KR101763356B1 - Method of Preparing Polymer Film Using iCVD - Google Patents

Abstract

By utilizing initiated chemical vapor deposition (iCVD) reactor using an initiator, various polymer films are formed on various substrates coated with a sulfur copolymer (poly (S-r-DIB)), especially, on a sulfur copolymer electrode of a lithium-sulfur secondary battery, and the coated polymer film exhibits good adhesion to the substrate coated with the sulfur copolymer, wherein the coated polymer film exhibits an effect of preventing polysulfide anion eluted between the charging and discharging processes of the coated polymer film from escaping from an anode to an electrolyte layer when the polymer film is applied to a sulfur copolymer electrode.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for preparing a polymer membrane using a chemical vapor deposition reactor (iCVD)

The present invention relates to a method of manufacturing a polymer membrane using a chemical vapor deposition reactor (iCVD) using an initiator, and more particularly, to a method of manufacturing a polymer membrane using an iCVD reactor in which a substrate coated with a sulfur copolymer is placed and fixed, (ICVD) using an initiator for introducing a polymer onto a substrate coated with the sulfur copolymer and polymerizing the polymer on the substrate coated with the sulfur copolymer.

Since the lithium secondary battery has a high energy density, it has been widely applied not only to portable devices such as cellular phones and personal computers but also to hybrid cars, electric vehicles, and electric power storage and storage systems. As one of such lithium secondary batteries, a lithium-sulfur secondary battery has recently been attracting attention, in which sulfur is used as the cathode active material, lithium is used as the anode active material, and the charge and discharge are performed by the reaction of lithium and sulfur.

In the lithium-sulfur secondary battery, there are a maximum of two lithium ions that react with one sulfur, and since sulfur is lighter than the transition metal, there is an advantage that the specific capacity of the lithium-sulfur secondary battery can be improved. However, although lithium-sulfur secondary batteries have a higher energy storage capacity than conventional lithium ion batteries, S _x ^2- generated from the sulfur electrode between charge and discharge is eluted into electrolyte and irreversibly precipitates on the surface, There is a continuous decrease in the chemical active substance. As a result, there is a problem that the energy capacity is rapidly reduced and the lifetime is very short, so that it is not commercialized.

In order to solve this problem, there have been reported many techniques for physically blocking or chemically adsorbing S _x ^{2 -} elution by wrapping sulfur, which is a cathode active material, on a nanometer scale, but the manufacturing process is complicated and expensive. As a relatively inexpensive and simple process, studies have been conducted on the synthesis of polymeric copolymers chemically bonded to molecular units of sulfur. Poly (S- r- DIB) was used as a secondary battery electrode to dramatically improve storage capacity and lifetime, but could not completely prevent the elution of S _x ^{2 -} .

In addition, S _x ² by making further the anti-diffusion between the sulfur electrode and the ^{membrane-being} precipitated after the out is been studied the technique to prevent the dissolution, because the contact is not uniform between the sulfur electrode and the diffusion prevention layer, the active material in the cracks spread There is a problem of reducing the active material generated.

The present inventors have made intensive efforts to solve the above problems. As a result, the present inventors have found that when an electrode is manufactured by uniformly adhering a polymer membrane to a surface of a sulfur electrode using an iCVD process, which is a vapor deposition process using an initiator, It is possible to economically manufacture an electrode for a lithium-sulfur secondary battery capable of effectively preventing the diffusion phenomenon of S _x ^{2 -} and ensuring an energy capacity and a service life, and completed the present invention.

An object of the present invention is to provide an economical method of manufacturing a polymer membrane, particularly a lithium-sulfur secondary battery electrode, which ensures an energy capacity and a service life that effectively prevent the diffusion phenomenon of S _x ^{2 - which} is a problem of a lithium- .

In order to achieve the above object, the present invention provides a method of manufacturing a semiconductor device, comprising: (a) placing and fixing a substrate coated with a sulfur copolymer on an iCVD reactor; And (b) depositing a monomer and an initiator in an iCVD reactor to deposit the polymer through polymerization of the monomers on the substrate coated with the sulfur co-polymer. And a manufacturing method thereof.

The present invention also provides a method for producing a lithium secondary battery, which is characterized in that pDEGDA is coated to a thickness of 1 nm to 10 탆 in poly (S- r -diisopropenylbenzene) and storage capacity is 900 to 1500 mAh / g after 100 cycles. Thereby providing an electrode for a sulfur secondary battery.

