CN1844947A - X diffraction in-situ testing device for electrode charge and discharge process - Google Patents
X diffraction in-situ testing device for electrode charge and discharge process Download PDFInfo
- Publication number
- CN1844947A CN1844947A CN 200610025206 CN200610025206A CN1844947A CN 1844947 A CN1844947 A CN 1844947A CN 200610025206 CN200610025206 CN 200610025206 CN 200610025206 A CN200610025206 A CN 200610025206A CN 1844947 A CN1844947 A CN 1844947A
- Authority
- CN
- China
- Prior art keywords
- electrode
- diffraction
- testing device
- discharge process
- tested
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to an X-ray diffraction in-situ (in-situ XRD) tester in the process of discharge/charge of battery and relative method. Wherein, it is formed by a XRD in-situ test sample support and a plate battery; the XRD in-situ test sample support is a cuboids plate made from insulated material, which is formed by a plate battery groove, a plate battery wire groove, and a cover plate with four fixing holes for fixing the plate battery; said plate battery is formed by a tested battery, auxiliary electrodes and an annular auxiliary electrode, while the tested electrode is between two auxiliary electrodes and separated by baffle films; the installed plate battery is dipped in electrolyte to be mounted on the XRD in-situ test sample support, sealed and fixed by protective film and cover plate; then connecting the external circuit to process said XRD in-situ test.
Description
Technical field
The present invention relates to a kind of X-ray diffraction in-situ testing device of battery charge and discharge process.
Background technology
The kill mechanism that battery charging and discharging reaction mechanism and battery recycle in the process is the important subject of battery industry always.For study battery discharge and recharge and/or cyclic process in the behavior of electrode material and the Changing Pattern of microstructure, improve charge-discharge performance to explore, prolong the battery method in serviceable life, the present application people and Ta once adopted static and accurate dynamic XRD measuring technology to make research [Lou Yuwan per capita, Yang Chuanzheng, positive electrode β-Ni (OH) in the .MH-Ni batteries such as Xia Baojia
2The comparative study of microstructure. Chinese science E collects, and 2006,36 (5)].
So-called static method is meant and discharges and recharges front and back and/or the primary state of cycling life test front and back and the research of final state sample.So-called quasi-dynamic method is to discharge and recharge and/or some stage of cyclic test stops the back sampling suddenly.These two kinds of methods all need to dissect battery, take off active substance with the ultrasonic vibration method from electrode, and wash oven dry again to the neutrality, carry out testing research with powder x-ray diffraction at last.Obviously, this static state and accurate dynamic approach are brought problems, the dispersiveness of for example inevitable interference and test result.
Battery charge and discharge process not only needs to connect external circuit, and must in battery, inject electrolytic solution for ion transfer, common employed electrolytic solution is to have corrosivity (alkalescence, acid battery electrolytic solution) or volatility (electrolyte for lithium ion battery) liquid, general device does not have corresponding hermetically-sealed construction, simultaneously encapsulant tends to again the x-ray diffraction line of tested electrode is produced bigger interference, and improved way is exactly the XRD in-situ test that discharges and recharges with cyclic process.Therefore the XRD in-situ testing device is that to carry out the in-situ test of battery charging and discharging necessary.Though there is this patented product Ulrik Palmqvist in Japan (Rigaku) company of science, Lars Eriksson, Javier Garcia-Garcia etal.On the misuseof the crystal structure model of the Ni electrode material.Journal of PowerSource 2001,99:15-25, not only cost an arm and a leg by (1-2 ten thousand U.S. dollars), on common X-ray diffractometer, also can't be used.The inventor attempts by designing the XRD in-situ testing device that a kind of test battery charge and discharge process changes, to meet the demands.
Summary of the invention
The object of the present invention is to provide a kind of X-ray diffraction in-situ testing device that is used for battery charge and discharge process, this device is to be made of two parts.
