JP2011089160A - Method and apparatus for manufacturing lithium film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and an apparatus for manufacturing a lithium film, with which losses of raw materials can be reduced and working efficiency can be enhanced. <P>SOLUTION: The lithium film manufacturing apparatus A includes a vacuum chamber 10, and a pass box 12 for collecting and introducing various members between the vacuum chamber 10 and itself. A base material reel 24 with a base film 21 wound around it, a product reel 25 with a lithium laminate film 23 wound around it, a rotary roll 26 for guiding the base film 21, a raw material crucible 13 in which raw materials such as lithium are put in, and a shield plate 14 having an opening 15 are arranged in the vacuum chamber 10. The shield plate 14 is a specified member formed of lithium or the like. Particles of the evaporated lithium or the like are deposited on the base film 21 and the shield plate 14. During maintenance, the shield plate 14 is replaced with a new one, and the shield plate 14 with lithium or the like being deposited thereon is heated and melted, and is reused. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a lithium film manufacturing method and a lithium film manufacturing apparatus for depositing a lithium film made of lithium or a lithium alloy on a base film used in a lithium battery or the like.

  In recent years, in response to the demand for higher functionality and smaller size of various electronic devices, particularly power storage devices, the batteries are also required to be lighter. Therefore, a film made of lithium or a lithium alloy (hereinafter referred to as “lithium film”) is used as a battery element such as a negative electrode, and further thinning of the lithium film is required.

  A typical method for producing a lithium film is a rolling method in which a lithium foil is formed by rolling from an ingot of lithium or a lithium alloy. However, in order to achieve a thinner film, for example, disclosed in Patent Document 1 Thus, a method for depositing a lithium film on a substrate by vapor deposition has been proposed. The vapor deposition method is a method in which a lithium or lithium alloy raw material is evaporated in a chamber and the scattered particles are deposited on a substrate.

JP 2002-97564 A

By the way, when the vapor deposition method is used, the evaporated particles are scattered in all directions from the evaporation source, so that lithium or a lithium alloy is deposited not only on the substrate but also on the peripheral members in the chamber. For example, in the vapor deposition method, a shielding plate that surrounds the evaporation source is disposed as a peripheral member so as to minimize the scattering of particles outside the vapor deposition region of the substrate. Therefore, a considerable amount of lithium or lithium alloy is deposited on the shielding plate.
For this reason, the raw material loss deteriorates the material yield and increases the manufacturing cost. Further, since lithium reacts when exposed to air, the work of cleaning lithium deposited on the surrounding members requires delicate attention and complicated work, leading to an increase in manufacturing cost.
In addition, when the chemical deposition method is used, since lithium or a lithium alloy is deposited on any member maintained at the thermal decomposition temperature, there is a similar problem.

  An object of the present invention is to provide a lithium film manufacturing method and a lithium film manufacturing apparatus capable of realizing reduction of raw material loss and improvement of workability while depositing lithium or a lithium alloy by a vapor phase method. .

The method for producing a lithium film of the present invention is a method for depositing a lithium film made of lithium or a lithium alloy on a base material by a vapor phase method in a chamber in which a production member is arranged. have.
In the method of the present invention, the specific member of the manufacturing member is made of lithium or a lithium alloy. The specific member is disposed in the chamber after the chamber is in an inert atmosphere in which no reaction between lithium and other substances occurs. Thereafter, a lithium film is deposited on the substrate by a vapor phase method in the chamber.
The “vapor phase method” includes a PVD method (physical deposition method) and a CVD method (chemical deposition method), and any of them may be used.
The “lithium film” includes not only pure lithium but also a film made of a lithium alloy such as a lithium-aluminum alloy. The lithium alloy is not particularly limited as long as it is a lithium-rich alloy.