The polymer-coated electrode for a lithium-sulfur secondary battery using iCVD according to the present invention can effectively prevent the diffusion phenomenon of S _x ^{2 -} , can ensure the energy capacity and the life, and is economically effective.

1 is a schematic view illustrating a process of coating a polymer on a poly (S- r- DIB) electrode using iCVD according to an embodiment of the present invention.
2 is a cross-sectional view showing a water contact angle of a wafer coated with a pDEGDA polymer according to an embodiment of the present invention.
3 is an FT-IR graph of a DEGDA monomer and a pDEGDA polymer according to an embodiment of the present invention.
4 is a view showing the water contact angle measured after coating various polymers on the SDIB surface through an iCVD process according to an embodiment of the present invention (p4VP: poly 4-vinyl pyridine: pDEGDA: poly diethyleneglycoldiacrylate: pV4D4: poly 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl cyclotetrasiloxane, pPFDMA: poly 3,3,4,4,5,5,6,6,7,7,8,8,9, 9,10,10,10 heptadecafluorodecyl methacrylate)
FIG. 5 is a graph showing the contact angle of water measured before and after the coating of the pMAA polymer on the SDIB film according to an embodiment of the present invention through the iCVD process.
FIG. 6 is a view showing a result of measuring the contact angle of water after washing the pDMAEMA polymer on the SDIB film according to one embodiment of the present invention, before and after coating the polymer with iCVD.
FIG. 7 is a view showing the adhesion between a polymer thin film and an SDIB film by a tape test after pEGDMA coating using iCVD according to an embodiment of the present invention.
8 is a view showing adhesion between a polymer thin film and an SDIB film by a tape test after pDVB coating using iCVD according to an embodiment of the present invention.
FIG. 9 is a graph showing water contact angles measured before and after chloroform spin coating on a pDEGDA-coated SDIB film and a bare SDIB according to an embodiment of the present invention.
10 is a graph showing the contact angle of DOL / DME solvent on bare SDIB and pDEGDA coated SDIB according to an embodiment of the present invention.
11 is a graph illustrating a result of measuring the performance of an iCVD coated electrode according to an embodiment of the present invention.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

In the present invention, when an electrode is manufactured by uniformly adhering a polymer membrane to the surface of a sulfur electrode using an iCVD process, which is a vapor deposition process using an initiator, it is possible to effectively prevent diffusion of S _x ^{2 -} , which is a problem of existing lithium- Thereby making it possible to economically produce a lithium-sulfur secondary battery with guaranteed energy capacity and lifetime.

Accordingly, in one aspect, the present invention provides a method of manufacturing a semiconductor device, comprising: (a) placing and fixing a substrate coated with a sulfur copolymer on an iCVD reactor; And (b) depositing a monomer and an initiator in an iCVD reactor to deposit the polymer through polymerization of the monomers on the substrate coated with the sulfur co-polymer. And a manufacturing method thereof.

A chemical vapor deposition reactor (iCVD) using an initiator used in the present invention is a device for decomposing an initiator of a gas phase into radicals to cause polymerization of a monomer. Peroxides such as tert-butyl peroxide (TBPO) are mainly used as the initiator. This material is a volatile substance having a boiling point of about 110, which causes pyrolysis at about 150 ° C. Benzophenone, which decomposes by heat such as tert-butyl peroxide (TBPO) to form radicals, and decomposes by light such as UV to form radicals, may also be used.

The iCVD process does not seem to be much different from the conventional inorganic thin film deposition CVD process because the thin film is deposited by the energy supply of the heated filament heat source or UV. However, the iCVD process is performed at a low filament temperature between 200 ° C. and 350 ° C. And the temperature of the substrate surface on which the polymer thin film is deposited can be kept as low as 10 to 50 ° C. Because of these low surface temperatures, iCVD can be used to coat polymer films on multiple substrates that are susceptible to mechanical and chemical impacts, such as paper or cloth. And since the process is done in vacuum from 50 mTorr to 1000 mTorr, no high vacuum equipment is needed and the amount of monomer and initiator is controlled by the injection valve.

iCVD technology is a dry process, which enables uniform, high quality coatings to be performed on a large scale. Especially, when coated on a poly (S- r- DIB) electrode, which has superior performance compared to the conventional sulfur electrode, it exhibits a more excellent adhesion effect due to strong attraction between the coated polymer and the copolymer.

