阅读说明：本技术 用于锂离子二次电池的隔板和包括该隔板的锂金属电池 (Separator for lithium ion secondary battery and lithium metal battery including the same ) 是由 尹泫雄 诸葛鍾泌 于 2018-12-06 设计创作，主要内容包括：本公开内容涉及一种用于锂金属电池的隔板和一种包括该隔板的锂离子二次电池。所述隔板具有包括高含量的粘合剂树脂的多孔涂层。多孔涂层中的粘合剂树脂的含量为基于100重量％的多孔涂层的25重量％或以上,并且所述多孔涂层面对负极。(The present disclosure relates to a separator for a lithium metal battery and a lithium ion secondary battery including the same. The separator has a porous coating layer including a high content of a binder resin. The content of the binder resin in the porous coating layer is 25 wt% or more based on 100 wt% of the porous coating layer, and the porous coating layer faces the negative electrode.)

1. A separator for an electrochemical device, the separator comprising:

a porous substrate;

a first porous coating layer formed on one surface of the porous substrate; and

a second porous coating layer formed on the other surface of the porous substrate,

wherein the first porous coating layer includes inorganic particles and a first binder resin, the content of the binder resin being 1 to 15% by weight based on 100% by weight of the first porous coating layer,

the second porous coating layer includes a filler containing at least one selected from the group consisting of an organic filler and an inorganic filler, and a second binder resin, and the content of the second binder resin is 25 to 40 wt% based on 100 wt% of the second porous coating layer.

2. The separator for an electrochemical device according to claim 1, wherein the inorganic filler of the second porous coating layer comprises porous particles.

3. The separator for an electrochemical device according to claim 2, wherein the porous particles comprise at least one selected from the group consisting of zeolite, aluminophosphate, aluminosilicate, titanosilicate, calcium phosphate, zirconium phosphate, and silica gel.

4. The separator for an electrochemical device according to claim 1, wherein the volume swelling degree of the second binder resin under electrolyte conditions is 5% or more.

5. The separator for an electrochemical device according to claim 4, wherein the volume swelling degree of the second binder resin in the presence of an electrolyte is 30 to 80%.

6. The separator for an electrochemical device according to claim 1, wherein the second binder resin comprises polyvinylidene fluoride-co-Hexafluoropropylene (PVdF-HFP) containing Hexafluoropropylene (HFP) as a comonomer.

7. The separator for an electrochemical device according to claim 6, wherein the PVdF-HFP is a swellable binder resin that undergoes volume swelling by absorbing an electrolyte.

8. The separator for an electrochemical device according to claim 1, wherein the thickness of the second porous coating layer is 1 to 20 μm.

9. The separator for an electrochemical device according to claim 1, wherein the porous substrate is a polymer sheet comprising a polyolefin polymer material and having at least one type of pores selected from open pores and closed pores.

10. A lithium ion secondary battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, wherein the separator is as defined in claim 1 and is disposed in such a manner that the second porous coating layer of the separator faces the negative electrode.

11. The lithium ion secondary battery according to claim 10, wherein the anode comprises lithium metal as an anode active material.

12. The lithium ion secondary battery according to claim 10, wherein a swelling degree of a PVdF-based binder resin contained in the second porous coating layer of the separator is 5% or more in the presence of an electrolyte, and the electrolyte includes an organic solvent for the electrolyte and a lithium salt.

Technical Field

This application claims priority to korean patent application No. 10-2017-0169991, filed in korea at 12/6/2017. The present disclosure relates to a separator for a lithium ion secondary battery and a lithium ion secondary battery including the same. More specifically, the lithium ion secondary battery is a lithium metal secondary battery including lithium metal as a negative electrode active material.

Background

As the technical development and demand for mobile devices increase, the demand for secondary batteries as an energy source also increases. Among such secondary batteries, lithium metal secondary batteries using lithium metal or lithium alloy as a negative electrode having high energy density have received much attention.

The lithium metal secondary battery refers to a secondary battery using lithium metal or a lithium alloy as a negative electrode. The lithium metal has a density of 0.54g/cm³And a very low standard reduction potential of-3.045V (SHE: based on standard hydrogen electrode), and thus is most spotlighted as an electrode material for a high energy density battery.

