KR101711855B1 - Specimen transfer vessel and specimen transferring method for air non-contact analysis - Google Patents

Abstract

The present invention discloses a specimen transfer vessel, and a specimen transferring method for an air-noncontact analysis. A specimen transfer vessel for the air-noncontact analysis comprises: (i) a specimen holder to hold a specimen; (ii) a body part having a specimen entrance on one side where a specimen holder enters; (iii) a member of a valve including a ball arranged inside a body part and connected to a specimen entrance as an open state to accept a specimen holder via an opening unit, and a rotation control unit opening or closing a specimen entrance by rotating a ball; and (iv) a body part installed to enable sliding, and a movable rod adjacent to a specimen holder as an open state of a member of a valve to push a specimen holder.

Description

TECHNICAL FIELD [0001] The present invention relates to a specimen transferring vessel and a specimen transferring method for atmospheric non-opening analysis,

The present invention relates to a sample transfer container, and more particularly, to a sample transfer container and a sample transfer method for atmospheric non-opening analysis.

Recently, an important part of material research is surface measurement and analysis of materials. Surface refers to the interface of one phase that interfaces with another phase, and the properties of the surface can be very different from those of the material itself. Surface measurement and analysis of materials is playing a very important role not only in academic research but also in industrial, biomedical, and other applications.

For example, in the case of a lithium ion battery, a solid electrolyte interphase (SEI) is formed on the surface of the positive / negative active material layer. Since the coating layer is closely related to the cell performance, many Research is underway. The coating layer is mainly formed in the negative electrode active material, the inorganic material layer and the organic material layer are sequentially formed on the surface of the active material, and the LiF precipitates are mixed in the oil / inorganic material layers.

However, the coating layer is very unstable in the air and easily changes. Therefore, care must be taken to ensure that the specimen does not come into contact with air in order to obtain reliable results in analyzing the coating layer. In other words, atmospheric non-opening analysis is required to conduct the analysis without exposing the specimen to the atmosphere. Atmospheric non-open analysis is not possible with conventional analytical equipment (eg, spectroscope, optical microscope, electron microscope, etc.).

The present invention is to provide a sample transferring container and a sample transferring method capable of performing atmospheric non-opening analysis by allowing an analytical sample to be injected into an analyzer without being exposed to the atmosphere.

The sample transporting container for air release analysis according to an embodiment of the present invention includes a sample holder for i) a sample holder for holding a sample, ii) a body having a sample opening for the sample holder into and out of one side, and iii) A valve member including a ball having an opening for receiving the specimen holder and connected to the specimen opening in the open state, and a rotation operating portion for opening and closing the specimen entrance by rotating the ball, iv) a valve member slidably installed in the main body, And a moving rod for pushing the specimen holder in contact with the specimen holder in the open state of the specimen holder.

The specimen holder may include a specimen support having a groove formed thereon for seating the specimen, and two discs may be fixed on both sides of the support.

A through hole may be formed in the body to penetrate the body along a first direction, and the through hole may be connected to a connector formed in the body along a second direction intersecting the first direction. And a connecting member having a sample entry and exit port can be fixed to one side of the through-hole.

The connecting member may be coupled with a specimen input port of the analytical instrument and may form a groove for o-ring alignment. The sealing member can be fixed to the other side of the through hole opposite to the connecting member, and the moving rod can be slidably mounted on the sealing member.

The ball can be positioned in the through-hole, and the opening can penetrate the ball along the first direction in the open state. The ball and the rotation operating portion may be connected by a rotation shaft accommodated in the connection port, and the rotation operating portion may be rotatably coupled to the body from the outside of the connection port.

At least two first stoppers may be fixed along the circumferential direction on the outer surface of the main body surrounding the connection port and the second stopper fixed to the rotation operating portion may move between the two first stoppers to limit the rotation amount of the rotation operating portion .

A method for transferring a sample for atmospheric non-opening analysis according to an embodiment of the present invention includes a first step in which a specimen is fabricated inside a glove box shut off from the atmosphere and a specimen is fixed to the specimen holder, A second step in which the entrance is opened and the specimen holder is accommodated in the main body and the specimen entrance is closed; a third step in which the specimen conveyance container is drawn out from the glove box and then coupled to the specimen input port of the analysis equipment; And a fourth step in which the entrance is opened and the specimen holder moves to a specimen analysis position of the analysis equipment.