The substrate coated with the sulfur copolymer can be produced by applying a mixture containing a sulfur copolymer, a carbon conductive material, a binder, and a solvent to a current collector.

The monomer may be added to the monomer vessel of the iCVD reactor before the step (a) and heated to 30 to 45, and the initiation agent may be added to the initiator vessel of the iCVD reactor and maintained at room temperature.

The sulfur copolymer is preferably poly (S- r -diisopropenylbenzene).

The process may be carried out at a temperature of 25 to 45 DEG C and a pressure of 150 to 350 mTorr for 10 minutes to 12 hours. If the temperature of the chamber is less than 150 mTorr or more than 350 mTorr, the deposition rate may be slowed down when the temperature is less than 25 ° C. When the temperature exceeds 45 ° C, Or the deposition rate is slowed. And. Since the deposition time is related to the deposition thickness, when the deposition time exceeds 10 minutes to 12 hours, there is a problem that the deposition thickness becomes thin or thick.

In the present invention, the charging temperature of the monomer and the initiator are 20 to 100 ° C and 20 to 100 ° C, respectively, and the temperature of the filament in the substrate and the chamber may be 10 to 100 ° C and 100 to 500 ° C, respectively. It is possible to deposit at a suitable flow rate at the above range of temperature.

In the present invention, it is preferable that the monomer is a monomer having a vinyl group such as 4-vinyl pyridine (4VP), 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetra Siloxane (2,4,6,8-tetramethyl-2,4,6,8-tetravinyl cyclotetrasiloxane, V4D4), 3,3,4,4,5,5,6,6,7,7,8,8, 9,9,10,10,10-heptadecafluorodecyl methacrylate (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10 , 10-heptadecafluorodecyl methacrylate, PFDMA), 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, hexavinyldisiloxane, glycidyl methacrylate, divinylbenzene, diethylene glycol divinyl Ether, diethyleneglycoldiacrylate (DEGDA), ethylene glycol dimethacrylate, dimethylaminoethyl methacrylate, methacrylic acid and 1,3-diethenyl-1,1,3,3-tetramethyl- 1H, 1H, 2H, 2H-perfluorodecyl acrylate, perfluorodecyl methacrylate, dodecafluoroheptyl acrylate Pentafluorophenyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecafluorononyl acrylate, 2- Methyl-3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecafluorononyl acrylate, 3,3,4,4,5, 5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate, 2-methyl-3,3,4,4,5,5,6,6,7,7,8, 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptyl acrylate, 2-methyl-3,3,4,5,5,6,6,7,7,7-tetradecafluorooctyl acrylate, 4,4,5,5,6,6,7,7,7-undecafluoroheptyl acrylate, 3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate , 2-methyl-3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate, 3,3,4,4,5,5,6,6,7,7, 8,8,9,9,10,10,11,11,11-nonadecafluoroundecyl acrylate, 2-methyl-3,3,4,4,5,5,6,6,7,7 , 8,8,9,9,10,10,11,11,11-nonadecafluoroundecyl acrylate, 3,3,4,4,5,5,6,6,7,7,8, 8,9,9,10,10,11,11,12,12,12-heneicosafluorododecyl acrylate, 2-methyl-3,3 , 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluorododecyl acrylate, 3 , 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13-Tricosafluorotrydyl Acrylate, 2-methyl-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13 , 13-tricosafluorotridecyl acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12 , 13,13,14,14,14-pentacosafluorotetradecyl acrylate, and 2-methyl-3,3,4,4,5,5,6,6,7,7,8,8,9 , 9,10,10,11,11,12,12,13,13,14,14,14-pentacosafluorotetradecyl acrylate, and preferably at least one selected from the group consisting of 4- 4-vinylpyridine (4VP), 2,4,6,8-tetramethyl-2,4,6,8-tetravethyl-tetradecylsilane (2,4,6,8-tetramethyl- 6,8-tetravinyl cyclotetrasiloxane, V4D4), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methane (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluor diethyleneglycoldiacrylate (DEGDA), ethylene glycol dimethacrylate, dimethylaminoethyl methacrylate, or methacrylic acid, but is not limited thereto.

In the step (b), the flow ratio of the monomer to the initiator may be 1: 1 to 4: 1. Preferably 1: 1 to 3: 1, and has an effect of being able to deposit within the above flow rate ratio range.