Although the lithium metal battery theoretically has an extremely high energy capacity, severe side reactions with an electrolyte are caused due to high chemical/electrochemical reactivity to form a thick resistive layer on the surface of an electrode, resulting in an increase in resistance and a decrease in capacity of the battery during charge/discharge. In addition, the lithium metal battery has a problem of rapid deterioration of battery performance due to exhaustion of the electrolyte caused by rapid decomposition of the electrolyte. Therefore, stabilizing the interface between lithium metal and the electrolyte is an important technical issue. According to the prior art, some studies have been made to reduce reactivity between a negative electrode and an electrolyte by forming a stable solid electrolyte interface layer (SEI layer) on the surface of a lithium metal negative electrode. In addition, it is conceivable to use a solid electrolyte instead of the lithium electrolyte in the lithium metal battery. However, in the case of a solid electrolyte, there is a problem that the ionic conductivity is low.

Disclosure of Invention

Technical problem

The present disclosure is directed to solving the problems of the prior art, and therefore, the present disclosure is directed to providing a separator for a lithium metal secondary battery. The present disclosure is also directed to providing a lithium metal secondary battery that prevents deterioration of battery performance due to depletion of an electrolyte. These and other objects and advantages of the present disclosure will be understood and will become more apparent from the following detailed description of exemplary embodiments thereof. Further, it will be readily understood that the objects and advantages of the present disclosure are achieved by the means shown in the appended claims and combinations thereof.

Technical scheme

According to an embodiment of the present disclosure, there is provided a separator for an electrochemical device, the separator including: a porous substrate; a first porous coating layer formed on one surface of the porous substrate; and a second porous coating layer formed on the other surface of the porous substrate, wherein the first porous coating layer includes inorganic particles and a first binder resin, the content of the binder resin is 1 to 15 wt% based on 100 wt% of the first porous coating layer, the second porous coating layer includes a filler containing at least one selected from the group consisting of an organic filler and an inorganic filler and a second binder resin, and the content of the second binder resin is 25 to 40 wt% based on 100 wt% of the second porous coating layer.

According to a second embodiment of the present disclosure, there is provided the separator as defined in the first embodiment, wherein the inorganic filler of the second porous coating layer comprises porous particles.

According to a third embodiment of the present disclosure, there is provided the separator as defined in the first or second embodiment, wherein the porous particles comprise at least one selected from the group consisting of zeolite, aluminophosphate, aluminosilicate, titanosilicate, calcium phosphate, zirconium phosphate, and silica gel.

According to a fourth embodiment of the present disclosure, there is provided the separator as defined in any one of the first to third embodiments, wherein the volume swelling degree of the second binder resin under the influence of the electrolyte is 5% or more.

According to a fifth embodiment of the present disclosure, there is provided the separator as defined in any one of the first to fourth embodiments, wherein the volume swelling degree of the second binder resin in the presence of the electrolyte is 30 to 80%.

According to a sixth embodiment of the present disclosure, there is provided the separator as defined in any one of the first to fifth embodiments, wherein the second binder resin comprises polyvinylidene fluoride-co-Hexafluoropropylene (PVdF-HFP) containing Hexafluoropropylene (HFP) as a comonomer.

According to a seventh embodiment of the present disclosure, there is provided the separator as defined in any one of the first to sixth embodiments, wherein PVdF-HFP is a swellable binder resin that undergoes volume swelling by absorbing an electrolyte.

According to an eighth embodiment of the present disclosure, there is provided the separator as defined in any one of the first to seventh embodiments, wherein the second porous coating layer has a thickness of 1 to 20 μm.

According to a ninth embodiment of the present disclosure, there is provided the separator as defined in any one of the first to eighth embodiments, wherein the porous substrate is a polymer sheet comprising a polyolefin polymer material and having at least one type of pores selected from open and closed pores.

According to a tenth embodiment of the present disclosure, there is provided a lithium ion secondary battery including a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, wherein the separator is any one of the above-defined separators and is disposed in such a manner that a second porous coating layer of the separator faces the negative electrode.

According to an eleventh embodiment of the present disclosure, there is provided the lithium ion secondary battery as defined in the tenth embodiment, wherein the anode includes lithium metal as an anode active material.

According to a twelfth embodiment of the present disclosure, there is provided the lithium ion secondary battery as defined in the tenth or eleventh embodiment, wherein the swelling degree of the PVdF-based binder resin contained in the second porous coating layer of the separator is 5% or more in the presence of an electrolyte, and the electrolyte includes an organic solvent for the electrolyte and a lithium salt.