By this method, the following effects can be obtained.
When a lithium film is formed by a vapor phase method, lithium or a lithium alloy (hereinafter also referred to as “lithium or the like”) is deposited not only on a substrate but also on a manufacturing member, resulting in loss of raw materials. . In addition, periodic maintenance for removing lithium and the like deposited on the manufacturing member is required.
For example, when a physical deposition method such as a vapor deposition method or a sputtering method is used, particles such as lithium are scattered in multiple directions from the raw material and are also deposited on the shielding member. In the present invention, the shielding member may be made of lithium or the like as the specific member.
During maintenance, the specific member such as a shielding member on which lithium or the like is deposited may be removed without removing the deposited lithium or the like and replaced with a new specific member.
Thereafter, the specific member and lithium or the like deposited thereon can be heated and melted and reused as a raw material or a new shielding member. That is, raw material loss can be reduced.
Moreover, since the operation | work which removes the lithium etc. which accumulated on the specific member becomes unnecessary, a complicated operation | work becomes unnecessary in the case of a maintenance.
As described above, the manufacturing cost can be significantly reduced by reducing the raw material loss and simplifying the maintenance work.
Note that when a lithium film is formed by decomposing a gas containing lithium or the like by using a chemical deposition method, the lithium film is deposited at any portion maintained at the thermal decomposition temperature of the gas. In this case as well, the above-described effects can be obtained by using a part of the manufacturing member as the specific member and configuring the specific member with lithium or a lithium alloy.

  Although a specific member may be created in a chamber, it may be created in another room under an inactive atmosphere. In that case, the created specific member can be safely moved to the chamber by being installed in the chamber while maintaining the atmosphere surrounding the specific member in an inert atmosphere.

  In particular, a lithium film is often manufactured by a physical deposition method in which lithium or lithium alloy particles are scattered in a chamber. Examples of physical deposition methods include resistance heating, electron beam evaporation, molecular beam epitaxy, ion plating, ion beam deposition, sputtering, and the like.

As a specific member, it can select arbitrarily from the members for manufacture arrange | positioned in a chamber, and can be made into a specific member.
In particular, when a physical deposition method is used, a lithium or lithium alloy material is placed on the holding member in a chamber held in an inactive state, and the lithium film of the base material is deposited as a specific member surrounding the holding member. A shielding member having an open area is disposed in the chamber. Then, a lithium film is deposited by scattering particles such as lithium from the raw material.
When the physical deposition method is used, almost the same amount of lithium particles and the like as the base material scatters in the vicinity of the opening of the shielding member. . Therefore, since the maintenance frequency of the shielding member is considerably increased, the above-described operational effects of the present invention can be obtained more significantly by using the shielding member as the specific member.

  The apparatus for producing a lithium film of the present invention is an apparatus for depositing a lithium film made of lithium or a lithium alloy on a substrate by a vapor phase method. And it has the chamber in which a base material is arrange | positioned, and the member for manufacture arrange | positioned in a chamber, At least 1 is a specific member comprised by lithium or a lithium alloy among members for manufacture.

  With this manufacturing apparatus, the method for manufacturing a lithium film can be carried out while exhibiting the above-described effects.

  In particular, when the physical deposition method is used in the vapor phase method, the manufacturing member includes a holding member that holds a raw material of lithium or a lithium alloy, and a shielding member that opens an area where the lithium film of the base material is deposited Including. And as mentioned above, when a shielding member is a specific member, the effect of this invention can be acquired more notably.

  ADVANTAGE OF THE INVENTION According to this invention, the lithium film manufacturing method and lithium film manufacturing apparatus which can implement | achieve reduction of a raw material loss and improvement of workability | operativity can be provided, depositing lithium or a lithium alloy by a gaseous-phase method.

It is a side view which fractures | ruptures the inside of a chamber and shows schematic structure of the lithium film manufacturing apparatus which concerns on embodiment of this invention. It is a back view of the shielding member concerning an embodiment of the invention. It is a flowchart which shows the manufacture procedure of the lithium film which concerns on embodiment of this invention. It is a longitudinal cross-sectional view which shows the modification of a shielding member. It is a side view which fractures | ruptures the chamber interior and shows schematic structure of the lithium film manufacturing apparatus which concerns on a modification.