In the first step, the specimen may be pretreated after dissection from the positive electrode plate or the negative electrode plate of the lithium ion battery, and may include a coating layer.

A ball and a rotating operation part may be installed in the body, and the ball may be formed in a state of being opened while passing through the inside along the one direction, and the opening corresponding to the sample doorway. In the second and fourth steps, the ball can be rotated by the rotation operating part to open or close the sample entry and exit.

In the third step, an o-ring may be installed at the sample inlet. The sample transfer vessel may include a connecting member which forms a groove for the O-ring alignment and is coupled to the sample input port.

A moving rod can be slidably installed on the other side of the body opposite to the sample loading port. In the fourth step, the specimen holder can be moved by the moving rod to the specimen analysis position.

According to the sample transferring container and the sample transferring method of this embodiment, it is possible to prevent the sample from being exposed to the atmosphere during the entire process of preparing the sample and inputting it into the analysis equipment. Therefore, it is possible to precisely analyze the surface by blocking the deterioration of the specimen due to exposure in the air, and to improve the reliability of the analysis data.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an open cross-sectional view of a sample transfer vessel for atmospheric release analysis according to an embodiment of the present invention; FIG.
2 is a closed sectional view of a sample transfer container for atmospheric release analysis according to an embodiment of the present invention.
3 is an exploded cross-sectional view of the sample transfer container for air release analysis shown in Fig.
Fig. 4 is a perspective view of a specimen holder of the sample transfer container for air / non-opening analysis shown in Fig. 1. Fig.
5 is a view showing one example of a glow discharge lamp mounted in a glow discharge spectroscope.
6 is a flowchart illustrating a method of transferring a specimen according to an embodiment of the present invention.
7 is a schematic view showing a coating layer of a lithium ion battery.
8 is a transmission electron microscope (TEM) photograph of a coating layer formed on natural graphite.
9 is a photograph showing the surface change of the negative electrode active material separated from the lithium ion battery.
FIG. 10 is a photograph showing a sample preparation process in the first step shown in FIG.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

When an element is referred to as "including" an element throughout the specification, it means that the element may further include other elements unless specifically stated otherwise. The sizes and thicknesses of the respective components shown in the drawings are arbitrarily shown for convenience of explanation, and the present invention is not limited to the illustrated ones.

1 and 2 are respectively an open state sectional view and a closed state sectional view of a sample transfer vessel for atmospheric non-opening analysis according to an embodiment of the present invention, and FIG. 3 is a sectional view of the sample transfer vessel for atmosphere non- Fig. 4 is a perspective view of the specimen holder in the specimen transport container for atmospheric non-opening analysis shown in Fig. 1. Fig.

1 to 4, a sample transporting container 100 (hereinafter referred to as a 'sample transporting container') for atmospheric release analysis according to the present embodiment includes a sample holder 10, a sample holder 10 A valve member 30 which opens and closes the specimen inlet 21 and accommodates the specimen holder 10 therein and a valve member 30 which opens and closes the specimen holder 20 in a state where the valve member 30 is opened, (40) for introducing the analyte (10) into the analytical instrument.

The specimen holder 10 includes a specimen pedestal 11 and a groove 12 for seating a specimen can be formed at the center of the specimen pedestal 11. The specimen holder 10 may be, for example, a dumbbell shape in which two discs are fixed on both sides of a fixing table. One of the two discs functions as a specimen pedestal 11, and the other disc can contact the moving rod 40. The specimen holder 10 may be made of metal.

The specimen for surface analysis is disassembled from the product inside the glove box, and is subjected to a preprocessing process and is seated and fixed in the groove 12 of the specimen pedestal 11. The inside of the glove box may be an inert gas atmosphere such as nitrogen or argon, or may be in a high vacuum state. The specimen may be part of a positive plate or a negative plate separated from a lithium ion battery.