Advantageous effects

The separator according to the present disclosure includes a high content of the binder resin in the second porous coating layer facing the anode, and thus exhibits a high amount of electrolyte held by the binder resin. Further, the present disclosure provides a lithium metal battery using lithium metal as an anode active material, in which a porous coating layer having a high binder resin content is disposed in a manner to face an anode. Therefore, the electrolyte of the lithium metal battery can be prevented from being exhausted. As a result, the lithium metal battery according to the present disclosure has significantly improved life characteristics.

Detailed Description

It should be understood that the terms used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present disclosure on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is illustrative of the preferred embodiments for purposes of illustration only and is not intended to limit the scope of the present disclosure, which is to be understood as: other equivalents and modifications may be made without departing from the scope of the present disclosure.

As used herein, the expression "one portion is connected to another portion" encompasses not only "one portion is directly connected to another portion" but also "one portion is electrically connected to another portion through other elements interposed therebetween".

Throughout the specification, the expression "a portion 'including' one element" does not exclude the presence of any other element, but means that the portion may further include other elements.

As used herein, the terms "about", "substantially", and the like, when used in reference to acceptable manufacturing and material errors that are characteristic of the stated meaning, are used to denote a meaning adjacent to the stated numerical value, and for the purpose of preventing unscrupulous infringers from inappropriately using the stated disclosure, including the exact numerical value or the absolute numerical value, provided to assist in understanding the present disclosure.

As used herein, the term "combination thereof" included in any markush-type expression refers to a combination or mixture of one or more elements selected from the group of elements disclosed in the markush-type expression, and to the presence of one or more elements selected from the group.

As used herein, the expression "a and/or B" means "A, B or both".

The present disclosure relates to a separator for a lithium ion secondary battery and a lithium ion secondary battery including the same. According to an embodiment of the present disclosure, the lithium ion secondary battery is a lithium metal battery including lithium metal as an anode active material.

Partition board

According to an embodiment of the present disclosure, the partition plate includes: a porous substrate; a first porous coating layer formed on one surface of the porous substrate; and a second porous coating layer formed on the other surface of the porous substrate.

Porous substrate

Here, the porous substrate is a porous ion-conducting barrier (porous ion-conducting barrier) that interrupts electrical contact between the negative electrode and the positive electrode while allowing ions to pass therethrough, and may be a polymer sheet including a plurality of pores. The pores comprise open and/or closed pores and are interconnected such that gas or liquid may pass from one surface of the substrate to the other surface of the substrate.

The material forming such a porous substrate may be any one of an organic material and an inorganic material having an electrical insulating property. Specifically, from the viewpoint of imparting a substrate shutdown function, it is preferable to use a thermoplastic resin as a material for forming the substrate. Here, the term "shutdown function" refers to a function of interrupting ion transport by closing pores of a porous substrate with a molten thermoplastic resin when the temperature of a battery increases, thereby preventing thermal runaway of the battery. The thermoplastic resin suitably comprises a resin having a melting point of less than 200 ℃. For example, the thermoplastic resin may include a polyolefin. The polyolefin resin is not particularly limited, but typical examples thereof may include at least one of polyethylene, polypropylene, and polybutylene.

Further, at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide, polycarbonate, polyimide, polyether ether ketone, polyether sulfone, polyphenylene ether, polyphenylene sulfide, and polyethylene naphthalene may be used separately from or in combination with the polyolefin.

The porous substrate may include at least one of an extruded/oriented film made of a polymer material and a nonwoven web obtained by filamentizing and compressing the polymer material. For example, the porous substrate may be any one of the following a) to e):

a) a porous film formed by melting and extruding a polymer resin,

b) a multilayer film formed by stacking two or more porous films as defined in a),

c) a nonwoven web made by integrating filaments obtained by melting/spinning a polymer resin,

d) a multilayer film formed by stacking two or more layers of the nonwoven web as defined in c), and

e) a multilayer porous composite membrane comprising two or more of a) to d).

According to the present disclosure, the porous substrate may have a thickness of 5-50 μm. Although the thickness of the porous substrate is not limited to the above range, the porous substrate having a thickness much smaller than the above lower limit may cause deterioration of mechanical properties, and thus the separator may be easily damaged during use of the battery. Further, although the pore diameter and porosity of the substrate are not particularly limited, the pore diameter and porosity may be 0.01 to 50 μm and 10 to 95%, respectively.

