber 6 in the outside of electrode guides 10.
In the inner peripheral surface of unit main body 2, the part opposed with small diameter portion 121 is formed with the recess portion of arc-shaped, the recess portion structure
At guiding the gas generated in 8 side of cathode to the path of navigation 23 of capture portion 22.That is, relative to separator 9 in cathode 8
The gas that side generates is directed to capture portion 22 via path of navigation 23.As a result, in the cathode 8 in the outside of electrode guides 10
The gas that side generates captures well via the path of navigation 23 for being formed in unit main body 2 portion 22 that is captured.
Like this, in the present embodiment, the gas that is generated in positive 7 sides relative to separator 9 and relative to
The gas that separator 9 is generated in 8 side of cathode is detached and is captured by 1 pair of capture portion 21, capture portion 22 respectively, therefore can be right
The gas that each capture portion 21,22 captures individually is analyzed.Therefore, with do not make to generate in positive 7 sides and 8 side of cathode
Gas the case where reciprocally detaching and being analyzed compare, can more precisely be analyzed.
Cover 5 is equipped with the 1 pair of partition holder 31,32 for example formed by stainless steel (SUS).Each partition holder
31,32 are formed as cylindric and are installed in cap in such a way that its lower face presses disk-shaped partition 33, partition 34 respectively
Part 5 (with reference to Fig. 5 A and Fig. 5 B).One of partition holder 31 is across partition 33 and the gas to being generated in positive 7 sides
The capture portion 21 captured is opposed.Another partition holder 32 is across partition 34 and the gas to being generated in 8 side of cathode
The capture portion 22 captured is opposed.
Like this, 1 pair of capture portion 21, capture portion 22 are closed by 1 pair of partition 33, partition 34 respectively.Partition 33, every
Piece 34 is for example formed by polytetrafluoroethylene (PTFE) (PTFE) or butyl rubber.As a result, by syringe (not shown) via 1 pair of partition
33, partition 34 is inserted into each capture portion 21,22, by the syringe, can will detach and capture to the gas of each capture portion 21,22
Body individually aspirates and is analyzed (interim analysis).Such interim analysis can be carried out by the way that syringe is manually operated,
It can also be carried out by automatically controlling syringe.
In the present embodiment, the interim analysis of syringe as described above is not used only, is also supplied to each capture portion 21,22
To carrier gas, the gas generated in unit main body 2 is set to be flowed out from each capture portion 21,22 together with carrier gas, thus, it is possible to the gas
Body is analyzed (continuous analysis).Therefore, each capture portion 21,22, which is formed with, makes carrier gas flow into capture portion 21, in capture portion 22
Inflow entrance 211, inflow entrance 221 and make carrier gas from capture portion 21, capture portion 22 flow out outflux 212, outflux 222 (ginseng
According to Fig. 3).
Each inflow entrance 211,221 is equipped with connector 213, connector 223.On the other hand, each outflux 212,222 is installed
There are connector 214, connector 224.Each connector 213,214,223,224 is respectively via pipeline connection triple valve 215, triple valve
216, triple valve 225, triple valve 226 (referring to Fig.1 and Fig. 2).
Fig. 6 is general for being illustrated to the action of triple valve 215, triple valve 216, triple valve 225, triple valve 226
Slightly vertical view.Triple valve 215, the triple valve 225 being connected to each inflow entrance 211,221 connect oriented each inflow entrance 211,221 and supply
To gas supply line (the 2nd gas supply line) 217, the gas supply line 227 of carrier gas.On the other hand, with each outflux
212, triple valve 216, the triple valve 226 of 222 connections are connected with the gas discharge duct that carrier gas is discharged from each outflux 212,222
218, gas discharge duct 228.
1 pair of triple valve 215, the triple valve 216 being connected to the capture portion 21 of a side are connected with bypass flow path 219.Therefore, lead to
Triple valve 215, triple valve 216 that switching constitutes bypass switching part are crossed, gas supply line 217 and capture portion 21 or side can be made
Either one connection in through-flow road 219.Similarly, 1 pair of triple valve 225, triple valve being connected in the capture portion 22 with another party
226 are connected with bypass flow path 229.Therefore, triple valve 225, the triple valve 226 that bypass switching part is constituted by switching, can make
Gas supply line 227 is connected to either one in capture portion 22 or bypass flow path 229.
In the state of so that gas supply line 217, gas supply line 227 is connected to capture portion 21, capture portion 22, gas
Body supply line 217, gas supply line 227 and gas discharge duct 218, gas discharge duct 228 via capture portion 21,
Capture portion 22 and connect, as shown in Fig. 6 arrows A, from gas supply line 217, gas supply line 227 supply carrier gas drawn
It is directed at capture portion 21, capture portion 22.In contrast, make gas supply line 217, gas supply line 227 and bypass flow path
219, in the state that bypass flow path 229 is connected to, gas supply line 217, gas supply line 227 and gas discharge duct
218, gas discharge duct 228 not via capture portion 21, capture portion 22 and connect, as shown in Fig. 6 arrows B, from gas supply stream
The carrier gas that road 217, gas supply line 227 supply is directed to gas discharge stream via bypass flow path 219, bypass flow path 229
Road 218, gas discharge duct 228.
Therefore, by making gas supply line 217, gas supply line 227 and bypass flow path 219, bypass flow path 229 connect
It is logical, the air in gas supply line 217, gas supply line 227 is discharged via bypass flow path 219, bypass flow path 229
Afterwards, gas supply line 217, gas supply line 227 is made to be connected to capture portion 21, capture portion 22, can to capture portion 21, catch
It obtains portion 22 and supplies carrier gas.Thereby, it is possible to prevent from catching because the air in gas supply line 217, gas supply line 227 flows into
Obtain portion 21, capture portion 22 and harmful effect is caused to analysis, therefore can more precisely be analyzed.But as long as energy
Enough switchings make gas supply line 217, gas supply line 227 and capture portion 21, capture portion 22 or bypass flow path 219, bypass
The composition of any of flow path 229 connection, bypass switching part are not limited to triple valve 215, triple valve 216, triple valve 225, three
Port valve 226 can also be made of other parts.