At first, the present invention includes a kind of flat plate cell of the XRD of being used for in-situ test.It comprises that one has the tested electrode of lead-in wire, a dull and stereotyped auxiliary electrode that has lead-in wire and an annular auxiliary electrode that has lead-in wire, tested electrode places between dull and stereotyped auxiliary electrode and the annular auxiliary electrode, and separate with barrier film with auxiliary electrode, the tested electrode upwards barrier film of a side has rectangle or the circular port of 13 * 20mm, and the perforate of annular auxiliary electrode is relative with it.
The second, the present invention includes a kind of specimen holder of the XRD of being applicable to in-situ test, it is made up of flat plate cell groove, flat plate cell lead-in wire groove and the cover plate that is used for fixing flat plate cell that has four fixed orifices; Insulating material such as described rectangular parallelepiped plate employing organic glass process, and an end is thinned to certain thickness, makes the XRD test surfaces pass through centre of diffractometer so that regulate.The middle part fluting is (a kind of in rectangle, circle and the ellipse, specifically decide) on tested cell shapes, in order to the flat plate cell of XRD in-situ test to be installed, the extended surface of slot length direction and Width leaves the lead-in wire groove of test battery, and this also is simultaneously the passage that adds electrolytic solution.The cover plate of specimen holder is used for fixing flat plate cell.The degree of depth of described groove is 0.5-1.5mm.
The present invention also is provided for the diaphragm that XRD in-situ test battery is used.This diaphragm is used for sealing whole flat plate cell; therefore claimed film looks like not have obvious interference to the XRD figure of measured matter; the X-ray diffraction peak that is diaphragm clearly separates with the X-ray diffraction peak energy of measured material, and it can be any organic or inorganic material that the thickness that possesses above-mentioned feature is no more than 0.2mm.
The assembling of the flat plate cell of XRD in-situ test, specimen holder and diaphragm in the following ways; during installation; on at first flat plate cell being positioned in the flat plate cell groove of specimen holder of XRD in-situ test; perforate outwardly; again diaphragm is covered on the whole tested flat plate cell, at last with cover plate for sealing and fixing.Need between tested flat plate cell, diaphragm and specimen holder by material seals such as epoxy resin, also leakage or the volatilization of mode to prevent electrolytic solution of mechanical seal such as available O-ring seal.
The flat plate cell of the present invention test can be the both positive and negative polarity of once any or secondary cell such as nickel electrode, hydrogen-occlussion alloy electrode, cadmium electrode, lithium ion anode.
Description of drawings
Fig. 1 (a) and (b) are respectively X-ray diffractometer and the XRD in-situ test specimen holders that is applicable to horizontal or vertical scanning, and structure is similar basically, only contact conductor position difference; Fig. 1 (c), (d) have the cover plate of hole and circular groove respectively, and required thickness is thin as far as possible, but certain rigidity must be arranged.
Fig. 2 is the structure of XRD in-situ test flat plate cell.
(a) tested electrode
(b) annular auxiliary electrode
(c) auxiliary electrode
(d) barrier film of one side perforate
(e) flat plate cell and specimen holder unitized construction synoptic diagram
Fig. 3 (a) is the flat plate cell of original position XRD test of nickel hydroxide electrode and the assembly drawing of supporting specimen holder.
(b) be the flat plate cell of original position XRD test of lithium cobalt oxygen electrode and the assembly drawing of supporting specimen holder.
1 auxiliary electrode lead channels among the figure; 2 tested contact conductor passages; 3 flat plate cell grooves; 4 are used to be installed in the inserting surface of the specimen holder on the XRD instrument; 5 cover plate perforates; 6 four fastening holes of using; 7 sealing circular grooves; 9 tested contact conductors; 10 annular auxiliary electrode lead-in wire; 11 auxiliary electrodes, 12 cover plates, 13 annular auxiliary electrode that go between; 14 tested electrodes; 15 dull and stereotyped auxiliary electrodes; 16 barrier films; 17 clamp nuts; 18 diaphragms; 19 flat plate cell grooves; 20 specimen holders.
Embodiment
Describe the present invention in detail below in conjunction with accompanying drawing, with further elaboration substantive distinguishing features of the present invention and obvious improvement.