First porous coating layer

According to an embodiment of the present disclosure, a first porous coating layer is provided on one surface of a separator substrate. As described hereinafter, in the separator according to the present disclosure, the first porous coating layer may face the positive electrode when the separator is applied to the lithium metal battery.

The first porous coating layer is formed by mixing a plurality of inorganic particles with a first binder resin. In the separator according to the present disclosure, the surface of the porous substrate is coated with inorganic particles, so that the porous substrate may have improved heat resistance and mechanical properties. The first porous coating layer includes inorganic particles closely packed therein and has a plurality of micropores derived from interstitial volumes formed between the inorganic particles. The pores are interconnected and exhibit a porous structure that allows the transfer of gas or liquid from one surface to another. According to an embodiment of the present disclosure, the inorganic particles are wholly or partially surface-coated with a binder resin and bonded to each other by face-to-face bonding and/or point-to-point bonding with the binder resin. Further, as used herein, the term "interstitial volume" refers to the space defined by adjacent inorganic particles that are substantially in contact with each other.

According to the present disclosure, the first porous coating layer includes the first binder resin in an amount of 1 to 15 wt% based on 100 wt% of the porous coating layer. When the content of the first binder resin is excessively high beyond the above range, the resistance of the separator increases, resulting in deterioration of battery performance. Further, when the content of the binder resin is less than the above range, the adhesion between the electrode and the separator may be decreased, and the inorganic particles contained in the first porous coating layer may be separated from the coating layer.

According to an embodiment of the present disclosure, the average pore size of the first porous coating layer is 20 to 1,000 nm. Within the above range, the average pore diameter of the first porous coating layer may be 800nm or less, or 500nm or less. Independently or in combination therewith, the average pore size of the first porous coating may be 20nm or more, 50nm or more, or 100nm or more. For example, the average pore diameter of the first porous coating layer is 20 to 800 nm. The pore size can be calculated by shape analysis of Scanning Electron Microscope (SEM) images. When the pore size is less than the above range, pores may be easily plugged due to swelling of the binder resin in the coating layer. When the pore diameter is not within the above range, the separator is difficult to use as an insulating layer, and self-discharge characteristics may be deteriorated after the secondary battery is manufactured.

According to an embodiment of the present disclosure, the porosity of the first porous coating layer may be 40 to 80%, or 50% or more in consideration of lithium ion permeability. Further, the porosity may be 70% or less, or 60% or less, in view of adhesion. In the above range, the surface opening ratio is not so high, and thus it is suitable for ensuring the adhesion between the separator and the electrode. Porosity can be measured by preparing a slurry for forming the first porous coating layer and applying the slurry to a release film to form a separate first porous coating layer. In other words, the composition and processing conditions capable of ensuring the porosity within the above range can be set by experimental methods and applied to the actual manufacturing process.

Further, according to the present disclosure, porosity and pore size can be determined by using a bessorp (BET device) using an adsorption gas (such as nitrogen) commercially available from BEL Japan co by using Scanning Electron Microscope (SEM) images or by methods such as Mercury intrusion porosimetry (Mercury intrusion porosimetry) or capillary flow porosimetry (california). In one variation, according to another embodiment of the present disclosure, the thickness and weight of the resulting coating may be measured to calculate the porosity from the theoretical density of the coating.

The first porous coating layer preferably has a thickness of 1.5-5.0 μm. More preferably, the first porous coating layer has a thickness of 1.5 μm or more. Within the above range, high adhesion to the electrode and increased cell strength may be provided. Meanwhile, it is advantageous that the thickness of the first porous coating layer is less than 5.0 μm in terms of cycle characteristics and resistance characteristics of the battery.

Non-limiting examples of the first binder resin that may be used in the present disclosure include any one selected from the group consisting of: polyvinylidene fluoride (PVdF), polyvinylidene fluoride-co-hexafluoropropylene (PVdF), polyvinylidene fluoride-co-trichloroethylene (polyvinylidene fluoride-co-trichloroethylene), polymethyl methacrylate (polymethylmethacrylate), polybutyl acrylate (polybutylacrylate), polyacrylonitrile (polyacrylonitrile), polyvinylpyrrolidone (polyvinylpyrrolidone 1), polyvinyl acetate (polyvinylacetate), polyethylene-co-vinylacetate (polyethyleneoxide), polyethylene oxide (polyethyleneimine oxide), polyarylate (polyarylate), cyanoethyl pullulan (cyanoethyl cellulose), cellulose acetate (cellulose acetate, cellulose acetate (cellulose acetate), cellulose acetate (cellulose acetate, cellulose.