As shown in fig. 6, in the present embodiment, on the extended line of the inflow direction D of the carrier gas flowed into from inflow entrance 211
Configured with outflux 212.Like this, since inflow entrance 211 and outflux 212 are configured at together along the inflow direction D of carrier gas
On one straight line, therefore flow path composition can be simplified.Outflux 222 is similarly configured at the carrier gas flowed into from inflow entrance 221
On the extended line of inflow direction.
In addition, the midway on the extended line of the inflow direction D of the carrier gas flowed into from inflow entrance 221, is provided with resistance part
Part.Like this, by the way that resistance elements are arranged on the flow path of carrier gas, which passes through as carrier gas in capture portion 21
Resistance.In this case, the carrier gas flowed into from inflow entrance 221 is due to by the resistance from resistance elements and in capture portion 21
It is stirred.It is equably stirred thereby, it is possible to the gas for being captured capture portion 21 and it is made to be flowed out from outflux 212, it is right
The gas is analyzed, therefore can obtain stable analysis result.
Fig. 7 A and Fig. 7 B are generated when showing in capture portion 21 without continuously being analyzed in the state of resistance elements
The figure of an example of the variation of the detection voltage of hydrogen.In addition, Fig. 8 A and Fig. 8 B are to show that there are resistance parts in capture portion 21
The figure of an example of the variation of the detection voltage of hydrogen is generated when continuously being analyzed in the state of part.In this embodiment, to following
Situation is illustrated：Hydrogen is generated in positive 7 sides, the captured portion 21 of the hydrogen captures and together with carrier gas from outflux
212 outflows, are thus continuously detected by detector.
In fig. 7, the flow velocity that the carrier gas (helium) in capture portion 21 is flowed into from inflow entrance 211 is 5ml/min.Another party
Face, in figure 7b, the flow velocity that the carrier gas (helium) in capture portion 21 is flowed into from inflow entrance 211 are 10ml/min.By these Fig. 7 A
And Fig. 7 B are clear that, in the state of in capture portion 21 without resistance elements, even if increasing the flow velocity of carrier gas, detect voltage
Unstable, the gas that captured portion 21 captures is not stirred homogeneously.
In fig. 8 a, the flow velocity that the carrier gas (helium) in capture portion 21 is flowed into from inflow entrance 211 is 5ml/min.Another party
Face, in the fig. 8b, the flow velocity that the carrier gas (helium) in capture portion 21 is flowed into from inflow entrance 211 are 10ml/min.By these Fig. 8 A
And Fig. 8 B are clear that, there are in the state of resistance elements in capture portion 21, although the situation slow in the flow velocity of carrier gas
Spread of voltage is detected under (such as 5ml/min), but is detected in the very fast situation of the velocity ratio of carrier gas (such as 10ml/min)
Voltage stabilization.It can thus be seen that the flow velocity in carrier gas is contacted more than certain value and with resistance elements and (is stirred with generating stirring stream
The flowing for the carrier gas mixed) flow velocity flow into the case of, the gas that captured portion 21 is captured is stirred homogeneously.
Like this, by making carrier gas be flowed into from inflow entrance 211 with flow velocity more than certain value, carrier gas can be made well
It is contacted with resistance elements and generates stirring stream.By generate stirring stream, the gas that capture portion 21 can be captured equably into
Row stirring, therefore stable analysis result can be obtained.Above-mentioned certain value, such as preferably 7.5ml/min or more, more preferably
10ml/min or more.
In addition, in capture portion 21 without resistance elements in the state of, from preventing the dense of gas that capture portion 21 captured
Spend it is low from the viewpoint of, the flow velocity for preferably flowing into the carrier gas in capture portion 21 is 5ml/min or so.In this embodiment party
Formula by being arranged resistance elements in capture portion 21, and the flow velocity of the carrier gas flowed into capture portion 21 is set as than logical
High flow velocity when normal analysis, can equably stir the gas of the capture of captured portion 21.
Resistance elements can be replaced by such as reference electrode 20.But resistance elements may not be reference electrode 20, and
It is made of other component.Although in addition, in figure 6 only on the extended line for the inflow direction D that carrier gas is flowed into from inflow entrance 211
Midway is provided with resistance elements (reference electrode 20), but the extension for the inflow direction D that can also be flowed into from inflow entrance 221 in carrier gas
Midway on line is also provided with resistance elements.
Using the voltage measured by reference electrode 20 as reference voltage, between reference electrode 20 and anode 7 current potential,
Or on the basis of the current potential between reference electrode 20 and cathode 8 is more precisely analyzed, 20 preferred disposition of reference electrode
In the central portion of capture portion 21.But it as shown in fig. 6, is deviated even if reference electrode 20 is configured at from the central portion of capture portion 21
Position, can also be sufficiently carried out high-precision analysis.
Fig. 9 is to show that the current potential relative to reference electrode 20 makes the potential change (i.e., cyclic voltammetry) of anode 7 and carries out
The figure of an example of the variation of electric current when charging and electric discharge.In this embodiment, for using cobalt acid lithium as anode 7, using lithium
The gas analysis unit of half-cell as cathode 8 shows to use 1MLiPF6 (EC-DEC1:1) as the experiment of electrolyte
As a result.As shown in fig. 6, reference electrode 20 is configured at from the position that the central portion of capture portion 21 deviates.
