WO2019009560A1 - Electrode and lithium secondary battery comprising same - Google Patents

Electrode and lithium secondary battery comprising same Download PDF

Info

Publication number
WO2019009560A1
WO2019009560A1 PCT/KR2018/007263 KR2018007263W WO2019009560A1 WO 2019009560 A1 WO2019009560 A1 WO 2019009560A1 KR 2018007263 W KR2018007263 W KR 2018007263W WO 2019009560 A1 WO2019009560 A1 WO 2019009560A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
pore
active material
lithium
sulfur
Prior art date
Application number
PCT/KR2018/007263
Other languages
French (fr)
Korean (ko)
Inventor
조은경
김윤경
손권남
양두경
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180073277A external-priority patent/KR102160710B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/623,844 priority Critical patent/US11424441B2/en
Priority to JP2020518382A priority patent/JP6918224B2/en
Priority to EP18828210.7A priority patent/EP3627593A4/en
Priority to CN201880039648.6A priority patent/CN110800135B/en
Publication of WO2019009560A1 publication Critical patent/WO2019009560A1/en

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrode for improving capacity and reactivity of a lithium secondary battery and a lithium secondary battery including the same.
  • a negative electrode mainly comprising a lithium metal negative electrode or a lithium metal provides an opportunity to construct a battery which is lighter and has a higher energy density than a battery such as a lithium ion, a nickel metal hydride or a nickel-cadmium battery.
  • Cathode active materials for lithium batteries of this type are known and include sulfur-containing cathode active materials containing sulfur-sulfur bonds and are used for electrochemical cleavage (reduction) and reforming (oxidation) of sulfur- Rechargeability is achieved.
  • the lithium-sulfur battery using lithium and alkali metal as the anode active material and sulfur as the cathode active material has a theoretical energy density of 2,800 Wh / kg and a theoretical capacity of sulfur of 1,675 mAh / g, which is much higher than other battery systems , Hwang has attracted attention as a portable electronic device because of its advantage that it is abundant in resources, cheaper, and environmentally friendly.
  • noble metal catalysts such as platinum are expensive, they are not only difficult to commercialize, but also have potential to be poisoned by the redox reaction of sulfur in charge and discharge processes, making it difficult to utilize them as a cathode material for lithium-sulfur batteries.
  • the inventors of the present invention have found that, in addition to the electrode active material, the binder and the conductive material, the microporous carbon particles are also added to the electrodes, It was confirmed that the reactivity and the initial capacity of the electrode were improved even under high loading.
  • an object of the present invention is to provide an electrode having improved porosity.
  • Another object of the present invention is to provide a lithium secondary battery including the electrode having improved porosity.
  • the present invention provides an electrode comprising a pore-forming additive which is porous particles having an average particle diameter (D50) of 1 ⁇ or more.
  • the porosity of the pores contained in the porous particles may be 50 to 95%.
  • the pore-forming additive may include carbon or graphite.
  • the content of the pore-forming additive may be 0.5 to 5 wt% based on the total weight of the electrode.
  • the electrode may have a porosity of 64% or more.
  • the electrode may include an electrode active material, a binder, a conductive material, and the pore-forming additive.
  • the electrode active material may be at least one selected from the group consisting of elemental sulfur (S8), sulfur-based compounds, and mixtures thereof.
  • the binder may be selected from the group consisting of styrene-butadiene rubber-carboxymethylcellulose (SBR-CMC), polyvinyl acetate, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, crosslinked polyethylene oxide, Poly (ethyl acrylate), polytetrafluoroethylene, polyvinyl chloride, polyacrylic acid, polyvinylidene fluoride, polyvinylidene fluoride, polyvinylidene fluoride, polyvinylidene fluoride, Polyvinylidene fluoride, Polyvinylpyridine, polystyrene, derivatives thereof, blends thereof, and copolymers thereof. It is also possible to use at least one of these compounds.