A through hole 22 is formed in the main body 20 along the first direction to penetrate the main body 20. The through hole 22 is formed in the main body 20 along the second direction crossing the first direction, As shown in Fig. The first direction and the second direction may be the horizontal direction and the vertical direction, respectively, with reference to the drawing.

For example, three openings are formed on the left, right and upper sides of the main body 20 with reference to the drawing. The openings formed on the right side, the left side and the upper side of the main body 20 are referred to as a first opening OP1, a second opening OP2 and a third opening OP3 (see Fig. 3).

A connecting member 24 having a sample opening 21 is fixed to one side (right side) of the main body 20. The connecting member 24 is fitted in the first opening OP1 and is fixed to the main body 20 and the specimen entrance 21 is connected to the through hole 22 of the main body 20. [ The connecting member 24 is a part that is coupled with the sample input port of the analysis equipment (not shown), and is hermetically coupled to the sample input port of the analyzing equipment in the sample input process.

To this end, an O-ring supporter 52 having an O-ring 51 fixed around the specimen input port of the analyzer and a fixing sheet 53 for fixing the O-ring supporter 52 to the analytical instrument by bolting or the like (See FIG. 3). A groove 25 for aligning the O-rings 51 may be formed on one surface of the connecting member 24 facing the O-ring supporter 52.

The valve member 30 includes a ball 31 accommodated in the main body 20, a rotation shaft 32 fixed to the ball 31, and a rotation operation portion 33 coupled to the rotation shaft 32. The ball 31 is located at the center of the through hole 22 of the main body 20 and forms an opening 34 communicating with the sample opening 21 in the open state to receive the sample holder 10 in the opening 34.

That is, the opening 34 is a through-hole penetrating the ball 31 along the first direction in the open state, and the specimen holder 10 is accommodated in the opening 34 of the ball 31 through the specimen entrance 21 do.

A part of the rotary shaft 32 fixed to the upper end of the ball 31 is received in the connecting hole 23 of the main body 20 and the other part is projected outside the third opening OP3 of the main body 20. [ The rotary operation portion 33 is fixed to the rotary shaft 32 and assembled to the body 20 in a rotatable manner. The rotation centers of the rotary shaft 32 and the rotary operation portion 33 are parallel to the second direction. When the rotation operating part 33 is rotated, the ball 31 and the opening 34 rotate together to open and close the sample entrance 21.

More specifically, when the ball 31 is rotated 90 degrees from the state in which the valve member 30 is opened (the state in which the opening 34 of the ball 31 is in contact with the sample piece opening 21), the opening 34 of the ball 31, Is opposed to the inner surface of the main body 20, and the specimen entrance 21 is closed by the ball 31. [ The valve member 30 can open or close the sample entry / exit port 21 by rotation of the ball 31.

When the valve member 30 is closed, the outside air does not flow into the opening 34 where the specimen holder 10 is located.

The main body 20 and the rotary operation portion 33 may be provided with first and second stoppers 61 and 62 for limiting the amount of rotation of the rotary operation portion 33. [ A plurality of first stoppers 61 are provided along the circumferential direction on the outer surface of the main body 20 surrounding the connector 23, and the first stoppers 61 may be disposed at intervals of 90 degrees. The second stopper 62 protrudes from the rotation operating portion 33 toward the first stopper 61 and moves between the two first stoppers 61. [

When the second stopper 62 contacts any one of the two first stoppers 61, the valve member 30 can be opened and the valve member 30 is rotated so that the second stopper 62 The valve member 30 may be in a closed state when it contacts the other one of the first stoppers 61. The amount of rotation of the valve member 30 is limited by the first and second stoppers 61 and 62 when the valve member 30 is closed.

The movable bar 40 is slidably mounted along the first direction at the second opening OP2 of the main body 20. [ A sealing member 41 is provided between the movable rod 40 and the main body 20 to enable sliding of the movable rod 40 while sealing the second opening OP2 of the main body 20. [ The end of the moving rod 40 enters the opening 34 of the ball 31 and comes into contact with the specimen holder 10 while pushing the specimen holder 10 to move the specimen holder 10 into the analytical instrument .