Using anode 7, cathode 8 and the electrolyte to consist of such materials the case where, when charging (oxidant side)
Spike potential is preferably 4.0~4.1V, and the spike potential of (reduction side) is preferably 3.8~3.9V when electric discharge.Result according to Fig.9,
It is found that even reference electrode 20 is configured in the case of the position that the central portion of capture portion 21 deviates, when due to charging
Spike potential in the range of 4.0~4.1V, the spike potential when electric discharge in the range of 3.8~3.9V, so can fully into
The high-precision analysis of row.In addition, it is believed that although in this embodiment, showing experiment knot when gas analysis with unit is half-cell
Fruit, but can also obtain same result in the gas analysis unit of full battery.
Referring again to Fig. 3, between unit main body 2 and each cover 3,4, it is respectively arranged with seal member 41, sealing
Part 42.Seal member 41 is for example made of the cricoid o-ring that perfluoroelastomer is formed.On the other hand, seal member 42 for example by
Butyl rubber is formed, and is made of the periphery cricoid o-ring longer than seal member 41.
Between unit main body 2 and cover 5, it is provided with seal member 43, seal member 44, seal member 45.Sealing
Component 43, seal member 44 are the cricoid o-ring for example formed by perfluoroelastomer, and seal member 44 is outer than seal member 43
Perimeter.On the other hand, seal member 45 is for example formed by butyl rubber, by the periphery cricoid o-ring longer than seal member 44
It constitutes.
Like this, measuring chamber 6 is closed by seal member 41~45.Between unit main body 2 and each cover 3,4,5,
Multiple seal members 41~45 are respectively arranged with, therefore the air-tightness of measuring chamber 6 can be improved, external air is made to be difficult to enter
In unit main body 2.But the quantity for being set to the seal member between unit main body 2 and each cover 3,4 is not limited to 2,
It can be 3 or more.Similarly, the quantity for being set to the seal member between unit main body 2 and cover 5 is not limited to 3, can
It can also be 4 or more to be 2.In addition, the shape of seal member, material are not limited to above-mentioned shape, material, it can also
It is other materials, material.
In turn, in the present embodiment, it is formed by between multiple seal members 41~45 into each cover 3,4,5
Space supply gas.Specifically, as shown in Figure 1 and Figure 2, cover 3 is equipped with 2 connectors 46, connector 47, via
Pipeline 61 is between the seal member 41 and seal member 42 that the gas that the connector 46 of a side flows out passes through 3 side of cover
After cricoid space, flowed out from the connector 47 of another party.2 connectors 48, connector 49 are installed, even on cover 5
It connects device 48 and is connected to connector 47 via pipeline 62.The gas flowed out as a result, from connector 47 flows into connector 48, by close
It seals after the cricoid space between component 44 and seal member 45, is flowed out from the connector 49 of another party.It is installed on cover 4
There are 2 connectors 50, connector 51, connector 50 to be connected to connector 49 via pipeline 63.It is flowed out as a result, from connector 9
Gas flows into connector 50, by the cricoid space between the seal member 41 and seal member 42 of 4 side of cover it
Afterwards, it is flowed out from the connector of another party 50.
Connector 51 is connected to T-tube 52 via pipeline 64, which is connected to via pipeline 65, pipeline 66 in turn
Connector 53, connector 54.Connector 53, connector 54 are installed in partition holder 31, partition holder 32 respectively.By
This, the gas flowed out from connector 51 via T-tube 52 and connector 53, connector 54, flow into partition holder 31, every
Piece holder 32 is released via the space in the partition holder 31, partition holder 32 to outside.Specifically, such as Fig. 5 A
Shown in middle arrow C, the gas of partition holder 31, partition holder 32 is flowed into via connector 53, connector 54, due to quilt
Partition 33, partition 34 block, and do not flow into capture portion 21, capture portion 22, but via the insertion hole of syringe be released to every
The outside of piece holder 31, partition holder 32.
Like this, pipeline 61, pipeline 62, pipeline 63 are constituted to the space being formed between multiple seal members 41~45
The gas supply line (the 1st gas supply line) of supply gas.Due to more from pipeline 61, pipeline 62, pipeline 63 to being formed in
Space supply gas between a seal member 41~45, because air is more thin, also can so even if external air is flowed into
It is enough drive air to outside out of.Enter in unit main body 2 accordingly, it may be possible to effectively inhibit external air.
The gas supplied from pipeline 61, flowed successively to pipeline 62, pipeline 63, pipeline 64, pipeline 65, pipeline 66, also may be used
With the identical load of carrier gas for being with being supplied from gas supply line 217, gas supply line 227 to capture portion 21, capture portion 22
Gas.In this case, in midway branch and pipeline 61 can also be directed to from the carrier gas of gas supply part supply (not shown).
Like this, as long as the carrier gas supplied into unit main body 2 is supplied to the space being formed between multiple seal members 41~45
The composition given, even if in the case where the gas supplied into above-mentioned space enters in unit main body 2, which will not be to dividing
Analysis causes harmful effect, therefore can more precisely be analyzed.Further, since without preparing the gas different from carrier gas,
So device composition can be simplified.
Figure 10 A are to show not to be repeated and fill to the space supply gas being formed between multiple seal members 41~45
The figure of in the case of electric discharge, charge/discharge capacity variation.Figure 10 B and Figure 10 C are shown respectively to being formed in multiple sealings
Space supply gas between part 41~45 and in the case of charge and discharge are repeated, the figure of the variation of charge/discharge capacity,
Figure 10 B show that the case where flow velocity of gas is 10ml/min, Figure 10 C show the case where flow velocity of gas is 50ml/min.
As shown in Figure 10 A, relative to the 1st time charging when (S11) and electric discharge when (S12) capacity, the 2nd time charging when
(S21) capacity of (S22) is reduced respectively when and discharging.Similarly, the 3rd time charging when (S31) and electric discharge when (S32) appearance
Measure so reduce, the 4th charge when (S41) and electric discharge when (S42) capacity be further reduced.