Furthermore, according to embodiments of the present disclosure, the binder polymer need not substantially have ionic conductivity. However, when the polymer resin having ion conductivity is used, the performance of the electrochemical device may be further improved. Therefore, a binder polymer having a dielectric constant as high as possible can be used.

In addition, a binder resin having a glass transition temperature (Tg) of-100 to 200 ℃ may be used. This is because such a binder resin can improve mechanical properties of the separator, such as flexibility and elasticity. In addition, such a binder resin stably fixes the bonding between the inorganic particles, and thus helps prevent deterioration of mechanical properties of the resulting porous coating layer.

According to an embodiment of the present disclosure, it is preferable that the inorganic particles do not change in physical properties even at a high temperature of 200 ℃ or more. Further, the inorganic particles are not particularly limited as long as they are electrochemically stable. In other words, the inorganic particles are not particularly limited as long as they are within the operating voltage range of the applicable electrochemical device (e.g., based on Li/Li)⁺0 to 5V) does not cause oxidation and/or reduction. According to an embodiment of the present disclosure, the inorganic particles may include any one selected from the group consisting of: BaTiO 2₃、Pb(Zr,Ti)O₃(PZT)、Pb_1-xLa_xZr_1-yTi_yO₃(PLZT,0<x<1,0<y<1)、Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃(PMN-PT,0<x<1) Hafnium oxide (hafnia, HfO)₂)、SrTiO₃、SnO₂、CeO₂、MgO、NiO、CaO、ZnO、ZrO₂、Y₂O₃、Al₂O₃、SiC、TiO₂And combinations thereof.

According to an embodiment of the present disclosure, the particle size of the inorganic particles in the porous coating layer is not particularly limited. However, in order to form a coating layer having a uniform thickness and sufficient porosity, the particle size may be 0.001 to 10 μm. When the inorganic particles satisfy the above-defined range, the dispersibility is easily maintained and the physical properties of the separator are easily controlled, and the thickness of the porous coating layer can be prevented from increasing. Thus, mechanical properties can be improved. Further, internal short circuits during charge/discharge caused by an excessively large aperture can be reduced.

The porous coating can be obtained by: inorganic particles are introduced into a mixture containing a binder resin dissolved or dispersed in a suitable solvent to form a homogeneous slurry, and one surface of a porous substrate is coated with the slurry. Coating may be performed by dip coating, die coating, roll coating, comma (comma) coating, or a combination thereof.

Second porous coating

According to an embodiment of the present disclosure, the second porous coating layer is disposed on the other surface of the separator substrate. As described below, when the battery is manufactured, the second porous coating layer faces the anode, and the anode includes lithium metal as an anode active material.

According to an embodiment of the present disclosure, the second porous coating layer is formed by mixing a filler including at least one selected from the group consisting of an organic filler and an inorganic filler with a second binder resin.

The second porous coating layer allows the surface of the porous substrate to be coated with inorganic particles, similarly to the first porous coating layer, thereby improving the heat resistance and mechanical properties of the separator. Further, the second porous coating layer has a higher binder resin content than the first porous coating layer, and thus can be used as an electrolyte reservoir capable of preventing the exhaustion of the electrolyte. In other words, the second binder resin in the second porous coating layer absorbs the electrolyte and stores a portion of the electrolyte therein during an initial charge/discharge cycle of the battery, i.e., while maintaining the amount of the electrolyte sufficient to drive the battery. Then, for example, when the amount of the electrolyte decreases due to decomposition of the electrolyte when the battery cycle is performed, the electrolyte stored in the second binder resin of the second porous coating layer allows the battery to be stably driven.

According to the present disclosure, the second porous coating layer includes the binder resin in an amount of 20 to 45 wt% or 25 to 40 wt% based on the total weight of the porous coating layer. When the content of the binder resin is excessively high beyond the above range, the resistance of the separator increases, resulting in a decrease in battery performance. Further, when the content of the binder resin is less than the above range, the binder resin may not provide a desired level of electrolyte storability.

Further, according to the present disclosure, the second binder resin preferably has a high degree of swelling (swelling ratio) in the presence of an electrolyte.