At first press Fig. 1 (a) with organic glass or other insulating material or (b) make the specimen holder of XRD in-situ test, it can repeated multiple times use.Make the cover plate that has the hole by Fig. 1 (c), and be equipped with the fixedly screw nut of usefulness; Make the cover plate that has groove by Fig. 1 (d), expand with the fastening flat plate cell that prevents of " O " RunddichtringO.XRD in-situ test specimen holder is shown among Fig. 1, and its a and b are respectively and are used for the horizontal scanning diffractometer that vertical scanning diffractometer that sample levels places and samples vertical are placed.Wherein shadow region 3 is (a kind of in rectangle, circle and the ellipse, specifically decide on cell shapes) for the rest area of tested battery, its degree of depth depends on the battery gross thickness, the opening 1,2 in electrode outlet line hole communicates with the battery rest area among the figure, replenishes the inlet that adds of electrolytic solution when also being cycling life test; The specimen holder lower end is an inserting surface 4, and its thickness grinds off 0.5-1mm, so that regulate tested electrode plate surface height to be in the center of X-ray diffractometer; Fig. 1 (c) is general cover plate, and central authorities have instrument connection 5, and width is greater than length (DHLS) 3-4mm of used x-ray focus.Four apertures 6 on the cover plate are used for fastening battery and specimen holder, also can adopt the sealing means of placing " O " shape O-ring seal in the circular groove 7.
Flat plate cell is formed (see figure 2) by three electrode plate and barrier film (or diaphragm bag) that they are separated: have lead-in wire 9 tested electrode 14, have lead-in wire 10 annular auxiliary electrode 13, have auxiliary electrode 15, the barrier film (bag) 16 of lead-in wire 11.Be handled easily, can the lead-in wire 10 of annular auxiliary electrode 13 is spot-welded together with the lead-in wire 11 of auxiliary electrode 15.Test electrode encases or is contained in the diaphragm bag with two barrier films, the outer diaphragm central authorities of bag, have the window of X ray incident, its width is greater than used X ray line focus length 3-4mm, and length is 20mm (consistent with the length of used X-ray diffraction specimen holder upper flat plate battery case).
The tested battery that soaked electrolytic solution is put into the flat plate cell groove 3 of specimen holder and (is seen Fig. 2; (e)); surface coverage diaphragm 18 and cover plate 12; the method that can adopt mechanical seal or glue envelope is with cover plate, diaphragm 18 and tested battery and specimen holder sealing, and the perforate of assembling process cover plate must be corresponding mutually with the tested electrode position of flat plate cell.
Make nickel hydroxide pole plate (anode of nickel-metal hydride battery) to be measured, hydrogen-storage alloy negative pole (auxiliary pole plate), diaphragm bag by Fig. 2.Assemble XRD in-situ test battery then according to the following steps.
A) spot-welded together the lead-in wire of two auxiliary pole plates;
B) during tested battery lead plate was packed diaphragm bag into, a diaphragm bag side outwardly had slot;
C) diaphragm bag that tested plates will be housed is put between two counter-electrodes, and corresponding with the perforate of auxiliary counter-electrodes the instrument connection on the diaphragm bag, and the perforate of diaphragm bag is slightly larger than the perforate of auxiliary ligand to battery lead plate, in order to avoid battery short circuit.
D) the above-mentioned flat plate cell that assembles 19 is soaked electrolytic solution; place again on the XRD in-situ test specimen holder; surface coverage diaphragm 18; 20 of diaphragm 18 and specimen holders are bonded and sealed with fluid sealants such as epoxy resin; the two places lead-in wire of flat plate cell also adopts same sealing means; make flat plate cell be in sealing system, add upper cover plate 12 at last and prevent fixedly that with clamp nut 17 flat plate cell 19 from expanding.
Make lithium cobalt oxygen pole plate (lithium ion cell positive) to be measured, carbon negative pole (auxiliary pole plate), barrier film by Fig. 2.Assemble XRD in-situ test battery then according to the following steps.