As shown in Figure 10 B known to, even if with the flow velocity of 10ml/min between being formed in multiple seal members 41~45
Space supply gas while charge and discharge are repeated in the case of, capacity is also reduced when each repeated charge, but it subtracts
It is a small amount of smaller.In addition, as illustrated in figure 10 c, when the flow velocity of gas being made to increase to 50ml/min, causing because charge and discharge are repeated
The decrement of capacity further becomes smaller.
In the case where charge and discharge are repeated, due to entering moisture contained in the extraneous air in unit main body 2
It influences, electrode (anode 7 or cathode 8) aging, so charge/discharge capacity gradually decreases.But as shown in Figure 10 B and Figure 10 C
It is found that if to the space supply gas being formed between multiple seal members 41~45, the reduction quantitative change of charge/discharge capacity
It is small, therefore external air can be effectively inhibited and entered in unit main body 2.
Figure 11 is the figure for showing the oxygen concentration that the gas in unit main body 2 is included and changing over time.In this embodiment, with when
Between process correspondingly show with by the state of 2 inner sealing of unit main body place 1 day in the case of, out of unit main body 2
The detection intensity of oxygen that goes out of gas detection.
With the variation of the oxygen concentration shown in straight line L1 it is not between being formed in multiple seal members 41~45 in Figure 11
Space supply gas in the case of measurement result.On the other hand, in fig. 11 with straight line L2, straight line L3 shown in oxygen concentration
Variation be measurement result to the space supply gas being formed between multiple seal members 41~45, straight line
L2 shows that the case where flow velocity of gas is 10ml/min, straight line L3 show the case where flow velocity of gas is 50ml/min.
These are compared and is understood, in the case of non-supply gas (straight line L1), oxygen concentration is easy to rise, with this phase
Right, in the case where having supplied gas (straight line L2, L3), oxygen concentration is difficult to rise, can effectively inhibit external air into
Enter in unit main body 2.In addition, the flow velocity of gas is faster, in external air unit main body 2 more difficult to get access.
Whether Figure 12 is for illustrating the influx of the oxygen flowed into syringe because making via connector 53, connector 54
Masking flows into partition holder 31, partition holder 32 and different figures with gas.Masking is, for example, carrier gas with gas or blows
Scavenging body, it is preferable to use carrier gas from the point of view of the viewpoints such as the pull-out of pipeline.Show in this embodiment, via partition holder 31, every
Piece holder 32 makes syringe perforation partition 33, partition 34 and in the case of acquiring capture portion 21, the gas in capture portion 22, gas
The relationship of the collection capacity of body and the result for measuring the oxygen concentration in acquired gas.
So that syringe is inserted into each capture portion 21,22 via partition 33, partition 34, by the syringe, individually aspirates
It is discretely captured to the gas of each capture portion 21,22, when syringe is extracted from partition 33, partition 34, place in syringe
In the state being depressurized.That is, the gas of a small amount of (several μ l or so) captured relative to each capture portion 21,22, to syringe
The acquisition quantitative change of gas is more, thus in the state being depressurized in syringe.Therefore, syringe is extracted from partition 33, partition 34
Moment, the gas of surrounding is sucked into syringe from the front end of the syringe needle in partition holder 31, partition holder 32
It is interior.The collection capacity of the gas acquired at this time into syringe is more, and the amount for being inhaled into the gas in syringe is more.
As shown in figure 12, masking gas (helium) is not made to flow into partition holder via connector 53, connector 54
31, (no helium) is then acquired if the acquisition quantitative change of the gas acquired into syringe is more in the case of partition holder 32
Oxygen concentration in gas becomes very high, it may thus be appreciated that external air is sucked into syringe in large quantities.In contrast, exist
In the case of so that masking gas (helium) is flowed into partition holder 31, partition holder 32 via connector 53, connector 54
(having helium), even if the acquisition quantitative change of the gas acquired into syringe is more, the oxygen concentration in the gas acquired is also relatively low.
This is because covering the partition holder 31 where being supplied to the front end of syringe with gas (helium), partition
In holder 32.That is, even if being supplied to partition holder 31, partition holder in the state of being depressurized in syringe
The masking in the space in 32 replaces external air with gas and enters in syringe, therefore can prevent external air from entering
In syringe.
2. the 1st embodiment of gas analysis system
Figure 13 A and Figure 13 B are the flow paths of the configuration example for the gas analysis system for showing the 1st embodiment of the present invention
Figure.The gas analysis system has：Gas analysis unit 1 as described above；Gas analysis portion 100, in the gas analysis
It is analyzed with the gas generated in the unit main body 2 of unit 1.
The gas analysis system is the system for using gas analysis continuously to be analyzed with unit 1, by 1 pair of capture portion
21, the gas that at least one party in capture portion 22 is captured is guided to gas analysis portion 100.That is, as shown in fig. 6, being arranged from gas
Go out flow path 218 discharge capture portion 21 in gas and from the gas in the capture portion 22 that gas discharge duct 228 is discharged
At least one party, the analysis object as gas analysis portion 100.The gas that captured by capture portion 21 and by 22 institute of capture portion
The gas of capture is respectively guided to different gas analysis portions 100 and is analyzed.In Figure 13 A and Figure 13 B, to utilizing gas
The case where gas that the analysis of body analysis portion 100 is captured by a side of capture portion 21 or capture portion 22, illustrates.
Gas analysis portion 100 has:Flow controller 101, sample introduction part 102, chromatographic column 103 and detector 104
Deng.Such as using helium as carrier gas.It is however not limited to which helium, can also use other gases such as argon as carrier gas.It is supplied from gas
The flow of the carrier gas of portion's supply (not shown) is controlled by flow controller 101.From flow controller 101 to gas analytic unit
The carrier gas of 1 supply is directed to sample introduction part 102 together with the gas generated in unit main body 2, from the sample introduction part
102 are fed to chromatographic column 103.