According to the embodiments of the present disclosure, the binder resin preferably has high electrolyte absorption and retention. In view of this, the swelling degree of the binder resin in the presence of the electrolyte may be 5% or more, 10% or more, 20% or more, 30% or more, or 40% or more. Further, the swelling degree may be 80% or less. The degree of swelling can be calculated according to the following formula 1:

[ formula 1]

Degree of swelling (%) [ (V)₁-V₂)/V₁]x 100，

Wherein V₁Represents the volume before swelling, V₂Represents the volume after swelling.

According to embodiments of the present disclosure, the electrolyte and the second binder resin may be those actually applied to manufacture a battery. After the combination of the electrolyte and the second binder resin is determined from the second binder and the electrolyte as described below, it may be applied to a battery.

According to an embodiment of the present disclosure, when determining the swelling degree in the presence of an electrolyte, the electrolyte includes an organic solvent. For example, the electrolyte may be a mixture comprising Ethylene Carbonate (EC) and Propylene Carbonate (PC) in a volume ratio of 30:70(EC: PC). The electrolyte used to determine the electrolyte absorbency may not include a lithium salt, or may optionally include a lithium salt. According to embodiments of the present disclosure, the electrolyte may include a lithium salt, such as LiPF₆Concentration thereof in a mixed organic solvent comprising EC and PC in a volume ratio of 30:70(EC: PC)Is 1 mol.

According to an embodiment of the present disclosure, the solubility parameter of the second binder resin is preferably 15 to 45MPa^1/2More preferably 15 to 25MPa^1/2And 30-45MPa^1/2. Therefore, the binder resin advantageously includes a hydrophilic polymer having many polar groups instead of a hydrophobic polymer, such as polyolefin. When the solubility parameter is not within the above range, that is, when the solubility parameter is less than 15MPa^1/2And is more than 45MPa^1/2When the binder resin is swollen, it is difficult to use a conventional organic solvent for an electrolyte.

Non-limiting examples of the second binder resin that may be used in the present disclosure include any one selected from the group consisting of: polyvinylidene fluoride (PVdF), polyvinylidene fluoride-co-hexafluoropropylene (PVdF), polyvinylidene fluoride-co-trichloroethylene (polyvinylidene fluoride-co-trichloroethylene), polymethyl methacrylate (polymethylmethacrylate), polybutyl acrylate (polybutylacrylate), polyacrylonitrile (polyacrylonitrile), polyvinylpyrrolidone (polyvinylpyrrolidone 1), polyvinyl acetate (polyvinylacetate), polyethylene-co-vinylacetate (polyethyleneoxide), polyethylene oxide (polyethyleneimine oxide), polyarylate (polyarylate), cyanoethyl pullulan (cyanoethyl cellulose), cellulose acetate (cellulose acetate, cellulose acetate (cellulose acetate), cellulose acetate (cellulose acetate, cellulose. Further, the binder resin preferably satisfies at least one condition selected from the above-mentioned swelling degree, dissolution rate and solubility.

According to an embodiment of the present disclosure, the second binder resin may include Polyvinylidene fluoride-co-Hexafluoropropylene (PVdF-HFP), which is a Polyvinylidene fluoride (PVdF) -based binder resin including Hexafluoropropylene (HFP) as a comonomer. Preferably, PVdF-HFP may have a substitution degree of HFP of 10 to 30 wt%. The substitution degree may be appropriately controlled within the above range in consideration of the resistance characteristics or the electrolyte holding amount. For example, the substitution degree may be controlled to 20% by weight or more, or 25% by weight in consideration of the electrolyte holding amount. Further, the substitution degree may be controlled to 20 wt% or less, or 15 wt% or less, in consideration of the resistance characteristics. When the substitution degree of HFP in PVdF-HFP satisfies the above range, the binder resin in the second porous coating layer sufficiently absorbs the electrolyte and can appropriately maintain the electrolyte holding amount.

The second porous coating layer may have a porous structure derived from interstitial volumes (interstitial volumes) between the inorganic particles. As used herein, the term "interstitial volume" refers to the space defined by adjacent inorganic particles that are substantially in contact with each other.