A) lead-in wire of two auxiliary pole plates is spot-welded together;
B) available two barrier films encase tested electrode, have slotted eye in the barrier film outwardly;
C) tested plates that will be surrounded by barrier film is put between two auxiliary electrodes, and corresponding with the perforate of auxiliary electrode the instrument connection on the barrier film, and the perforate of barrier film is slightly larger than the perforate of auxiliary electrical pole plate, in order to avoid battery short circuit.
D) the above-mentioned flat plate cell that assembles 19 is soaked electrolytic solution; place again on the XRD in-situ test specimen holder; surface coverage diaphragm 18; 20 of diaphragm 18 and specimen holders are bonded and sealed with fluid sealants such as epoxy resin; the two places lead-in wire of flat plate cell 19 also adopts same sealing means; make flat plate cell 19 be in a sealing system, add upper cover plate at last and also fix, prevent that flat plate cell 19 from expanding with " O " RunddichtringO.
E) operate in more than under the argon shield and carry out.
F) connection line carries out original position XRD test.
The invention is not restricted to the foregoing description, anyly be equal to replacement all in protection scope of the present invention of the present invention.
Claims (10)
1, a kind of X diffraction in-situ testing device that is used for electrode charge and discharge process, its feature is become with dull and stereotyped electric battery by specimen holder; The rectangular parallelepiped plate of described specimen holder for being processed into insulating material, it is made up of flat plate cell groove, flat plate cell lead-in wire groove and the cover plate that is used for fixing flat plate cell that has a fixed orifice; Described flat plate cell has the tested electrode of lead-in wire, a dull and stereotyped auxiliary electrode that has lead-in wire and an annular auxiliary electrode that has lead-in wire by one and forms, and tested electrode places between two auxiliary electrodes and separates with the protection barrier film.
2, by the described X diffraction in-situ testing device that is used for electrode charge and discharge process of claim 1, it is characterized in that described rectangular parallelepiped plate middle part fluting, the groove of being opened is a kind of in rectangle, circle and the ellipse, specifically decide on tested cell shapes, be the rest area of tested battery, its degree of depth is 0.5-1.5mm.
3,, it is characterized in that the extended surface of the length direction of described groove and Width leaves the lead-in wire groove of test battery by the described X diffraction in-situ testing device that is used for electrode charge and discharge process of claim 2.
4, by the described X diffraction in-situ testing device that is used for electrode charge and discharge process of claim 1, it is characterized in that tested electrode upwards the protection barrier film of a side have rectangle, circle hole shape or slotted eye, the perforate of annular auxiliary electrode is relative with it.
5, by the described X diffraction in-situ testing device that is used for electrode charge and discharge process of claim 1, it is characterized in that described protection barrier film does not have obvious interference to the X diffraction image of measured matter, its thickness is less than the organic or inorganic material of 0.2mm.
6, by the described X diffraction in-situ testing device that is used for electrode charge and discharge process of claim 1, it is characterized in that described cover plate has groove, and fastening with " O " RunddichtringO.
7, by the described X diffraction in-situ testing device that is used for electrode charge and discharge process of claim 1, it is characterized in that the specimen holder lower end is an inserting surface, its thickness grinds off 0.5-1mm.
8, use the method that is used for the X diffraction in-situ testing device of electrode charge and discharge process as claimed in claim 1; when it is characterized in that installing; at first flat plate cell is positioned on the specimen holder of original position XRD test; perforate outwardly; again diaphragm is covered on the whole tested flat plate cell, at last with cover plate for sealing and fixing.
9, by the described using method that is used for the X diffraction in-situ testing device of electrode charge and discharge process of claim 8, the negative or positive electrode of once any or secondary cell in electrode, hydrogen-occlussion alloy electrode, cadmium electrode and the lithium ion cell positive.