It is fed to the ingredient contained by the gas of chromatographic column 103 to be detached during by chromatographic column 103, be detached
Each ingredient detected by detector 104.As detector 104, using for example using barrier discharge ionization detector (BID) or
Pulsed discharge ionization detector (PDD).It is put as a result, using the high barrier discharge ionization detector of detection sensitivity or pulse
Ionization detector can be analyzed more precisely.
Especially containing hydrogen, oxygen, nitrogen, carbon monoxide, two from the gas that anode 7 used in battery and cathode 8 generate
Carbonoxide or methane etc., although the detection of barrier discharge ionization detector or pulsed discharge ionization detector to these gases
High sensitivity, but can not detect helium.Therefore, if using helium as carrier gas, barrier discharge ionization detector or arteries and veins are utilized
The gas that the detection of impulse electricity ionization detector generates in gas analysis unit 1, then can not be by the shadow of the ingredient of carrier gas
It rings and the extensive gas of type generated in gas analysis unit 1 is more precisely analyzed.But detector
104 are not limited to these, can also be the others such as thermal conductivity detector (TCD) (TCD) or flame ion type detector (FID)
Detector.Thermal conductivity detector (TCD) to the poor sensitivity of the ingredient of the whole such as hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide or methane, though
Right flame ion type detector has sensitivity for methane, but does not have for hydrogen, oxygen, nitrogen, carbon monoxide and carbon dioxide
Sensitivity, therefore for the good barrier discharge of whole components sensitivity of hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide and methane
Ionization detector or pulsed discharge ionization detector, it is more appropriate as the detector 104 in present embodiment.
In the example of Figure 13 A and Figure 13 B, between flow controller 101 and sample introduction part 102, via conduct
The six-way valve 105 of supply switching part is connect with gas analysis unit 1.Specifically, at 6 ends that six-way valve 105 has
In mouth 151~156, the 1st port 151 is connected with flow controller 101, and sample introduction part 102 is connected in the 2nd port 152.This
Outside, in unit 1, gas supply line 217, gas supply line 227 are connect with the 3rd port 153 for gas analysis, gas discharge
Flow path 218, gas discharge duct 228 are connect with the 4th port 154.5th port 155 connects the flow control with gas analysis portion 100
Different the 106, the 6th port 156 of flow controller of device 101 processed is used as exhaust port.From flow controller 106 for giving from flow
The identical carrier gas of carrier gas (such as helium) that controller 101 supplies.
In the state of Figure 13 A, the 1st port 151 is connected to the 2nd port 152.Therefore, it is supplied from flow controller 101
Carrier gas is conveyed with unit 1 to sample introduction part 102 not via gas analysis, is supplied from the sample introduction part 102 to chromatographic column 103
It gives.In this state, be not fed to chromatographic column 103 with the gas that unit 1 generates in gas analysis, and only by carrier gas supply to
Chromatographic column 103.
In addition, in the state of Figure 13 A, the 3rd port 153 is connected to the 5th port 155, the 4th port 154 and the 6th port
156 connections.Therefore, the carrier gas supplied from flow controller 106 is connected to via the 5th port 155 and the 3rd port 153 is to analysis
With supply in unit 1, via the 4th port 154 and the 6th port 156 to outside together with the gas generated in unit main body 2
Discharge.
If six-way valve 105 is made to be rotated from the state, become state as Figure 13 B, then the 1st port 151 and the 3rd port
153 connections, the 2nd port 152 is connected to the 4th port 154.In the state of Figure 13 B, the carrier gas from flow controller 101
It supplies into gas analysis unit 1, is fed to from sample introduction part 102 together with the gas generated in unit main body 2
Chromatographic column 103.In addition, the 5th port 155 is connected to the 6th port 156, the carrier gas from flow controller 106 is as former state to outside
Discharge.
State shown in Figure 13 B is to supply the 1st supply of carrier gas to gas analysis portion 100 via gas analysis unit 1
State.On the other hand, state shown in Figure 13 A is to supply carrier gas to gas analysis portion 100 not via gas analysis unit 1
The 2nd supply state.Such as by making six-way valve 105 be rotated come alternately with 5~40 minutes or so defined intervals
Switch the 1st supply state and the 2nd supply state.
In the present embodiment, can be switched to supply state by six-way valve 105 will be in gas analysis unit 1
The 1st supply state (3B referring to Fig.1) or will not contain that the gas of generation supplies together with carrier gas to gas analysis portion 100
The 2nd supply state that the carrier gas of the gas generated in gas analysis unit 1 is supplied to gas analysis portion 100 is (with reference to figure
Any one of 13A).Also, in the 1st supply state, pass through the gas that will be generated in gas analysis unit 1 and carrier gas
It directly supplies, can be continuously analyzed to gas analysis portion 100 together.Therefore, it will be used in gas analysis with syringe is used
The gas generated in unit 1 is injected into such constitute in gas analysis portion 100 and compares, and external air is difficult to entrained gas
In flow path.Thereby, it is possible to prevent being mixed into for air from being impacted to analysis result, therefore more precisely can continuously be divided
Analysis.
Further, since each interval during six-way valve 105 switches, it can be by generation in gas analysis unit 1
Gas is supplied and is analyzed to gas analysis portion 100, therefore can correctly carry out quantifying for the gas generated at each interval
Analysis.
In turn, if gas analysis unit 1 is installed on six-way valve 105 under the 2nd supply state shown in Figure 13 A,
The connection of pipeline can be carried out in the state that the gas analysis is not connected to gas analysis portion 100 with unit 1.It is not necessarily to as a result,
The pipeline being connected to gas analysis portion 100 is connected to gas analysis unit 1 in a great rush, therefore installation exercise becomes easy.