  • SBR-CMC styrene-butadiene rubber-carboxymethylcellulose
  • the conductive material may be a carbon-based material selected from carbon black, acetylene black, and ketjen black; And a conductive polymer selected from polyaniline, polythiophene, polyacetylene, and polypyrrole.
  • the present invention also provides a lithium secondary battery comprising the electrode.
  • the porosity of the electrode is increased by the pore-forming additive, so that the reactivity of the electrode is excellent even under high loading and the initial capacity is improved.
  • an electrode having increased porosity by the pore-forming additive of the present invention When an electrode having increased porosity by the pore-forming additive of the present invention is applied as a positive electrode of a lithium-sulfur battery, a sufficient amount of an electrolyte solution is supported in pores included in the positive electrode to produce a discharge product
  • the polysulfide can be efficiently removed, and the lifetime characteristics of the lithium secondary battery including the lithium-sulfur battery can be improved.
  • FIG. 1 is a graph showing the results of charging / discharging tests of the lithium-sulfur battery produced in Example 1 of the present invention and Comparative Examples 1 and 2.
  • FIG. 1 is a graph showing the results of charging / discharging tests of the lithium-sulfur battery produced in Example 1 of the present invention and Comparative Examples 1 and 2.
  • FIG. 2 is a graph showing the results of charge-discharge experiments of the lithium-sulfur battery produced in Examples 1 and 2 and Comparative Example 1.
  • FIG. 2 is a graph showing the results of charge-discharge experiments of the lithium-sulfur battery produced in Examples 1 and 2 and Comparative Example 1.
  • the present invention relates to an electrode having high reactivity and high initial capacity even under high loading.
  • the electrode of the present invention includes a pore-forming additive having an average particle diameter (D50) of 1 ⁇ ⁇ or more.
  • the shape of the pore-forming additive is not particularly limited, but may be an average particle diameter (D50) of 1 ⁇ ⁇ or more, preferably 1 ⁇ ⁇ to 20 ⁇ ⁇ . If the amount is less than the above range, the rate of increase in the degree of porosity of the electrode is insignificant, so that it is not expected to improve the reactivity and initial capacity of the electrode under high loading. Particularly, as the anode of lithium- The lifetime characteristics of the battery may be deteriorated. If the amount is larger than the above range, the particle size is excessively large, which is not suitable as an additive for electrodes.
  • D50 average particle diameter
  • the pore-forming additive may have an internal porosity of 50% to 95%, preferably 50% to 90%, more preferably 50% to 85%. In this way, the pore- The porosity of the electrode can be improved by the pores included in the pore-forming additive when applied to an electrode.
  • the rate of increase in porosity of the electrode is insignificant, so that it is not expected to improve the reactivity and initial capacity of the electrode under high loading. Particularly, The removal efficiency may be lowered and the lifetime characteristics of the battery may be deteriorated. If the above range is exceeded, the durability of the electrode may be deteriorated.
  • the pore-forming additive may be porous carbon or graphite.
  • the content of the pore-forming additive may be 0.5 to 10% by weight, preferably 1 to 10% by weight, more preferably 1.5 to 10% by weight based on the total weight of the electrode. If the amount is less than the above range, the rate of increase in the degree of porosity of the electrode is insignificant, so that it is not expected to improve the reactivity and initial capacity of the electrode under high loading. Particularly, as the anode of lithium- The life characteristics of the battery may be deteriorated. If the above range is exceeded, the porosity of the electrode becomes excessively high, and the durability of the electrode may be deteriorated.
  • the pore-forming additive may be produced by a known method for producing a porous carbon product in the art.
  • the pore-forming additive may be produced by a method comprising the following steps (S1) to (S5) Can be prepared in the form of a product.
  • the mold material at the (S1) step may be SiO 2.
  • the carbon precursor material may be a pitch in the step (S2), and in particular, the " mesophase pitch " may be a carbonaceous material having a regular liquid crystal structure.
  • the method of removing the template in the step (S5) may be performed by chemical dissociation, wherein the formed porous carbon product may be a pore-forming additive according to the present invention.