10, by the described using method that is used for the X diffraction in-situ testing device of electrode charge and discharge process of claim 8; it is characterized in that sealing with epoxide resin material between tested flat plate cell, diaphragm and the specimen holder; or with the mode of O-ring seal mechanical seal, with leakage or the volatilization that prevents electrolytic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100252065A CN100373168C (en) | 2006-03-29 | 2006-03-29 | X diffraction in-situ testing device for electrode charge and discharge process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100252065A CN100373168C (en) | 2006-03-29 | 2006-03-29 | X diffraction in-situ testing device for electrode charge and discharge process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1844947A true CN1844947A (en) | 2006-10-11 |
| CN100373168C CN100373168C (en) | 2008-03-05 |
Family
ID=37063890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100252065A Expired - Fee Related CN100373168C (en) | 2006-03-29 | 2006-03-29 | X diffraction in-situ testing device for electrode charge and discharge process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100373168C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102435625A (en) * | 2011-12-27 | 2012-05-02 | 东莞新能源科技有限公司 | Method and sample shelf for X-ray diffraction in-situ test |
| CN102638351A (en) * | 2012-04-18 | 2012-08-15 | 苏州泽佑科技有限公司 | Rechargeable router |
| CN103900744A (en) * | 2014-03-18 | 2014-07-02 | 中国科学院上海微系统与信息技术研究所 | Improved X-ray diffraction in-situ testing device used for charging and discharging processes of battery |
| CN104597064A (en) * | 2014-12-30 | 2015-05-06 | 北大先行科技产业有限公司 | Electrochemical analysis in-situ cell for X-ray diffraction and testing method |
| CN104730096A (en) * | 2015-04-02 | 2015-06-24 | 天能集团江苏科技有限公司 | Qualitative and quantitative analysis method for old negative plate of lead acid battery |
| CN109752657A (en) * | 2017-11-03 | 2019-05-14 | 中国科学院大连化学物理研究所 | Nuclear magnetic resonance original position battery testing attachment and its test method |
| CN110031516A (en) * | 2019-03-29 | 2019-07-19 | 福建师范大学 | A kind of three electrode original position X-ray electrolytic cell devices that reaction environment is controllable |
| US10439172B2 (en) | 2014-07-29 | 2019-10-08 | Samsung Electronics Co., Ltd. | Coin cell battery analyzed with in-situ X-ray analysis, method of manufacturing the same, and method of analyzing the same using X-ray |
| CN110651193A (en) * | 2017-03-29 | 2020-01-03 | 亚马逊科技公司 | Power supply monitoring system using optical estimation |
| CN111366860A (en) * | 2020-04-17 | 2020-07-03 | 中国科学院物理研究所 | Method for detecting electrical property of battery diaphragm |
| CN111398322A (en) * | 2020-03-30 | 2020-07-10 | 扬州大学 | Preparation method of nickel-metal hydride battery sample for synchrotron radiation XRD (X-ray diffraction) in-situ test technology |
-
2006
- 2006-03-29 CN CNB2006100252065A patent/CN100373168C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102435625A (en) * | 2011-12-27 | 2012-05-02 | 东莞新能源科技有限公司 | Method and sample shelf for X-ray diffraction in-situ test |
| CN102638351A (en) * | 2012-04-18 | 2012-08-15 | 苏州泽佑科技有限公司 | Rechargeable router |
| CN103900744A (en) * | 2014-03-18 | 2014-07-02 | 中国科学院上海微系统与信息技术研究所 | Improved X-ray diffraction in-situ testing device used for charging and discharging processes of battery |
| CN103900744B (en) * | 2014-03-18 | 2016-02-10 | 中国科学院上海微系统与信息技术研究所 | For the X-ray diffraction in-situ testing device through improving of battery charge and discharge process |
| US10439172B2 (en) | 2014-07-29 | 2019-10-08 | Samsung Electronics Co., Ltd. | Coin cell battery analyzed with in-situ X-ray analysis, method of manufacturing the same, and method of analyzing the same using X-ray |
| CN104597064A (en) * | 2014-12-30 | 2015-05-06 | 北大先行科技产业有限公司 | Electrochemical analysis in-situ cell for X-ray diffraction and testing method |