According to an embodiment of the present disclosure, the particle size of the inorganic particles in the porous coating layer is not particularly limited. However, in order to form a coating layer having a uniform thickness and sufficient porosity, the particle size may be 0.001 to 10 μm. When the inorganic particles satisfy the above-defined range, the dispersibility is easily maintained and the physical properties of the separator are easily controlled, and the thickness of the porous coating layer can be prevented from increasing. Thus, mechanical properties can be improved. Further, internal short circuits during charge/discharge caused by an excessively large aperture can be reduced.

According to the present disclosure, it is preferable that the inorganic particles do not change in physical properties even at a high temperature of 200 ℃ or more. Further, the inorganic particles are not particularly limited as long as they are electrochemically stable. In other words, the inorganic particles are not particularly limited as long as they are within the operating voltage range of the applicable electrochemical device (e.g., based on Li/Li)⁺0 to 5V) does not cause oxidation and/or reduction. According to an embodiment of the present disclosure, the inorganic particles may include any one selected from the group consisting of: BaTiO 2₃、Pb(Zr,Ti)O₃(PZT)、Pb_1-xLa_xZr_1-yTi_yO₃(PLZT,0<x<1,0<y<1)、Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃(PMN-PT,0<x<1) Hafnium oxide (hafnia, HfO)₂)、SrTiO₃、SnO₂、CeO₂、MgO、NiO、CaO、ZnO、ZrO₂、Y₂O₃、Al₂O₃、SiC、TiO₂And combinations thereof.

Further, according to embodiments of the present disclosure, the second porous coating layer may include porous inorganic particles separate from or in combination with the above inorganic particles. For example, the porous inorganic particles may include at least one selected from the group consisting of zeolite, aluminophosphate, aluminosilicate, titanosilicate, calcium phosphate, zirconium phosphate, and silica gel. When such porous inorganic particles are used, the electrolyte holding amount can be increased. In addition, the porous inorganic particles allow HF or moisture to be segregated in the pores, thus contributing to smooth charge/discharge. In view of this, the inorganic particles may have a pore size of 1 to 50 nm. Further, according to an embodiment of the present disclosure, the second porous coating layer may have a multi-layer structure including a plurality of single layers stacked continuously, wherein the layer formed on the surface of the porous substrate preferably includes porous inorganic particles as the inorganic particles.

According to embodiments of the present disclosure, the second porous coating layer may have a porosity of 10 to 40%. Within the above range, the lower limit may be controlled to 15%, 20%, or 25%, or the upper limit may be controlled to 35% or 30%. Porosity can be measured by preparing a slurry for forming the second porous coating layer and applying the slurry to a release film to form a separate second porous coating layer. In other words, the composition and processing conditions capable of ensuring the porosity within the above range can be set by experimental methods and applied to the actual manufacturing process.

Further, the second porous coating layer may have a thickness of 1 to 20 μm. Within the above range, the thickness may be 3 μm or more, 5 μm or more, or 7 μm or more in view of mechanical strength and safety. Further, the thickness may be 10 μm or less, or 5 μm or less in consideration of energy density. For example, the second porous coating layer may have a thickness of 2 to 7 μm or 2 to 5 μm in consideration of the above conditions.

The second porous coating layer may be obtained by: inorganic particles are introduced into a mixture containing a binder resin dissolved or dispersed in a suitable solvent to form a homogeneous slurry, and one surface of a porous substrate is coated with the slurry. Coating may be performed by dip coating, die coating, roll coating, comma (comma) coating, or a combination thereof.

Lithium metal battery

The present disclosure provides a secondary battery including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode. In the secondary battery, the separator has the above-described structural feature in which the second porous coating layer having a relatively high content of the binder resin faces the anode, and the anode includes lithium metal as an anode active material.

Hereinafter, the lithium metal battery will be explained in detail with reference to its construction.

According to an embodiment of the present disclosure, the anode may include a current collector and an anode active material layer formed on a surface of the current collector. The anode active material layer may include at least one selected from the group consisting of alkali metals, alkaline earth metals, group 3B metals, and transition metals. Non-limiting examples of metal may include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), or francium (Fr), preferably lithium, according to embodiments of the present disclosure. According to an embodiment of the present disclosure, the anode may be obtained by stacking an anode current collector with lithium metal foil having a desired thickness by compression and adhesion.