  • the electrode may further include an electrode active material and a conductive material and an electrode active material or an electrode active material, a binder, and a conductive material for allowing electrons to move smoothly in the electrode.
  • the electrode active material may include, without limitation, a positive electrode active material or a negative electrode active material used in a battery.
  • the cathode active material may include elemental sulfur (S8), a sulfur-based compound, or a mixture thereof.
  • the conductive material may be a carbon-based material such as carbon black, acetylene black, and Ketjenblack; Or a conductive polymer such as polyaniline, polythiophene, polyacetylene, and polypyrrole, and the conductive material is used in an amount of 5 to 20% by weight, preferably 5 to 15% by weight, more preferably 5 to 10% By weight based on the total weight of the composition. If the content of the conductive material is less than the above range, the effect of improving the conductivity of the conductive material is insignificant. If the content of the conductive material exceeds the above range, the content of the electrode active material becomes relatively small.
  • the binder may be selected from the group consisting of poly (vinyl acetate), polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, alkylated polyethylene oxide, crosslinked polyethylene oxide, polyvinyl ether, poly (methyl methacrylate) (Trade name: Kynar), poly (ethyl acrylate), polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyvinylpyridine, polyvinylidene fluoride, polyvinylidene fluoride, Polystyrene, derivatives thereof, blends, copolymers and the like can be used.
  • the binder may be contained in an amount of 5 to 20 wt%, preferably 5 to 15 wt%, more preferably 5 to 10 wt% based on the total weight of the electrode. If the content of the binder is less than the above range, the effect of improving the adhesion between the electrode active material or between the electrode active material and the current collector may be insufficient. On the other hand, if the content of the electrode active material is less than the above range, There is a concern.
  • the electrode may be prepared by a conventional method. Specifically, a composition for forming an electrode active material layer, which is prepared by mixing the electrode active material, the conductive material, and the binder in an organic solvent, is coated on the electrode current collector, And optionally rolled. At this time, the pore-forming composition may be mixed with the electrode active material, the conductive material, and the binder in an organic solvent.
  • the organic solvent which can uniformly disperse the cathode active material, the binder and the conductive material, and is easily evaporated.
  • Specific examples thereof include N-methyl-2-pyrrolidone (NMP), acetonitrile, methanol, ethanol, tetrahydrofuran, water and isopropyl alcohol.
  • the electrode comprising the pore-forming additive according to the present invention may have a porosity of 50% or more, preferably 55% or more, and more preferably 64% or more. Or the porosity may be 64% to 80%.
  • the porosity of the electrode is less than the above range, the effect of improving the reactivity and initial capacity of the electrode is insignificant. If the porosity is more than the above range, the durability of the electrode may be deteriorated.
  • the present invention also relates to a lithium secondary battery comprising an electrode comprising the pore-forming additive as described above.
  • the electrode can be used for both the positive electrode and the negative electrode of the lithium secondary battery. However, when used as the positive electrode of the lithium-sulfur battery, the electrode has an effect of removing the polysulfide as a discharge product.
  • the pore-forming additive includes pores such that the porosity is 50 to 95%, and the electrolyte is supported in the pores, and the polysulfide can be removed by the electrolyte in the pores.
  • the present invention also relates to an electrode comprising a pore-forming agent selected from the group consisting of monomers of an unzipping polymer, a plasticizer, an organic template, and mixtures thereof.
  • the pore-forming agent may be included in the active material layer of the electrode to generate a gas by a chemical reaction and simultaneously form pores to improve porosity of the electrode.
  • the electrode is applied to a lithium secondary battery, particularly, a lithium sulfur battery, and exhibits a buffering effect against a change in volume of an active material due to charge and discharge, thereby improving lifetime characteristics of the lithium-sulfur battery.
  • the active material in the electrode shrinks and expands as the charge and discharge proceeds.
  • the pore-forming agent as described above is introduced into the electrode to exhibit the buffering effect and the electrolyte-supporting effect on the volume change of the active material.