| CN104730096A (en) * | 2015-04-02 | 2015-06-24 | 天能集团江苏科技有限公司 | Qualitative and quantitative analysis method for old negative plate of lead acid battery |
| CN110651193A (en) * | 2017-03-29 | 2020-01-03 | 亚马逊科技公司 | Power supply monitoring system using optical estimation |
| CN109752657A (en) * | 2017-11-03 | 2019-05-14 | 中国科学院大连化学物理研究所 | Nuclear magnetic resonance original position battery testing attachment and its test method |
| CN109752657B (en) * | 2017-11-03 | 2021-03-30 | 中国科学院大连化学物理研究所 | Nuclear magnetic resonance in-situ battery testing accessory and testing method thereof |
| CN110031516A (en) * | 2019-03-29 | 2019-07-19 | 福建师范大学 | A kind of three electrode original position X-ray electrolytic cell devices that reaction environment is controllable |
| CN110031516B (en) * | 2019-03-29 | 2021-03-09 | 福建师范大学 | Three-electrode in-situ X-ray electrolytic cell device with controllable reaction environment |
| CN111398322A (en) * | 2020-03-30 | 2020-07-10 | 扬州大学 | Preparation method of nickel-metal hydride battery sample for synchrotron radiation XRD (X-ray diffraction) in-situ test technology |
| CN111366860A (en) * | 2020-04-17 | 2020-07-03 | 中国科学院物理研究所 | Method for detecting electrical property of battery diaphragm |
| CN111366860B (en) * | 2020-04-17 | 2021-02-05 | 中国科学院物理研究所 | Method for detecting electrical property of battery diaphragm |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100373168C (en) | 2008-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100373168C (en) | X diffraction in-situ testing device for electrode charge and discharge process | |
| KR101550754B1 (en) | In situ coin cell with slit for measuring x-ray diffraction, and holder therof | |
| CN110320476B (en) | Simulated battery device for in-situ detection of gas production of liquid battery | |
| KR102214834B1 (en) | In-situ coin cell for X-ray analysis and method of manufacturing the same and method of analyzing the same using X-ray | |
| CN108140767A (en) | Battery module | |
| CN110763713A (en) | Sample cell combining in-situ X-ray diffraction and X-ray fluorescence and assembling method thereof | |
| CN1949422A (en) | Separator sheet and method for manufacturing electric double layer capacitor using the separator sheet | |
| CN109752657B (en) | Nuclear magnetic resonance in-situ battery testing accessory and testing method thereof | |
| JP2002516465A (en) | Liquid-cooled fuel cell stack and method of cooling fuel cell stack | |
| CN110854322A (en) | Modularized lithium battery module | |
| CN112697850A (en) | Can observe electrochemistry testing arrangement of electrode cross section | |
| CN210465316U (en) | In-situ XRD battery reaction chamber | |
| CN103900744B (en) | For the X-ray diffraction in-situ testing device through improving of battery charge and discharge process | |
| CN110361337B (en) | Transmission mode electrochemistry normal position optical testing arrangement | |
| CN101504378A (en) | Lithium ion battery electro-chemical test box used for on-site X-ray diffraction analysis | |
| CN201348613Y (en) | Lithium ion battery electrochemical test box for on site X-ray diffraction analysis | |
| CN117871630A (en) | In-situ X-ray diffraction electrolytic cell and detection process thereof | |
| CN111141716A (en) | In-situ Raman testing device for battery | |
| CN110865102A (en) | Mold for researching metal-based water-based battery | |
| CN215834604U (en) | Secondary battery cover plate convenient to detect and secondary battery | |
| CN112259777B (en) | Optical cell for observing electrochemical reaction and observation system | |
| CN113140820B (en) | Three-electrode button cell device for accurate measurement and application | |
| CN219475471U (en) | Accurate testing arrangement of electrochemical performance | |
| CN214622971U (en) | Multifunctional device for testing lithium ion soft package battery core package | |
| CN217466745U (en) | Sample stage device for characterization of scanning electron microscope of lead storage battery electrode plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080305 Termination date: 20140329 |