KR20020014195A - Lithium-Sulfur batteries - Google Patents

Abstract

PURPOSE: A lithium sulfur secondary battery is provided, which is improved in the lifetime and the physical properties by using an anode plate which employs poly(vinyl acetate) and acetonitrile. CONSTITUTION: The lithium sulfur secondary battery comprises an anode plate which employs 5-30 wt% of poly(vinyl acetate) as a binder and acetonitrile as a slurry mixing solvent. Preferably the molecular weight of poly(vinyl acetate) is 10,000 to 5,000,000. The cathode active material of the battery is selected from the group consisting of a lithium metal electrode, a lithium alloy electrode and a composite electrode of lithium and inactive sulfur. The anode active material of the battery is at least one material selected from the group consisting of sulfur, solid Li2Sn (n>=1), Li2Sn (n>=1) dissolved in kasolite, an organic sulfur and a carbon-sulfur polymer, (C2Sx)n (x=2.5-50, n >=2).

Description

Lithium Sulfur Secondary Battery

The present invention relates to a lithium sulfur secondary battery, and more particularly, to a lithium sulfur secondary battery having improved physical properties by improving physical properties of a binder used in the production of a positive electrode of a lithium sulfur secondary battery.

With the recent growth of the mobile business, the demand for power supplies to drive them has increased. Lithium secondary batteries have been studied a lot as a suitable product and are currently commercialized. With the start of the IMT-2000 business, more demand for secondary batteries is expected, and further research on secondary batteries is needed.

Li-ion batteries that are currently commercialized are widely used because of their stability and flat voltage range of 3.6V. However, considering battery capacity and lifespan, it is necessary to research new battery systems to cope with the mobile market to be expanded in the future.

Lithium ion battery is a system that reversibly charges and discharges Li ions using various cathode active materials, and converts chemical energy into electrical energy as lithium is charged and discharged between pores of lithium oxide. LiCoO _{2 which} is currently commercialized is widely used because of its reversibility and capacity advantages over flat discharge curves and other positive electrode active materials, whereas LiMn ₂ O ₄ is pollution-free compared to LiCoO ₂ and has the advantages of low cost. Due to the relative problems in terms of life, it has not been commercialized yet.

Lithium sulfur secondary batteries are the most promising in terms of energy density and are being researched as a battery system to replace lithium ion batteries because active materials themselves are inexpensive and environmentally friendly materials.

The rapid development of portable electronic devices is increasing the demand for secondary batteries that make this possible. In particular, the emergence of a battery of high energy density that can meet the trend of light and short of portable electronic devices is continuously required, and also to meet the cheap, safe and environmentally friendly aspects.

Among various batteries satisfying these conditions, lithium sulfur secondary batteries are the most promising energy density among the batteries developed to date, and the active materials themselves are cheap and environmentally friendly materials.

In terms of energy density, the energy density of lithium is 3830 mAh / g, and the energy density of sulfur is 1675 mAh / g.

However, there is no commercially available example in the form of such a lithium sulfur secondary battery. The reason for this is that when sulfur is used as the positive electrode active material, the utilization rate indicating the amount of sulfur participating in the in-cell electrochemical redox reaction with respect to the amount of sulfur added is very low, indicating a very low capacity.

In addition, degradation of the battery life caused by the outflow of sulfur to the electrolyte during the redox reaction appears. In addition, when the appropriate electrolyte solution is not selected, there is a problem that lithium sulfide (Li ₂ S), which is a reduced product of sulfur, is precipitated and no longer participates in the electrochemical reaction.

To date, a variety of binders have been used to manufacture the electrode plates of lithium batteries as well as other batteries. For lithium ion batteries, polyvinylidene fluoride (PVDF) is currently used as a binder for both positive and negative electrodes. In the nickel-hydrogen battery, polytetrafluoroethylene (PTFE) was added to the positive electrode, and styrene-butadiene rubber (SBR) was added to the negative electrode.

Lithium sulfur secondary battery should have adhesive force to prevent active materials and conductive materials from falling off the current collector of the electrode plate, and should not react electrochemically even when charging and discharging continues. Should be good.

Research on binders used in lithium sulfur secondary batteries is disclosed in US Patent Nos. 5919587 and 5961672 filed by Moltech.

U.S. Patent No. 5919587 consists of a material comprising sulfur which is electroactive containing the -SSS- moiety and a chalcogenated compound of an electrically active transition metal surrounding it, which is applied to an electroactive transition metal chalcogenide compound solution. A method of preparing a positive electrode mixture by adding a substance containing active sulfur and then adding a conductive agent. Basically, an electroactive transition metal chalcogenide compound effectively covers and holds an electrode material containing electroactive sulfur. The transition metal chalcogenated compound serves as a binder.