FIG. 1 is a side view of a lithium film manufacturing apparatus A according to an embodiment of the present invention. FIG. 2 is a back view of the shielding member according to the embodiment of the present invention.
As shown in FIG. 1, the lithium film manufacturing apparatus A according to the embodiment includes a vacuum chamber 10 and a pass box 12 that collects and introduces various members between the vacuum chamber 10. This pass box 12 uses a part of a clustering structure well known in a semiconductor manufacturing apparatus or the like. That is, since lithium has a property of reacting with oxygen at room temperature, the vacuum chamber 10 needs to be maintained in an inert atmosphere such as an inert gas atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere containing an inert gas. In the present embodiment, the vacuum chamber 10 is maintained in a reduced pressure atmosphere. Therefore, a pass box 12 maintained in an inert atmosphere similar to the vacuum chamber 10 is disposed adjacent to the vacuum chamber 10, and products, raw materials, manufacturing members, and the like are placed in the vacuum chamber 10 via the pass box 12. Introduction or recovery from the vacuum chamber 10.

  In the vacuum chamber 10, a manufacturing member for depositing a lithium film 22 made of lithium or a lithium alloy to form a lithium laminated film 23 on a base film 21 is disposed. A base material reel 24 wound with the base material film 21 before the lithium film 22 is deposited is rotatably attached to a support member 27 fixed to the ceiling surface, and the product around which the lithium laminated film 23 is wound. The reel 25 is rotatably attached to a support member 29 fixed to the ceiling surface. Further, while the base film 21 is fed from the base reel 24 to the product reel 25, a rotating roll 26 for guiding the base film 21 is disposed. The rotary roll 26 is rotatably attached to a support member 28 fixed to the ceiling surface.

  A raw material crucible 13 (or a raw material boat) (holding member) in which a raw material of lithium or a lithium alloy (lithium or the like) is placed is disposed below the rotary roll 26. The lithium or the like in the raw material crucible 13 is configured to evaporate lithium or the like by heating the crucible 13 or irradiating with an electron beam from the side.

Further, as used in a general vapor deposition method, a shielding plate 14 (shielding member) that surrounds the raw material crucible 13 and has an opening 15 in the film formation region of the base film 21 is disposed. The evaporated particles such as lithium are deposited on the base film 21 in a region located in the opening 15 of the shielding plate 14.
FIG. 2 is a back view showing the structure of the shielding plate 14 as seen from the back side (downward side). In the present embodiment, the end faces of the pair of shielding plates 14 having a U-shaped groove are in contact with each other, and the opening 15 is formed by the pair of U-shaped grooves. However, the end surface of each shielding plate 14 may have a flat shape without a U-shaped groove. In that case, the end surfaces of the shielding plates 14 are separated from each other without being in contact with each other, and an opening 15 is formed between both end surfaces (see the broken line in FIG. 2).

Here, the feature of this embodiment is that the shielding plate 14 is made of lithium or the like.
However, the composition of lithium or lithium alloy constituting the shielding plate 14 need not be exactly the same as that of the deposited lithium film 22. This is because even if the composition is slightly deviated, it is sufficient if it can be reused as a raw material.

In the present embodiment, a plastic film is used as the substrate film 21, but a metal film may be used.
The base film 21 made of plastic is not particularly limited as long as it is a film having a mechanical strength enough to function as a protective film for a lithium film (a film having a waist), but polyester, nylon, polypropylene, polyethylene, polyethylene -There are films of general-purpose resins such as polypropylene copolymers and films of engineering plastics.

  Among these, polyolefin, PET, polyvinylidene chloride and polymers having vinylidene chloride as a main component whose molecular formula is represented by CnH2n + 2-2m are unlikely to react with the lithium film 10, so that the material of the base film 21 As a result, generation of flare in the base film 21 and the lithium film 22 can be suppressed.