  • the electrode includes a current collector; And an active material layer formed on the current collector and including an active material, wherein the active material layer comprises S and C; And a pore-forming agent selected from the group consisting of a monomer, a plasticizer, an organic template, and a mixture thereof, of an unzipping polymer, and the active material layer may further include an active material layer such as a binder, , ≪ / RTI >
  • the pore-forming agent is contained in the active material layer in an amount of 10 wt% or less, preferably 0.1 to 5 wt%, more preferably 0.1 to 2 wt%.
  • the active material layer may have an additive density of 0.8 g / cc to 2.0 g / cc, preferably 0.9 to 1.6 g / cc, more preferably 1.19 to 1.3 g / cc. If the mixing density of the active material layer is less than the above range, it is not preferable due to the decrease in capacity per volume, and if it exceeds this range, the volume expansion of the active material layer increases, which is not preferable.
  • the electrode for a lithium-sulfur battery including the above-described active material layer may be produced by preparing a composition for forming an active material layer containing an active material and an additive for forming pores, applying the composition for forming the active material layer to a current collector, And a step of forming an electrode for a lithium-sulfur battery.
  • the size, shape, and porosity of the pores formed in the active material layer can be controlled according to the size, shape, and content of the pore-forming additive used in forming the active material layer.
  • the porosity in the active material layer is less than the above range, the buffering effect due to a change in the volume of the active material is insufficient, which is undesirable. If the porosity is above the above range, electrodeconductivity decreases and capacity per volume decreases.
  • the lithium secondary battery including the electrode including the pore-forming additive exhibits a buffering effect against the volume change of the active material according to the improvement of the porosity to improve the life characteristic of the lithium secondary battery.
  • the pitch was carbonized at a temperature of 700 ° C to form a porous composite.
  • porous composite was supported in a hydrofluoric acid bath to remove the SiO 2 template to synthesize a pore-forming additive in the form of a porous carbon product.
  • the porosity of the synthesized porous carbon product is 50% or more, and the average particle diameter (D50) is 4 ⁇ ⁇ .
  • Example 1 Preparation of a positive electrode and a lithium-sulfur battery containing the same
  • the SBR-CMC styrene-butadiene rubber-carboxymethylcellulose 5 weight%, the carbon black 5 weight% as a conductive material, and the sulfur-carbon composite as a cathode active material were prepared in a ratio of 7: And 2% by weight of the pore-forming additive of Production Example 1 were added to water as a solvent to prepare a positive electrode slurry and then coated on an aluminum foil current collector to prepare a positive electrode by loading at 5 mAh / Respectively.
  • SBR-CMC styrene-butadiene rubber-carboxymethylcellulose
  • a lithium foil having a thickness of 200 ⁇ m as a cathode and an electrolyte solution containing 2 wt% of a LiNO 3 additive dissolved in 1 M LiTFSI (DME / DOL, 1: 1 volumer ratio) - Sulfur batteries were prepared.
  • the SBR-CMC styrene-butadiene rubber-carboxymethylcellulose 5 weight%, the carbon black 5 weight% as a conductive material, and the sulfur-carbon composite as a cathode active material were prepared in a ratio of 7: And 5% by weight of the pore-forming additive of Production Example 1 were added to water as a solvent to prepare a positive electrode slurry and then coated on an aluminum foil current collector to prepare a positive electrode by loading at 5 mAh / Respectively.
  • SBR-CMC styrene-butadiene rubber-carboxymethylcellulose
  • a lithium foil having a thickness of 200 ⁇ m as a cathode and an electrolyte solution containing 2 wt% of a LiNO 3 additive dissolved in 1 M LiTFSI (DME / DOL, 1: 1 volumer ratio) - Sulfur batteries were prepared.
  • a positive electrode and a lithium-sulfur battery were prepared in the same manner as in Example 1 except that no pore-forming additive was used.