The sample transfer container 100 of the present embodiment can be used in various analysis equipments such as a spectroscope, an electron microscope, and an optical microscope. For example, the sample transfer vessel 100 of this embodiment can be used in a glow discharge spectroscope (GDS) using glow discharge spectroscopy. The analyzing equipment to which the sample transfer container 100 of the present embodiment is applied is not limited to the above examples, and the sample transfer container 100 of the present embodiment can be used for various analysis equipments depending on the type and characteristics of the sample.

For example, when the specimen is a coating layer separated from a lithium secondary battery, the specimen delivery container 100 of the present embodiment can be used in a glow discharge spectroscope.

When a direct current or a high frequency voltage is applied between the anode and the cathode in an argon (Ar) atmosphere at a gas pressure of about 4 to 10 Torr, glow discharge occurs and argon ions are generated. The argon ion collides with the surface of the specimen, sputtering the specimen to a certain thickness, and the element that is separated from the specimen by sputtering emits light of the element intrinsic wavelength when it is excited in the plasma and then falls to the ground state. A method of analyzing such luminescence with a spectrometer is glow discharge spectroscopy.

5 is a view showing one example of a glow discharge lamp mounted in a glow discharge spectroscope.

5, the glow discharge lamp 70 includes a negative electrode block 71 in contact with the test piece 200 and a positive electrode block 73 spaced apart from the negative electrode block 71 with the insulator 72 interposed therebetween . The cathode block 71 forms an opening 71a for exposing the surface of the test piece 200 and the insulator 72 contacts most of the side walls of the opening 71a. A sealing member 74 such as an o-ring may be positioned between the cathode block 71 and the specimen 200.

The anode block 73 integrally forms a hollow anode tube 75 protruding toward the specimen 200 in the insulator 72. [ The end of the hollow cathode tube 75 is close to the surface of the test piece 200. An argon gas inlet 76 is formed in the anode block 73 to inject argon gas into the anode block 73. A connection block 77 and a window 78 are located outside the anode block 73.

When a high voltage is applied between the anode block 73 and the cathode block 71, a glow discharge occurs, and argon ions generated by the glow discharge impinge on the surface of the test piece 200, thereby sputtering the surface of the test piece 200. An element detached from the specimen 200 by sputtering emits light when it is excited in the plasma and then falls to the ground state, and a spectrometer provided outside the window 78 analyzes the light.

The negative electrode block 71 may be provided with a cooling jacket 79 through which the cooling liquid circulates and the cooling liquid cools the test piece 200, the negative electrode block 71 and the hollow positive electrode tube 75.

Next, a specimen transferring method using the specimen transferring container 100 of the present embodiment will be described.

6 is a flowchart illustrating a method of transferring a specimen according to an embodiment of the present invention.

Referring to FIG. 6, the method for transferring a specimen according to the present exemplary embodiment includes a first step (S10) of securing a specimen to a specimen holder in a glove box, a second step (S10) of inserting the specimen holder into the interior of the globe box, A third step (S30) in which the sample transfer container is drawn out from the glove box and assembled to the sample input port of the analysis equipment, and a fourth step (S40) in which the sample holder moves to the sample analysis position of the analyzer And a fifth step (S50) in which the sample transfer container is separated from the analysis equipment.

In the first step S10, the specimen may be cut from the positive electrode plate or the negative electrode plate of the lithium ion battery for the investigation of the coating layer, and the specimen is fabricated inside the glove box in an inert gas or high vacuum state.

BACKGROUND ART [0002] Recently, research on a secondary battery, an energy storage device, has been actively conducted. Among them, lithium-ion batteries, which have high energy density and high power and excellent low-temperature characteristics, are attracting attention. However, since they are more dangerous than other batteries, understanding the deterioration process inside the battery,

The deterioration of the lithium ion battery is affected by the ambient temperature and the charge / discharge current, thereby accelerating the deterioration of the battery. This phenomenon may be caused by the coating layer formed on the surface of the positive / negative active material inside the battery And solid electrolyte interphase (SEI).

7 is a schematic view showing a coating layer of a lithium ion battery.

7, the coating layer is mainly formed on the negative electrode active material (graphite), the inorganic material layer and the organic material layer are sequentially formed on the surface of the active material, and LiF precipitates are mixed in the oil / inorganic material layers.