In addition, what is necessary is just to select and use the optimal thing for the thickness of the base film 21 according to work conditions, such as the width | variety and thickness of the lithium film | membrane 22, and the winding speed to the product reel 25, etc. In the case of using a general-purpose resin, a thickness of 5 μm or more, preferably 10 μm or more is required to maintain a firm strength, and the upper limit is not limited, but preferably 3 mm or less, more preferably a lithium laminated film In order to continuously wind 23 around the product reel 25, the thickness is preferably 100 μm or less.
The thickness of the lithium film 22 is preferably about 1 to 20 μm, but is not limited to this range.

  In addition, when the base film 21 and the lithium laminated film 23 are not wound on a reel, for example, when processed as a thin plate having a side of 15 cm or more (such as a single wafer type using an XY stage), the thickness is about 1 mm. The above base film 21 can be used, and the lithium film 22 can be laminated on the surface thereof.

Next, the manufacturing procedure (deposition procedure) of the lithium film in the present embodiment will be described.
FIG. 3 is a flowchart showing a procedure for manufacturing a lithium film in the present embodiment.
First, in step ST1, the vacuum chamber 10 is evacuated. At this time, an inert gas such as helium, argon, neon, krypton, or nitrogen may be mixed under reduced pressure.

Next, in step ST <b> 2, the specific member (the shielding plate 14 in the present embodiment) is placed in the vacuum chamber 10. Further, the base material reel 24 and the product reel 25 are attached to the support members 27 and 29.
Next, a raw material of lithium or a lithium alloy is introduced into the raw material crucible 13 in step ST3. However, step ST3 may be performed before step ST2.

  Next, in step ST4, the raw material crucible 13 is heated, and the raw material such as lithium is maintained at a temperature not lower than the melting point and not higher than the boiling point, thereby evaporating lithium and the like. Scatter. At this time, most particles such as lithium are scattered in multiple directions.

  As a result, as shown in step ST5, lithium or the like is deposited on the base film 21, and the lithium film 22 is formed. In ST6, the product reel 25 is removed from the vacuum chamber 10 via the pass box 12. The lithium film 22 is transferred from the base film 21 to a part of an electronic component such as a power storage device, or is used as a member of the power storage device while being deposited on the base film 21.

  On the other hand, as shown in step ST7, since lithium or the like is deposited on the specific member (in this embodiment, the shielding plate 14), the specific member is taken out and replaced with a new specific member in step ST8.

  Thereafter, as shown in step ST9, the specific member is heated and melted together with the deposited lithium or the like and reused as a raw material or a new specific member.

According to the present embodiment, the following effects can be exhibited.
As described above, when a lithium film is deposited by an evaporation method, particles of lithium or a lithium alloy (such as lithium) are scattered in multiple directions. And since lithium etc. of considerable thickness accumulates not only on the base film 21 but on the shielding plate 14 (specific member), a raw material loss occurs. In addition, periodic maintenance for removing lithium and the like deposited on the shielding plate 14 is required.
However, in the present invention, during maintenance, the specific member such as the shielding plate 14 on which lithium or the like is deposited may be removed without removing the deposited lithium or the like and replaced with a new specific member. The specific member and lithium deposited thereon can be reused as a raw material by heating and melting. That is, raw material loss can be reduced.
Moreover, since the operation | work which removes the lithium etc. which accumulated on the specific member becomes unnecessary, a complicated operation | work becomes unnecessary in the case of a maintenance.
As described above, the manufacturing cost can be significantly reduced by reducing the raw material loss and simplifying the maintenance work.