The initiator may be a peroxide compound selected from the group consisting of formulas (1) to (5), preferably tert-butyl peroxide of formula (4). In addition, benzophenone, which is decomposed by light such as UV to form radicals, may also be used, but is not limited thereto.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

The thickness of the polymer may be 1 nm to 10 탆, preferably 1 nm to 1 탆, and more preferably 10 to 100 nm.

The substrate is made of polyacrylonitrile, polydimethylsiloxane, polyethersulfone (PES), polysulfone (PSF) and polyvinylidene fluoride (PVDF). Lt; / RTI > may be one species selected from the group.

In the present invention, the polymer membrane can be preferably used as an electrode for a lithium-sulfur secondary battery.

A poly (S- r- DIB) electrode which is superior in performance to a conventional sulfur electrode and capable of effectively adsorbing a polymer when an electrode is coated using iCVD can be produced according to the following method as a preferred embodiment of the present invention. Figure 1 shows the coating of the poly (S- r- DIB) electrode with iCVD polymer.

Poly (S- r -DIB) is a polymeric material containing sulfur and di-isopropenyl benzene (DIB). DIB is added to the sulfur of the heated liquid phase, . The poly (S- r- DIB) electrode was prepared by mixing ball Super-P carbon conductive material and PVDF binder together with NMP solvent by ball milling to form an initial carbon layer by doctor blading, completely dry, Sr-DIB), a carbon conductive material and a PE binder are mixed with chloroform and coated in the same manner.

The electrode coating using iCVD uses a poly (Sr-DIB) electrode. iCVD coatings can be run using DEGDA monomers and initiators. In the monomer vessel connected to the chamber, the DEGDA monomer is heated to 20 to 100 DEG C, and the initiator initiator is maintained at room temperature. The S- r- DIB electrode was placed on the substrate and fixed. The monomer and the initiator were allowed to flow in the chamber at a ratio of 1: 1, the internal pressure of the chamber was 50 to 300 mTorr, the temperature of the substrate was 10 to 100 ° C, The temperature of the filaments in the chamber is maintained at 100 to 500 ° C. The thickness of the coated pDEGDA polymer (15-100 nm) can be controlled by the reaction time.

Accordingly, in another aspect of the present invention, there is provided a lithium secondary battery comprising a lithium secondary battery, which is characterized in that poly (Sr-diisopropenylbenzene) is coated with pDEGDA in a thickness of 1 nm to 10 占 퐉 and storage capacity after 100 cycles is 900 to 1500 mAh / - an electrode for a sulfur secondary battery.

In addition to pDEGDA polymers, various polymers can be coated on poly (S- r- DIB) through the iCVD process.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are for illustrative purposes only and that the scope of the present invention is not limited by these embodiments.

[Example]

Preparation Example 1: Preparation of poly (S-r-DIB) electrode deposited with pDEGDA

(1) Preparation of poly (S-r-DIB)

Poly (Sr-DIB) is a polymer material containing 90 wt% sulfur and 10 wt% di-isopropenyl benzene (DIB). DIB is added to the sulfur of the liquid phase heated to 180 ° C, And then reacted until completely solidified. The poly (Sr-DIB) electrode was prepared by mixing 80 wt% of Super P carbon conductive material and 20 wt% of PVDF binder together with NMP solvent by ball milling to form an initial carbon layer by doctor blading, 75 wt% of poly (Sr-DIB), 20 wt% of carbon conductive material, and 5 wt% of PE binder were mixed with chloroform and coated in the same manner.

(2) Electrode coating using iCVD

The electrode coating using iCVD was performed using a poly (S-r-DIB) electrode. iCVD coating was carried out by using diethyleneglycoldiacrylate (DEGDA) as a monomer and tert-butyl peroxide (TBPO) as an initiator. DEGDA was added to the monomer bottle connected to the chamber and heated to 90 DEG C, and TBPO of the initiator bottle was kept at room temperature. After the Sr-DIB electrode was placed on the substrate and fixed, the monomer and initiator were caused to flow in the chamber at a ratio of 1: 1, the inner pressure of the chamber was set to 60 mTorr, the temperature of the substrate was set to 30 ° C, Lt; 0 > C. The thickness of the coated polymer (15 nm, 50 nm, 100 nm) was controlled by the reaction time.

Production Example 2: Preparation of poly (S- r -DIB) Electrode Fabrication

A poly (S- r- DIB) electrode on which p4VP was deposited was prepared in the same manner as in Production Example 1, except that 4-vinyl pyridine was used as a monomer in Production Example 1.