Especially in the present embodiment, it in the 1st supply state shown in Figure 13 B, is generated in gas analysis unit 1
Gas out of the gas analysis unit 1 directly to gas analysis portion 100 supply.Therefore, it is possible to simply to be constituted higher
Analyzed to precision.But supply switching part is not limited to six-way valve 105, can also be made of other valves.
It warms to room temperature~90 DEG C in addition, gas analysis unit 1 and six-way valve 105 can also for example be adjusted, be more preferably
80 DEG C or so of relatively high temperature.Thereby, it is possible to carry out stringent durability inspection.According to gas analysis in unit 1
Temperature adjustment temperature is set as value appropriate by the boiling point of electrolyte.
3. the 2nd embodiment of gas analysis system
Figure 14 A and Figure 14 B are the flow paths of the configuration example for the gas analysis system for showing the 2nd embodiment of the present invention
Figure.The gas analysis system is point for continuously being analyzed with unit 1 using gas analysis in a same manner as in the first embodiment
Analysis system has：Gas analysis unit 1；Gas analysis portion 100, to the production in the unit main body 2 of gas analysis unit 1
Raw gas is analyzed.Since the composition in gas analysis portion 100 is identical as the 1st embodiment, for same in figure
Composition assign identical reference numeral and omit detailed description.
In the gas analysis system, in a same manner as in the first embodiment by 1 pair of capture portion 21, capture portion 22 at least
The gas that one side is captured is guided to gas analysis portion 100.That is, the capture being discharged from gas discharge duct 218 as shown in FIG. 6
Gas in portion 21 and from at least one party in the gas in the capture portion 22 that gas discharge duct 228 is discharged, as gas
The analysis object of analysis portion 100.The gas captured in capture portion 21 and the gas captured in capture portion 22 are drawn respectively
Different gas analysis portions 100 is directed to be analyzed.In Figure 14 A and Figure 14 B, to being analyzed using gas analysis portion 100
The case where gas that one side of capture portion 21 or capture portion 22 is captured, illustrates.
In the example of Figure 14 A and Figure 14 B, via as confession between flow controller 101 and sample introduction part 102
Gas analysis unit 1 and trap portion (buffer part) 107 are connected to the six-way valve 105 of switching part.Trap portion 107 is so-called sample
Pipe is the component in the internal hollow form with the buffer area bigger than the internal volume of gas analysis unit 1.
In 6 ports 151~156 that six-way valve has 105, the 1st port 151 is connected with flow controller 106,
Gas analysis unit 1 is installed between flow controller 106 and the 1st port 151.That is, gas of the gas analysis with unit 1
Supply line 217, gas supply line 227 are connect with flow controller 106, gas discharge duct 218, gas discharge duct
228 connect with the 1st port 151.In addition, the 2nd port 152 is connect with the 5th port 155, in these the 2nd ports 152 and the 5th port
Trap portion 107 is installed between 155.6th port 156 is connect with flow controller 101, the 4th port 154 and sample introduction part 102
Connection.3rd port 153 is used as exhaust port.From flow controller 106 for giving the carrier gas phase supplied from flow controller 101
Same carrier gas (such as helium).
In the state of Figure 14 A, the 4th port 154 is connected to the 6th port 156.Therefore, it is supplied from flow controller 101
Carrier gas is conveyed not via trap portion 107 and to sample introduction part 102, is supplied from the sample introduction part 102 to chromatographic column 103.At this
Under state, it is not fed to chromatographic column 103 with the gas that unit 1 generates in gas analysis, and only supplies carrier gas to chromatographic column 103
It gives.
In addition, in the state of Figure 14 A, the 1st port 151 is connected to the 2nd port 152, the 3rd port 153 and the 5th port
155 connections.Therefore, the carrier gas supplied from flow controller 106 is supplied into gas analysis unit 1, and in unit main body 2
After the gas of generation is together via the 1st port 151 and the 2nd port 152 by trap portion 107, via the 5th port 155 and the 3rd
Port 153 is discharged to outside.The gas generated in unit main body 2 as a result, is accommodated in trap portion 107.
If six-way valve 105 is made to become the state of Figure 14 B from state rotation, the 2nd port 152 and the 4th port 154 connect
Logical, the 5th port 155 is connected to the 6th port 156.In the state of Figure 14 B, the carrier gas from flow controller 101 is to trap portion
Supply, chromatographic column 103 is directed into together with the gas in the trap portion 107 from sample introduction part 102 in 107.In addition, the 1st port
151 are connected to the 3rd port 153, and the carrier gas from flow controller 106 is expelled to via gas analysis with unit 1 outer as former state
Portion.
State shown in Figure 14 B is to supply the 1st supply state of carrier gas to gas analysis portion 100 via trap portion 107.It is another
Aspect, state shown in figure 14 A be not via trap portion 107 and to gas analysis portion 100 supply carrier gas the 2nd supply state.It is logical
Crossing makes six-way valve 105 for example be rotated with 5~40 points or so of defined interval, alternately switches the 1st supply state and the 2nd
Supply state.
In the present embodiment, can be switched to supply state by six-way valve 105 will be in gas analysis unit 1
Generate and be contained in the 1st supply state (the reference figure that the gas in trap portion 107 supplies together with carrier gas to gas analysis portion 100
The 2nd 14B) or by the carrier gas without containing the gas generated in gas analysis unit 1 supplied to gas analysis portion 100
Any one of supply state (4A referring to Fig.1).Also, in the 1st supply state, by will be in gas analysis unit 1
It generates and the gas for being contained in trap portion 107 is directly supplied to gas analysis portion 100 together with carrier gas, can continuously be analyzed.