However, this patent also has a problem that even if the transition metal chalcogenide compound acts as a provider, its wrapping force is weak and the positive electrode active material is dropped.

In addition, U.S. Patent No. 5,66172 uses a Teflon (PTFE-K30, manufactured by DuPont) as a binder to improve the lifespan and safety by coating a polymer film on the lithium metal anode. However, there is no mention that the performance is improved.

The present invention has been made to solve the problems described above, the object of the present invention is to improve the physical properties by using a binder in the positive electrode and excellent reaction properties without an electrolyte in the electrolyte without melting in the electrolyte 2 It is to provide a car battery.

1 is a graph comparing the life characteristics of a lithium sulfur secondary battery using a binder according to an embodiment of the present invention and a comparative example (■: Example 1 ◆: Comparative Example 1).

The present invention to achieve the above object, the present invention

Provided is a lithium sulfur secondary battery comprising a positive electrode plate using polyvinylacetate (PVAc) as a binder for a positive electrode mixture and acetonitrile as a slurry mixed solvent.

Hereinafter, the present invention will be described in more detail.

In the present invention, the positive electrode plate of the lithium sulfur secondary battery is composed of sulfur, a binder and a conductive agent.

At this time, it is important to select a binder and a solvent.

The binder must first be well dissolved in the solvent, form a conductive network of sulfur and a conductive agent, and have good impregnation with the electrolyte.

On the other hand, the solvent must be able to dissolve the binder well, be easy to dry, and also not to dissolve sulfur. This is because when the solvent dissolves sulfur, the sulfur of the slurry has a high specific gravity (d = 2.07), so that the sulfur sinks in the slurry, which causes sulfur to collect in the current collector during coating, causing problems in the conductive network, thereby making it difficult to operate the battery.

Accordingly, the present inventors have found a combination of a binder and a solvent having all of the properties of the binder and the solvent used in the positive electrode plate for a lithium sulfur secondary battery through experiments and the present invention.

In the present invention, polyvinylacetate (PVAc) is used as a binder constituting the positive electrode plate, and a slurry mixed solvent uses acetonitrile to form the positive electrode plate.

The polyvinylacetate used is preferably used having a molecular weight of 10,000 to 5,000,000, more preferably 500.000 to 2,000,000.

The amount of polyvinylacetate used is preferably 5 to 30% by weight, more preferably 15 to 25%.

On the other hand, the amount of acetonitrile used is preferably about 5-6 times the mass of sulfur.

As a cathode active material for use in the present invention group sulfur, solid Li ₂ S _n (n≥1), the kaessol Li ₂ S _n (n≥1) dissolved in light organic sulfur and carbon-sulfur polymer [(C ₂ S _x ) _n , x = 2.5-50, n ≧ 2] and use at least one active material selected from the group consisting of, and preferably sulfuric acid.

In addition, as the negative electrode active material, an electrode selected from the group consisting of a lithium metal electrode, a lithium metal alloy electrode, and a lithium / inactive sulfur composite electrode used in a lithium sulfur secondary battery is used.

As electrolyte, benzene, fluorobenzene, toluene, trifluorotoluene, xylene, cyclohexane, tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), cyclohexanol, ethanol, isopropyl alcohol , Dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate (MPC), methyl propionate (MP), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), dimethyl ether (DME) , A mixed electrolyte of 2 to 4 components selected from the group consisting of 1,3-dioxolane, diglyme, tetralime, ethylene carbonate, propylene carbonate, gamma butyrolactone, and sulfolane is used.

As the supporting electrolytic salt dissolved in the electrolytic salt, an electrolytic salt selected from the group consisting of lithium hexafluorophosphate (LiPF ₆ ), LiBF ₄ , LiAsF ₆ , LiClO _4, and LiSO ₃ CF ₃ is used. M to 2.0 M is used.

Hereinafter, a preferred embodiment of the present invention. However, the following examples are only presented to aid the understanding of the present invention, and the present invention is not limited to the following examples.

Example 1

60% single sulfur, 20% super-P, 20% polyvinylacetate (PVAc) was mixed in an acetonitrile solvent and coated on a carbon coated aluminum current collector until the slurry was thoroughly mixed. After the coated positive plate was dried, it was dried under vacuum for at least 12 hours. The dried positive plate and the vacuum dried separator were transferred to a glove box. An appropriate amount of 1,3-dioxolane / dilime / sulforan / dimethoxyethane (volume ratio 50/20/10/20) using 1M LiSO ₃ CF ₃ as a salt was dropped on the positive electrode plate. The separator was placed on it. Then, a little more electrolyte was added. The lithium electrode was put on it. After aging the assembled battery for 24 hours at room temperature, 0.1 C once charge and discharge, 0.2 C 3 charge and discharge, 0.5 C 5 charge and discharge, 1.0 C 100 charge and discharge under the condition that the cut-off voltage is 1.5 to 2.8 V Was carried out.