Preparation Example 3: Preparation of poly (S- r -DIB) Electrode Fabrication

A poly (S- r- DIB) electrode deposited with pDEGDA was prepared in the same manner as in Preparation Example 1 except that diethyleneglycoldiacrylate was used as a monomer in Preparation Example 1.

Preparation Example 4: Preparation of poly (S- r -DIB) Electrode Fabrication

In Production Example 1, 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl cyclotetrasiloxane (2,4,6,8-tetravinyl- ), Poly (S- r- DIB) electrode on which pV4D4 was deposited was prepared.

Production Example 5: Preparation of poly (S- r -DIB) Electrode Fabrication

In Production Example 1, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9,10,10,10 heptadecafluorodecyl methacrylate (3, 4,4,5,5,6,6,7,7,8,8,9,9,9,10,10,10 heptadecafluorodecyl methacrylate) was used in place of pPFDMA a (r S- -DIB) deposited poly electrode was prepared.

Preparation Example 6: Preparation of poly (S- r -DIB) Electrode Fabrication

A poly (S- r- DIB) electrode deposited with pPFDMA was prepared in the same manner as in Preparation Example 1, except that methacrylic acid was used as a monomer in Production Example 1.

Preparation Example 7: Preparation of poly (S- r -DIB) Electrode Fabrication

A poly (S- r- DIB) electrode deposited with pDMAEMA was prepared in the same manner as in Preparation Example 1, except that dimethylaminoethylmethacrylate was used as a monomer in Production Example 1.

Comparative Example: Preparation of bare (poly) (S-r-DIB) electrode

DIB was added to sulfur in the liquid phase heated to 180 ° C. and reacted until crosslinking reaction was complete to obtain a poly (Sr-DIB) containing 90 wt% of sulfur and 10 wt% of di-isopropenyl benzene ) Were synthesized. The poly (Sr-DIB) electrode was prepared by mixing 80 wt% of Super P carbon conductive material and 20 wt% of PVDF binder together with NMP solvent by ball milling to form an initial carbon layer by doctor blading, 75 wt% of poly (Sr-DIB), 20 wt% of carbon conductive material, and 5 wt% of PE binder were mixed with chloroform and coated in the same manner.

Example 1: Measurement of water contact angle

A drop (10 μl) of distilled water was dropped on the poly (Sr-DIB) electrode coated with the pDEGDA polymer prepared in Preparation Example 1, and the contact angle was measured with a contact angle analyzer (DSA, KRUSS) . 2 is a cross-sectional view showing a water contact angle of a wafer coated with a pDEGDA polymer according to an embodiment of the present invention.

The electrode for the deposited pDEGDA lithium-sulfur secondary battery has a hydrophilic property with a water contact angle of about 45 degrees.

As shown in FIG. 3, which is an FT-IR graph of the DEGDA monomer and the pDEGDA polymer according to an embodiment of the present invention, the deposited electrode for a lithium-sulfur secondary battery of pDEGDA was deposited on a FT- It can be seen that the carbonyl group remained intact while the vinly group decreased.

The water contact angle measured after coating each SDIM surface with various polymers prepared in iCVD in Production Examples 2 to 5 is shown in Fig. 4 (p4VP: poly 4-vinyl pyridine: pDEGDA: poly diethyleneglycoldiacrylate: pV4D4: poly 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl cyclotetrasiloxane, pPFDMA: poly 3,3,4,4,5,5,6,6,7,7,8,8,9, 9,10,10,10 heptadecafluorodecyl methacrylate).

From FIG. 4, it was confirmed that a poly (S- r- DIB) electrode with polymer deposition can be produced by coating various polymers on the SDIB surface through the iCVD process.

After the deposition of pMAA (poly methacrylic acid, Production Example 6) through the iCVD process, the area of the adhesion with SDIB showed a lower contact angle than that before coating.

FIG. 5 shows the water contact angle before and after coating the pMAA polymer on the SDIB film through the iCVD process. When pDMAEMA (poly dimethylaminoethylmethacrylate) coating according to Production Example 7 was coated, the contact angle was lower than that of Comparative Example after coating and washing with pDMAEMA.

FIG. 6 compares pDMAEMA polymer (Preparation Example 7) on the SDIB film with a comparative example by measuring the contact angle after washing in water before and after coating by iCVD process.