The positive electrode may be obtained by coating a mixture of a positive electrode active material, a conductive material, and a binder on a positive electrode current collector and drying. The mixture may further include a filler, if desired. Specific examples of the positive electrode active material include, but are not limited to: such as lithium cobalt oxide (LiCoO)₂) And lithium nickel oxide (LiNiO)₂) Such layered compounds, or those substituted with one or more transition metals; such as Li by the formula_1+xMn_2-xO₄(wherein x is 0-0.33), LiMnO₃、LiMn₂O₃And LiMnO₂Lithium manganese oxide of the formula; lithium copper oxide (Li)₂CuO₂) (ii) a Vanadium oxides, such as LiV₃O₈、LiV₃O₄、V₂O₅Or Cu₂V₂O₇(ii) a From the formula LiNi_1-xM_xO₂(wherein M is Co, Mn, Al, Cu, Fe, Mg, B or Ga, and x is 0.01 to 0.3); represented by the chemical formula LiMn_2-xM_xO₂(where M is Co, Ni, Fe, Cr, Zn or Ta and x is 0.01-0.1) or Li₂Mn₃MO₈(wherein M ═ Fe, Co, Ni, Cu, or Zn); LiMn₂O₄Wherein Li is partially substituted with an alkaline earth metal ion; a disulfide compound; fe₂(MoO₄)₃(ii) a Or the like.

Typically, the current collector is formed to have a thickness of 3 to 500 μm. The current collector is not particularly limited as long as it does not cause chemical changes in the corresponding battery and has high conductivity. Specific examples of the current collector may include stainless steel; aluminum; nickel; titanium; calcining carbon; stainless steel surface-treated with carbon, nickel, titanium, or silver; or the like. Any suitable current collector may be used depending on the polarity of the positive or negative electrode.

The binder for the positive electrode active material is a component that facilitates the binding of the active material with the conductive material and to the current collector. Typically, the binder is added in an amount of 1 to 50 wt% based on the total weight of the positive electrode mixture. The binder may be a high molecular weight polyacrylonitrile-co-acrylate, but is not limited thereto. Other examples of binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluororubber, various copolymers, and the like.

The conductive material is a component that does not cause any chemical change in the corresponding battery. Specific examples of the conductive material include: graphite, such as natural graphite and artificial graphite; carbon black such as carbon black, acetylene black, ketjen black (trade name), carbon nanotube, channel black, furnace black, lamp black, or thermal black; conductive fibers such as carbon fibers or metal fibers; metal powders such as carbon fluoride powder, aluminum powder, or nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives.

According to the present disclosure, the electrolyte includes an organic solvent and a predetermined amount of a lithium salt. Specific examples of the organic solvent include Propylene Carbonate (PC), Ethylene Carbonate (EC), Butylene Carbonate (BC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), Methyl Propionate (MP), dimethyl sulfoxide, acetonitrile, dimethoxyethane, diethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), Ethyl Methyl Carbonate (EMC), γ -butyrolactone (GBL), fluoroethylene carbonate (FEC), methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, pentyl acetate, methyl propionate, ethyl propionate, butyl propionate, or a combination thereof. Further, halogen derivatives and linear ester compounds of organic solvents can also be used. The lithium salt is a component easily soluble in the nonaqueous electrolyte, and specific examples thereof include LiCl, LiBr, LiI, LiClO₄、LiBF₄、LiB₁₀Cl₁₀、LiPF₆、LiCF₃SO₃、LiCF₃CO₂、LiAsF₆、LiSbF₆、LiAlCl₄、CH₃SO₃Li、(CF₃SO₂)₂NLi, lithium chloroborane, lithium lower aliphatic carboxylate, lithium tetraphenylborate, imide, or the like.

The secondary battery according to the present disclosure may be obtained by accommodating and sealing an electrode assembly, which includes positive electrodes and negative electrodes alternately stacked with separators interposed therebetween, together with an electrolyte in a case material such as a battery case. Any conventional method for manufacturing a secondary battery may be used without particular limitation.

In another aspect, there is provided a battery module including the secondary battery as a unit cell, and a battery pack including the battery module. Since the battery module and the battery pack include secondary batteries exhibiting excellent rapid charging characteristics at a high load amount, they may be used as power sources for electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, and energy storage systems.

In addition, with respect to other battery elements not described herein, such as conductive materials, reference may be made to the description of elements conventionally used in the field of batteries, particularly in the field of lithium secondary batteries.

Hereinafter, the present disclosure will be described in detail with reference to examples. The following examples may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth therein. Rather, these exemplary embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.

(1) Manufacture of separator plates