The coating layer is a layer formed by decomposition of the electrolyte during charging / discharging of the battery, and has a function of protecting the active material of the battery. However, as the charging / discharging cycle progresses, the production amount increases and the resistance of the battery increases. Reduces lifetime. In addition, generation of the coating layer, which is an electrochemical reaction, is promoted by the temperature and the charge / discharge cycle, thereby accelerating the deterioration of the battery.

Since the coating layer is closely related to the cell performance, many studies have been conducted for the purpose of understanding the physicochemical nature of the coating layer. However, the coating layer is very unstable in the air and easily changes.

8 is a transmission electron microscope (TEM) photograph of a coating layer formed on natural graphite, wherein (a) shows no exposure to the atmosphere and (b) shows exposure to the atmosphere for 10 seconds. Referring to FIG. 8, it can be seen that a coating layer (indicated by 'surface film') of about 40 nm thickness is formed on the surface of a graphite electrode (indicated by 'graphite'). It can be seen that the shape of the coat layer largely changes due to short air contact.

9 is a photograph showing the surface change of the negative electrode active material separated from the lithium ion battery, showing that the left side is before the air exposure and the right side is after being exposed to the atmosphere for 5 minutes. In this way, specimens for coating layer studies are altered by exposure to the atmosphere, metal lithium ignition increases the risk of fire, and data reliability due to exposure to the atmosphere is reduced.

FIG. 10 is a photograph showing a sample preparation process in the first step shown in FIG. Referring to FIG. 10, in the glove box, the operator disassembles the pouch cell to separate the positive and negative plates, and prepares the prepared positive / negative plates to prepare the specimen.

Referring to Figs. 1 to 4, in the second step S20, the specimen is cut into a specific shape by a punch and attached to the groove 12 formed in the specimen pedestal 11. Thereafter, the operator opens the specimen inlet / outlet 21, places the specimen holder 10 on the opening 34 of the ball 31, and then rotates the rotary manipulation part 33 to close the specimen inlet / outlet 21. The entire process of the second step S20 is performed inside the glove box as in the first step S10, and the specimen is blocked from the outside air in the state where the valve member 30 is closed.

In the third step (S30), the sample transfer container 100 is drawn out from the glove box and assembled into a specimen input port of the analysis equipment. An O-ring 51, an O-ring support 52, and a fixing sheet 53 can be mounted around the sample entry port of the analysis equipment. Even though the sample transfer vessel 100 is drawn out from the glove box and placed in the atmosphere, the ball 31 closes the sample entrance 21, so that the external air does not flow into the specimen inside the body 20.

In the fourth step S40, the operator opens the specimen input port of the analyzer, switches the valve member 30 to the open state, and communicates the specimen input port of the analyzer with the opening 34 of the ball 31, Pushing the specimen holder 10 to the specimen analysis position of the analytical instrument.

In the fifth step (S50), the sample input port of the analyzing equipment is closed, the sample transfer container 100 for the analysis equipment is separated from the analyzing equipment, and sample analysis such as coating layer analysis and lithium quantitative analysis is performed in the analyzing equipment.

As described above, according to the sample transfer container 100 and the sample transferring method of the present embodiment, the sample can be prevented from being exposed to the atmosphere during the entire process of preparing the sample and inputting it to the analysis equipment. Therefore, it is possible to prevent the deterioration of the specimen due to exposure in the air, to perform accurate surface analysis, and to improve the reliability of the analysis data.

On the other hand, the above-mentioned coating layer is a main factor that interferes with the movement of lithium formed on the surface of the active material between the electrolyte and the active material in the charging and discharging process of the lithium ion battery. The main constituents of the coating layer are organic matter, inorganic matter and precipitate. The major constituent element of these three materials is lithium. Lithium is mainly analyzed by surface analysis equipment such as X-ray photoelectron spectroscopy (XPS), but accurate analysis may be difficult due to differences in principle of analysis depending on equipment characteristics.

For example, when depth direction analysis is performed in XPS, analysis of the coating layer by etching with argon makes it impossible to accurately analyze due to damage (change of bonding state) of the coating layer.