Example 2: Tape test

There was a change in the contact angle on the wafer after the tape test but no significant change on the SDIB sample.

The adhesion test between the electrode for the lithium-sulfur secondary battery and the SDIB film was confirmed by a tape test after coating with pEGDMA using iCVD and is shown in FIG. As shown in FIG. 7, pDVB having poor adhesion with the substrate was coated on a wafer and an S-r-DIB sample to perform a tape test. The contact angles of the wafers were greatly changed, while the SDIB showed only slight changes, and the SDIB showed almost no polymer degradation.

8 shows the adhesion between the electrode for a lithium-sulfur secondary battery and the SDIB film by a tape test after pDVB coating using iCVD. The contact angles of the wafers were greatly changed, while the SDIB showed only slight changes, and the SDIB showed almost no polymer degradation.

Example 3: Contact angle of solvent

After spin coating with chloroform, the pDEGDA maintained a similar contact angle, while bare SDIB decreased contact angle. FIG. 9 shows the contact angle before and after chloroform spin coating on pDEGDA-coated SDIB film and bare SDIB.

Not only the water contact angle but also the hydrophilic property at the DOL / DME contact angle. Figure 10 shows the contact angle of the DOL / DME solvent on bare SDIB and pDEGDA coated SDIB.

Example 4 Preparation of Secondary Battery Cell and Evaluation of Battery Performance

The iCVD-coated sulfur electrode was composed of a circular secondary battery cell with a lithium anode, separator, and electrolyte inside the glove box. The lithium negative electrode was bonded to the bottom of the circular cell in combination with the nickel piece, and a polypropylene separator was placed thereon. Lithium nitrate (LiNO ₃ , 0.38M), LiTFSI (0.38M), diglycolmethylether / dioxolane, 1: 1) was added, and a sulfur electrode was sealed thereon.

The performance evaluation of the poly (S-r-DIB) electrode coated with the iCVD method is also shown in FIG. 11 under the same conditions. In the uncoated poly (Sr-DIB) electrode, the storage capacity was 910 mAh / g after 100 cycles, while the electrodes coated with iCVD at 15 nm and 50 nm p (DEGDA) were 951 mAh / g and 1000 mAh / g Capacity increased. In the case of 100 nm coating, it was judged that charge / discharge overvoltage was increased and the storage capacity increase due to coating was canceled.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereto will be. Accordingly, the actual scope of the invention will be defined by the claims and their equivalents.

Claims (9)

A process for preparing a polymer membrane using a chemical vapor deposition reactor (iCVD) using an initiator comprising the steps of:
(a) placing and fixing a substrate coated with a sulfur copolymer on an iCVD reactor; And
(b) depositing a monomer and an initiator into an iCVD reactor to deposit a polymer on the substrate coated with the sulfur copolymer through polymerization of the monomer,
The sulfur copolymer is poly (S r -diisopropenylbenzene)
These monomers include 4-vinyl pyridine (4VP), 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl cyclotetrasiloxane (2,4,6,8-tetramethyl -2,4,6,8-tetravinyl cyclotetrasiloxane, V4D4), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-hepta Decafluorodecyl methacrylate (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate, PFDMA), diethylene Diethyleneglycoldiacrylate (DEGDA), dimethylaminoethyl methacrylate or methacrylic acid.
delete The method according to claim 1,
Wherein the step (b) is performed at a temperature of 25 to 45 ° C and a pressure of 150 to 350 mTorr for 10 minutes to 12 hours.
The method according to claim 1,
Wherein the charging temperature of the monomer and the initiator is 20 to 100 캜 and 20 to 100 캜, respectively, and the temperature of the filament in the substrate and the chamber is 10 to 100 캜 and 100 to 500 캜, respectively.
delete The method according to claim 1,
Wherein the flow ratio of the monomer to the initiator in the step (b) is 1: 1 to 4: 1.
The method according to claim 1,
Wherein the initiator is at least one selected from the group consisting of a peroxide compound represented by Chemical Formulas 1 to 5 and a benzophenone compound.
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

.
The method according to claim 1,
Wherein the polymer has a thickness of 1 nm to 10 占 퐉.
The electrode for a lithium-sulfur secondary battery, wherein pDEGDA is coated to a thickness of 1 nm to 100 nm on poly (S-r-diisopropenylbenzene) and storage capacity is 900 to 1500 mAh / g after 100 cycles.

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