Therefore, the gas generated in gas analysis unit 1 is injected into the such composition in gas analysis portion 100 with syringe is used
It compares, external air is difficult in the flow path of entrained gas.Thereby, it is possible to prevent being mixed into for air from causing shadow to analysis result
It rings, therefore more precisely can continuously be analyzed.
Further, since each interval during six-way valve 105 switches, it can be by generation in gas analysis unit 1
The gas for being contained in trap portion 107 is supplied and is analyzed to gas analysis portion 100, therefore can be to the gas in each interval generation
Correctly carry out quantitative analysis.
Especially in the present embodiment, it in the 2nd supply state shown in figure 14 A, will be generated in gas analysis unit 1
Gas be contained in trap portion 107, be then switched to the 1st supply state as shown in Figure 14B, then can will be contained in trap portion 107
Gas together with carrier gas to gas analysis portion 100 supply.It therefore, as in the present embodiment, as long as can be in trap portion 107
In interior buffer area receiving than gas analysis with more constituting as gases in single 1, can by more gases from
Trap portion 107 is supplied to gas analysis portion 100, therefore can improve the detection sensitivity in gas analysis portion 100, can be more high-precision
Analyzed to degree.
In addition, gas analysis unit 1, six-way valve 105 and trap portion 107, for example, can also adjust warm to room temperature~90 DEG C,
More preferably 80 DEG C or so of relatively high temperature.Thereby, it is possible to carry out stringent durability inspection.It is single according to gas analysis
Temperature adjustment temperature is set as value appropriate by the boiling point of the electrolyte in member 1.In addition, being provided in trap portion 107 for example makes higher boiling
Object can not by filter (not shown), thus, it is possible to prevent the pollution of chromatographic column 103.
In either one or two of the 1st embodiment and the 2nd embodiment, in the gas supply stream of gas analysis unit 1
Triple valve 215, triple valve 225 are connected on road 217, gas supply line 227, in gas discharge duct 218, gas discharge stream
Triple valve 216, triple valve 226 are connected on road 228 (with reference to Fig. 6).Triple valve 215, the composition of triple valve 225 make gas supply stream
Road 217, gas supply line 227 be opened and closed supply side valve, triple valve 216, triple valve 226 composition make gas discharge duct 218,
The discharge-side valve that gas discharge duct 228 is opened and closed.
As a result, when manufacturing gas analysis unit 1, if there is no air (to be set with the specific gas such as argon or helium
Change) in the environment of assembling gas analysis unit 1, make supply side valve (triple valve 215, triple valve 225) and discharge-side valve (three
Port valve 216, triple valve 226) in the state closed, then be not in that air is mixed into interior to gas analysis unit 1 and causes
The case where aging of internal part.Also, supply the gas supply line 217 of gas analysis unit 1, gas
After flow path 227 and gas discharge duct 218, gas discharge duct 228 are connected to the operation of six-way valve 105, beaten if being switched to
The state for having opened supply side valve (triple valve 215, triple valve 225) and discharge-side valve (triple valve 216, triple valve 226), then can
Being mixed into for air is prevented, and is easy to carry out installation exercise.But supply side valve and discharge-side valve are not limited to triple valve
215, triple valve 225, triple valve 216, triple valve 226 can also be other valves of two-port valve etc..
In the above embodiment, electrode guides 10 are illustrated in the internal composition for keeping anode 7, but simultaneously
It is without being limited thereto, can also be in the internal composition for keeping cathode 8.In this case, it is produced in 8 side of cathode relative to separator 9
Raw gas can be captured via 15 captured portions 22 of opening.In addition, path of navigation 23 is not limited to relative to separator 9 to exist
The gas that 8 side of cathode generates is guided to capture portion 22 is such and is constituted, can also be by relative to separator 9 in anode 7 one
The gas that side generates is guided to capture portion 21 is such and is constituted.
In addition, in the above embodiment, to the gas that is generated in positive 7 sides relative to separator 9 and opposite
In the composition that the gas that separator 9 is generated in 8 side of cathode detaches respectively and is captured by 1 pair of capture portion 21, capture portion 22 into
Explanation is gone.But it is improved in the space by the space supply gas being formed between multiple seal members 41~45
Such constitute of pressure can also apply to not by the separated composition of 1 pair of capture portion 21, capture portion 22, that is, can also answer
Gas for being generated in positive 7 sides relative to separator 9 and the gas generated in 8 side of cathode relative to separator 9
The composition captured by 1 capture portion.In addition, the gas used at this time can also be the gas other than carrier gas.
Reference sign
1 gas analysis unit
2 unit main bodies
3,4,5 cover
6 measuring chambers
7 anodes
8 cathode
9 separators
10 electrode guides
11,12 curren-collecting part
13 separator gaskets
14 springs
15 openings
16 thread spindles
17 nuts
18,19 current collecting bar
20 reference electrodes
21,22 capture portion
23 path of navigation
31,32 partition holder
33,34 partition
41~45 seal members
46~51 connectors
52 T-tube
53 connectors
61~65 pipelines
100 gas analysis portions
101 flow controllers
102 sample introduction parts
103 chromatographic columns
104 detectors
105 six-way valves
106 flow controllers
107 trap portions
211 inflow entrances
212 outfluxes
213,214 connector
215,216 triple valve
217 gas supply line
218 gas discharge ducts
219 bypass flow paths
225,226 triple valve
227 gas supply line
228 gas discharge ducts
229 bypass flow paths
Claims (12)
1. a kind of gas analysis unit, which is characterized in that have：
Unit main body has measuring chamber in inside；
1 pair of electrode is made of the anode and cathode for being configured at the measuring chamber；
Separation membrane is configured between 1 pair of electrode；
1 pair of capture portion, by the gas generated in the side of the positive electrode relative to the separation membrane and mutually in the separation membrane in institute
The gas for stating negative side generation is detached and is captured respectively.