The above-described glow discharge spectrometer performs plasma quantitative analysis as a mean value for components separated by sputtering a predetermined thickness of the surface of a specimen surface, and obtains a calibration curve of the reference specimen for the measurement specimen, Therefore, a very accurate quantitative value can be obtained. It is reported that this quantitative value can be obtained almost the same as the result obtained by chemical analysis such as Inductively Coupled Plasma (ICP) spectrometer. (H. Takahara et al., Journal of Power Sources 244 (2013) 252-258)

In addition, the glow discharge spectroscope has the advantage of obtaining the data of the depth direction analysis and the quantitative analysis up to the thickness to be measured on the surface of the specimen in a short time. For example, if we compare the measurement time with the ICP spectrometer for quantitative analysis of lithium, we assume that the ICP spectrometer takes about 24 hours, including specimen preprocessing, have.

The sample transferring method of the present embodiment can be easily applied to other analytical instruments other than the glow discharge spectroscope according to the type and characteristics of the sample.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Of course.

100: Specimen transfer vessel 10: Specimen holder
11: a specimen pedestal 20; main body
21: specimen entrance 22: through hole
23: connector 24: connecting member
30: valve member 31: ball
32: rotating shaft 33:
34: opening 40: moving bar
61: first stopper 62: second stopper

Claims (12)

Specimen holder for specimen fixation;
A connecting member having a through hole formed therein, a connecting member fixed to one side of the through hole and having a specimen entrance port through which the specimen holder enters and exits, and a sealing member fixed to the other side of the through hole;
A valve having a through-hole and a ball having an opening for receiving the specimen holder, the valve being connected to the specimen opening in an open state, and a rotating operation portion for rotating the ball to open or close the specimen opening; And
A movable bar slidably mounted on the sealing member, for moving the specimen holder in contact with the specimen holder in the open state of the valve member,
A sample transfer vessel for atmosphere non-opening analysis. The method according to claim 1,
Wherein the specimen holder includes a specimen support having grooves for seating a specimen, and two discs are fixed on both sides of the specimen holder. delete The method according to claim 1,
The connecting member is coupled to a specimen input port of the analyzing equipment and forms a groove for the o-ring alignment. The method according to claim 1,
The through-hole is formed along the first direction inside the main body, and extends along a second direction intersecting the first direction with a connecting hole formed in the main body,
And the opening passes through the ball along the first direction in an open state. 6. The method of claim 5,
Wherein the balls and the rotary operation portion are connected by a rotation shaft accommodated in the connection port, and the rotary operation portion is rotatably coupled to the body at the outside of the connection port. The method according to claim 6,
At least two first stoppers are fixed along the circumferential direction on the outer surface of the main body surrounding the connector, and a second stopper fixed to the rotation operating portion moves between the two first stoppers to rotate the rotation operating portion The sample transfer vessel for atmospheric non-open analytical analysis. A first step of preparing a specimen inside the atmosphere and the glove box blocked and fixing the specimen to the specimen holder;
A second step of opening a specimen doorway of the body in the glove box, receiving the specimen holder in the body, and closing the specimen doorway;
A third step in which the sample transfer container is drawn out from the glove box and then bonded to the sample input port of the analysis equipment; And
And a fourth step in which the sample inlet and the sample outlet are opened and the sample holder moves to a specimen analyzing position of the analyzer,
Wherein the ball has a ball and a rotation operating part, the ball passing through the inside along one direction to form an opening which opens to the sample entrance in an open state,
Wherein the balls are rotated by the rotating operation unit to open or close the sample entry / exit port in the second step and the fourth step. 9. The method of claim 8,
In the first step, the specimen is pretreated after being cut from a positive electrode plate or a negative electrode plate of a lithium ion battery, and includes a coating layer. delete 9. The method of claim 8,
In the third step, an o-ring is installed in the sample inlet,
Wherein the sample transporting container includes a connecting member that forms a groove for the o-ring alignment and is coupled to the sample loading port. 9. The method of claim 8,
A movable bar is slidably installed on the other side of the body opposite to the specimen input port,
In the fourth step, the specimen holder is pushed by the moving rod to move to a specimen analysis position.

Images