Comparative Example 1

60% single sulfur, 20% super-P, 20% polyvinylidene fluoride (PVDF) is mixed in DMF (N, N-Dimethylformamide) solvent and coated on a carbon coated aluminum current collector until the slurry is thoroughly mixed It was. After the coated positive plate was dried, it was dried under vacuum for at least 12 hours. The dried positive plate and the vacuum dried separator were transferred to a glove box. A 1,3-dioxolane / dilime / sulforan / dimethoxyethane (volume ratio 50/20/10/20) using 1M LiSO ₃ CF ₃ as a salt was dropped on the positive electrode plate in an appropriate amount. The separator was placed on it. Then, a little more electrolyte was added. The lithium electrode was put on it. The assembled battery was aged at room temperature for 24 hours, and then cut-off voltage was performed at 1.5 to 2.8 V at 0.1 C, one charge / discharge, 0.5 C five charge / discharge, and 1.0 C 100 charge / discharge.

The charging and discharging results of the coin cells prepared in Example 1 and Comparative Example 1 are shown in Table 1 below.

Table 1

characteristic Life Characteristics (100 Times) / Initial% Initial discharge capacity (mAh / g) PVAc / ACN 44 571 PVDF / DMF 11 550

When comparing Example 1 and Comparative Example 1, Table 1 and Figure 1 (■: Example 1 ◆: Comparative Example 1), there is no difference in the discharge capacity, but the life is greatly increased from 11% to 44% by selecting the appropriate binder It can be seen that the increase. This is because the impregnation of PVDF and PVAc with electrolytes is very different. In other words, PVDF plays a role as a binder such as adhesion but is poorly impregnated with the electrolyte, and thus it does not continuously stay in the positive electrode mixture (sulfur / binder / conductor) in which oxidation / reduction reaction of sulfur occurs.

Therefore, the oxidation / reduction reaction does not occur due to the lack of solvents, and thus it is impossible to continuously charge and discharge the battery, which is considered to have a very poor lifespan. The dismantling and analysis of the finished cell showed that the electrolyte did not stay in the positive electrode mixture and remained in the empty space of the cell and thus did not function as the electrolyte.

On the other hand, PVAc has an excellent impregnation into the electrolyte solution, and the oxidation / reduction reaction of sulfur proceeds relatively smoothly. Also, as a result of dismantling the cell, it was found that the electrolyte was maintained in the positive electrode mixture unlike the case of PVDF.

The lithium sulfur secondary battery manufactured according to the present invention was found that the discharge capacity is not different from the conventional battery, but the life is greatly increased.

Claims (8)

A lithium sulfur secondary battery comprising a positive electrode plate using polyvinylacetate (PVAc) as a binder for a positive electrode mixture, and using acetonitrile as a slurry mixed solvent. The method of claim 1, And a lithium sulfur secondary battery using an electrode selected from the group consisting of lithium metal electrodes, lithium metal alloy electrodes, and lithium / inactive sulfur composite electrodes as a negative electrode active material. The method of claim 1, The lithium sulfur secondary battery group sulfur, solid Li ₂ S _n (n≥1), the Li ₂ S _n (n≥1), organo-sulfur and carbon dissolved in kaessol light in the positive electrode active material-sulfur polymer [(C ₂ S _x ) _n , x = 2.5 to 50, n≥2] using a lithium sulfur secondary battery using at least one active material selected from the group consisting of. The method of claim 1, The polyvinyl acetate has a molecular weight of 10,000 to 5,000,000 lithium sulfur secondary battery. The method of claim 1, The polyvinyl acetate is used 5 to 30% by weight lithium sulfur secondary battery. The method of claim 1, The lithium sulfur secondary battery is benzene, fluorobenzene, toluene, trifluorotoluene, xylene, cyclohexane, tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), cyclohexanol, ethanol , Isopropyl alcohol, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate (MPC), methyl propionate (MP), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), dimethyl A mixed electrolyte solution containing 2 to 4 components selected from the group consisting of ether (DME), 1,3-dioxolane, diglyme, tetralime, ethylene carbonate, propylene carbonate, gamma butyrolactone, and sulfolane Lithium Sulfur Secondary Battery. The method of claim 1, The lithium sulfur secondary battery is trifluoromethanesulfonyl imide (LiN (CF ₃ SO ₂ ) ₂ ), lithium hexafluorophosphate (LiPF ₆ ), LiBF ₄ , LiAsF ₆ , LiClO ₄ and LiSO ₃ CF ₃ Lithium sulfur secondary battery comprising an electrolytic salt selected from the group consisting of. The method of claim 7, wherein A lithium sulfur secondary battery having a concentration of the electrolyte salt is 0.5 to 2.0 M.