Here, specifically, the thickness of lithium or the like deposited on the shielding plate 14 is roughly estimated as follows.
For example, the total area of the base film 21 on which the lithium film 22 is deposited is W × L1, and the area of the base film 21 that is located in the opening 15 is W × L2 (L2 is the feed direction of the base material). It is substantially equal to the dimension of the opening 15 (dimension in the feed direction). Since the base film 21 moves but the shielding plate 14 does not move, lithium or the like is constantly accumulated on the shielding plate 14 while the lithium film 22 is formed on the entire area of the base film 21.
That is, in the region adjacent to the opening 14 of the shielding plate 14, roughly estimated, lithium or the like having a thickness t = W × L1 / W × L2 = L1 / L2 is deposited.
Therefore, when the total length L2 of the base film 21 is about 100 m and the feed direction dimension L1 of the opening 15 is about 10 cm, the lithium film 22 formed on the base film 21 in the region near the opening 15 of the shielding plate 14. Lithium or the like having a thickness of about 1000 times the thickness is deposited. Since the thickness of the lithium film 22 is about 1 to 20 μm, lithium or the like having a thickness of several millimeters is deposited in a region near the opening 15 of the shielding plate 14 at the time of one film formation.

  As can be seen from the above estimation, lithium or the like is deposited very thick on the shielding plate 14, and therefore the replacement frequency of the shielding plate 14 must be increased. Therefore, it can be seen that the effect of the present invention described above is very large.

-Modification of shielding plate-
FIG. 4 is a longitudinal section showing a modification of the shielding plate 14. In the above-described embodiment, a pair of shielding plates 14 are arranged. However, as shown in FIG. 4, a shielding plate 14 may be formed by bending a single plate of lithium or the like. In this case, the shape of the opening 15 may be a shape indicated by a solid line in FIG. 2 or a shape indicated by a broken line.
In particular, the higher the purity of lithium, the softer the plate of lithium or the like, so that it can be easily folded by hand or using an instrument.

In the above embodiment, an example in which the specific member is only the shielding plate 14 (shielding member) has been described. However, the specific member is not limited to the shielding plate 14.
For example, when the opening 15 of the shielding plate 14 has a shape indicated by a broken line in FIG. 2, a considerable amount of particles such as lithium are scattered above the shielding plate 14. Therefore, in such a case, it is preferable to install another shielding plate above the shielding plate 14.

-Variation of lithium film manufacturing equipment-
FIG. 5 is a side view showing a schematic configuration of a lithium film manufacturing apparatus A according to a modification, with the interior of the chamber being broken.
In this modified example, a protective plate 17 that covers the inner wall of the vacuum chamber 10 is disposed as the specific member in addition to the shielding plate 14 in the embodiment or the above-described modified example. Most evaporative particles such as lithium go straight and collide with the shielding plate 14, but some of them emanate backward from the gap of the shielding plate 14. Further, when the shielding plate 14 has a shape indicated by a broken line in FIG. 2, a considerable amount of particles such as lithium are scattered to the rear of the shielding plate 14. Therefore, lithium and the like are gradually deposited on the inner wall of the vacuum chamber 10. Even in such a case, as the maintenance work, it is only necessary to replace the protective plate 17 without cleaning the inner wall of the vacuum chamber 10, so that the same effect as the above embodiment can be obtained.
In addition, you may comprise the raw material crucible 13 (holding member) holding a raw material with lithium or a lithium alloy. Moreover, also when arrange | positioning the various members shown in FIG. 1, FIG. 5 and other members in the vacuum chamber 10, those members can be suitably comprised with lithium or a lithium alloy.

  In each of the above embodiments, the base film 21 is made of a single plastic film. However, a polyvinylidene chloride or a polymer film mainly composed of vinylidene chloride is laminated on the plastic film as a surface material. A surface material may be interposed between the plastic film and the lithium film 22. Thereby, the peelability from the base film 21 of the lithium film 22 improves.

  However, the “polymer having vinylidene chloride as a main component” means a polymer having a vinylidene chloride content of 50 weight percent or more, and if the vinylidene chloride content is 50 weight percent or more, vinylidene chloride and other monomers It is a concept that includes an alternating copolymer, a block copolymer, a graft copolymer and a mixture thereof, and a mixture of polyvinylidene chloride and another polymer. Examples of other monomers include olefins and halides thereof, and examples of other polymers include polyolefins and halogen-substituted products thereof. Among other monomers, it is preferable to use vinyl chloride or 1,2-dichloroethylene, and it is preferable to use polyvinyl chloride or poly1,2-dichloroethylene as the other polymer. In view of versatility and low cost, it is preferable to use a copolymer of vinylidene chloride and vinyl chloride.