2. gas analysis unit as described in claim 1, which is characterized in that be also equipped with and seal 1 pair of capture portion respectively
The 1 pair of partition closed.
3. gas analysis unit as described in claim 1, which is characterized in that being respectively formed in 1 pair of capture portion makes
The inflow entrance and make the outflux that carrier gas is flowed out out of this capture portion that carrier gas flows into the capture portion.
4. gas analysis unit as claimed in claim 3, which is characterized in that the carrier gas flowed into from the inflow entrance is made to generate
Stirring stream.
5. gas analysis unit as claimed in claim 3, which is characterized in that be also equipped with：
Gas supply line supplies carrier gas to the inflow entrance；
Gas discharge duct makes carrier gas be discharged from the outflux；
Bypass flow path connects the gas supply line and the gas discharge duct not via the capture portion；
Switching part is bypassed, is switched over so that the gas supply line and any in the capture portion or the bypass flow path
A connection.
6. gas analysis unit as described in claim 1, which is characterized in that be also equipped with and be impregnated in filling to the measuring chamber
Electrolyte reference electrode.
7. gas analysis unit as described in claim 1, which is characterized in that be also equipped with electrode guides, the electrode is led
It is contained in the measuring chamber to part, the side in 1 pair of electrode is held in inside, is formed in the electrode guides
The opening being connected to the side in 1 pair of capture portion.
8. gas analysis unit as claimed in claim 7, which is characterized in that another party in 1 pair of electrode is described
It is configured on the outside of electrode guides in the measuring chamber, path of navigation is formed in the unit main body, it will be described another
The gas that the electrode side of side generates is guided to another party in 1 pair of capture portion.
9. a kind of gas analysis system, which is characterized in that have：Gas analysis as described in any one of claim 1~8
Use unit；Gas analysis portion, the gas captured at least one party in 1 pair of capture portion are analyzed.
10. gas analysis system as claimed in claim 9, which is characterized in that be also equipped with supply switching part, supply state is cut
It is changed to any of the 1st supply state or the 2nd supply state, the 1st supply state is will be single in the gas analysis
The gas generated in first supplies together with carrier gas to the gas analysis portion, and the 2nd supply state is will not contain described
The carrier gas of the gas generated in gas analysis unit is supplied to the gas analysis portion.
11. gas analysis system as claimed in claim 10, which is characterized in that in the 1st supply state, via described
Gas analysis unit supplies carrier gas to the gas analysis portion,
In the 2nd supply state, carrier gas is supplied to the gas analysis portion not via the gas analysis unit.
12. gas analysis system as claimed in claim 10, which is characterized in that be also equipped in the gas analysis unit
The trap portion that the gas of interior generation is accommodated,
In the 1st supply state, carrier gas is supplied to the gas analysis portion via the trap portion,
In the 2nd supply state, carrier gas is supplied to the gas analysis portion not via the trap portion, in the gas analysis
It is accommodated in the trap portion with the gas generated in unit.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2015219954 | 2015-11-09 | ||
| JP2015-219954 | 2015-11-09 | ||
| JP2016-136088 | 2016-07-08 | ||
| JP2016136088 | 2016-07-08 | ||
| PCT/JP2016/083145 WO2017082264A1 (en) | 2015-11-09 | 2016-11-08 | Gas analysis cell, and gas analysis system |
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| Publication Number | Publication Date |
|---|---|
| CN108352556A true CN108352556A (en) | 2018-07-31 |
| CN108352556B CN108352556B (en) | 2021-03-09 |
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| CN201680064835.0A Expired - Fee Related CN108352556B (en) | 2015-11-09 | 2016-11-08 | Gas analysis cell and gas analysis system |
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| Country | Link |
|---|---|
| JP (1) | JP6611819B2 (en) |
| CN (1) | CN108352556B (en) |
| WO (1) | WO2017082264A1 (en) |
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| CN110165322A (en) * | 2019-05-22 | 2019-08-23 | 江苏集萃华科智能装备科技有限公司 | A kind of method and its application introducing quantitative gas in inside lithium ion cell |
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| CN113960230B (en) * | 2021-11-26 | 2023-05-30 | 天目湖先进储能技术研究院有限公司 | In-situ chromatographic analysis system for gas production analysis of battery |
| WO2023218694A1 (en) * | 2022-05-12 | 2023-11-16 | 株式会社島津製作所 | Greenhouse gas measuring method and measuring device |
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| JP6245468B2 (en) * | 2013-09-12 | 2017-12-13 | 住友金属鉱山株式会社 | Nonaqueous electrolyte secondary battery laminate cell and laminate cell holder for evolved gas evaluation |
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- 2016-11-08 JP JP2017550339A patent/JP6611819B2/en not_active Expired - Fee Related
- 2016-11-08 WO PCT/JP2016/083145 patent/WO2017082264A1/en active Application Filing
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| CN101059525A (en) * | 2007-05-16 | 2007-10-24 | 西南交通大学 | Self-adaptive monitoring method for gas dissolved in oil of traction transformer, and the device thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110165322A (en) * | 2019-05-22 | 2019-08-23 | 江苏集萃华科智能装备科技有限公司 | A kind of method and its application introducing quantitative gas in inside lithium ion cell |
| CN110165322B (en) * | 2019-05-22 | 2021-04-20 | 江苏集萃华科智能装备科技有限公司 | Method for introducing quantitative gas into lithium ion battery and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108352556B (en) | 2021-03-09 |
| JP6611819B2 (en) | 2019-11-27 |
| WO2017082264A1 (en) | 2017-05-18 |
| JPWO2017082264A1 (en) | 2018-09-20 |
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