  In each of the above embodiments, a plastic film is used as the base film 21, but a metal film that does not substantially react with lithium may be used. In the case where a metal film is used as the base film 21, the metal film and the lithium film 21 are in phase conduction, so that the number of cases where the metal film can be used as a part of the electricity storage device increases. As the metal, Cu, Ni, Fe, Ta, W, etc., which have little reactivity with lithium, are preferable.

  The structure of the embodiment of the present invention disclosed above is merely an example, and the scope of the present invention is not limited to the scope of these descriptions. The scope of the present invention is indicated by the description of the scope of claims, and further includes meanings equivalent to the description of the scope of claims and all modifications within the scope.

  INDUSTRIAL APPLICABILITY The present invention can be used for manufacturing a lithium film incorporated in a power supply device such as a mobile phone, a notebook computer, a hybrid vehicle, and an electric vehicle, or an uninterruptible power supply device.

A Lithium film production equipment 10 Vacuum chamber 12 Pass box 13 Raw material crucible (holding member)
14 Shield plate (shield member, specific member)
DESCRIPTION OF SYMBOLS 15 Opening 17 Protection board 21 Base film 22 Lithium film | membrane 23 Lithium laminated film 24 Base material reel 25 Product reel 26 Rotating roll 27-29 Support member

Claims (7)

A method of depositing a lithium film made of lithium or a lithium alloy on a substrate by a vapor phase method in a chamber in which a manufacturing member is disposed,
A step (a) of setting the inside of the chamber to an inactive atmosphere in which reaction between lithium and another substance does not occur;
A step (b) in which at least the specific member of the manufacturing member is made of lithium or a lithium alloy, and the specific member is placed in the chamber after the step (a);
A step (c) of depositing a lithium film on the substrate;
A method for producing a lithium film comprising: In the manufacturing method of the lithium film | membrane of Claim 1,
In the step (b), the specific member is created in a room different from the chamber under an inert atmosphere, and the atmosphere surrounding the specific member is maintained in the inert atmosphere, and moved into the chamber. A method for producing a lithium film. In the manufacturing method of the lithium film | membrane of Claim 1 or 2,
The method for producing a lithium film, further comprising a step (d) of heating and melting and mixing the specific member and lithium or lithium alloy deposited thereon after the step (c). In the manufacturing method of the lithium film as described in any one of Claims 1-3,
In the step (b), a lithium or lithium alloy raw material is installed in the holding member in the chamber, and as the specific member, a shielding member that surrounds the holding member and opens a region on which the lithium film of the substrate is deposited Placed in the chamber,
In the step (c), a lithium film is deposited by scattering lithium or lithium alloy particles from the raw material under reduced pressure using a physical deposition method. It is a specific member used for the manufacturing method of the lithium film of Claim 4,
A shielding member that is made of lithium or a lithium alloy, surrounds a holding member that holds a raw material of lithium or a lithium alloy, and has an opening in a region where the lithium film of the substrate is deposited. An apparatus for depositing a lithium film made of lithium or a lithium alloy on a substrate by a vapor phase method,
A chamber in which the substrate is disposed;
A manufacturing member disposed in the chamber;
With
At least one of the manufacturing members is a lithium film manufacturing apparatus that is a specific member made of lithium or a lithium alloy. The lithium film manufacturing apparatus according to claim 6,
A lithium film manufacturing apparatus used for physical deposition,
The manufacturing member includes a holding member that holds a raw material of lithium or a lithium alloy, and a shielding member that surrounds the holding member and opens a region where the lithium film of the base material is deposited,
The lithium film manufacturing apparatus, wherein the shielding member is the specific member.

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