  • porous carbon having an average particle diameter (D50) of less than 1 ⁇ m was used in place of the pore-forming additive, but a positive electrode and a lithium-sulfur battery in which porosity improvement effect of the electrode was not obtained due to insufficient pore size .
  • Example 1 The porosity of each of the prepared positive electrode prepared in Example 1 and Comparative Example 1 was measured. As a result, the porosity of Comparative Example 1, which is a positive electrode containing no pore forming additive, was 56% The porosity of Example 1, which is an anode containing additives, was improved to 64%.
  • the lithium-sulfur batteries of Examples 1 and 2 and Comparative Examples 1 and 2 were subjected to charge-discharge experiments.
  • FIG. 1 is a graph showing the results of charge and discharge tests of the lithium-sulfur battery prepared in Example 1 of the present invention and Comparative Examples 1 and 2, and FIG. 2 is a graph showing the results of charge- A graph showing the charge / discharge test results of the battery.
  • the charging and discharging tests were performed under the condition of the voltage of 1.5-2.8 V and the condition of 0.1 C, and the experimental results in one cycle were observed. As a result, It can be seen that the lithium-sulfur battery has improved Coulombic efficiency, initial discharge capacity, and reproducibility.

Abstract

The present invention relates to an electrode and a lithium secondary battery comprising the same, wherein the porosity of the electrode is increased by an additive for forming pores such that the electrode reactivity at a high degree of loading and the initial capacity of the electrode can be improved.

Description

전극 및 이를 포함하는 리튬 이차전지Electrode and lithium secondary battery comprising same
본 출원은 2017년 7월 4일자 한국 특허 출원 제10-2017-0084684호 및 2018년 6월 26일자 한국 특허 출원 제10-2018-0073277호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함한다.This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0084684, filed on July 4, 2017, and Korean Patent Application No. 10-2018-0073277, filed on June 26, 2018, All of which are incorporated herein by reference.
본 발명은 리튬 이차전지의 용량 및 반응성 향상을 위한 전극 및 이를 포함하는 리튬 이차전지에 관한 것이다.The present invention relates to an electrode for improving capacity and reactivity of a lithium secondary battery and a lithium secondary battery including the same.
최근까지, 음극으로 리튬을 사용하는 고에너지 밀도 전지를 개발하는 데 있어 상당한 관심이 있어 왔다. 예를 들어, 비-전기 활성 재료의 존재로 음극의 중량 및 부피를 증가시켜서 전지의 에너지 밀도를 감소시키는 리튬 삽입된 탄소 음극, 및 니켈 또는 카드뮴 전극을 갖는 다른 전기화학 시스템과 비교하여, 리튬 금속은 저중량 및 고용량 특성을 갖기 때문에, 전기화학 전지의 음극 활물질로서 매우 관심을 끌고 있다. 리튬 금속 음극, 또는 리튬 금속을 주로 포함하는 음극은, 리튬-이온, 니켈 금속 수소화물 또는 니켈-카드뮴 전지와 같은 전지보다는 경량화되고 고에너지 밀도를 갖는 전지를 구성할 기회를 제공한다. 이러한 특징들은 프리미엄이 낮은 가중치로 지불되는, 휴대폰 및 랩-탑 컴퓨터와 같은 휴대용 전자 디바이스용 전지에 대해 매우 바람직하다.Until recently, there has been considerable interest in developing high energy density cells using lithium as the cathode. For example, compared to other lithium-intercalated carbon cathodes and nickel-or-cadmium electrodes, which increase the weight and volume of the cathodes in the presence of non-electroactive materials to reduce the energy density of the cells, Has attracted much attention as an anode active material for an electrochemical cell because of its low weight and high capacity characteristics. A negative electrode mainly comprising a lithium metal negative electrode or a lithium metal provides an opportunity to construct a battery which is lighter and has a higher energy density than a battery such as a lithium ion, a nickel metal hydride or a nickel-cadmium battery. These features are highly desirable for batteries for portable electronic devices, such as cell phones and lab-top computers, where premiums are paid at low weights.
이러한 유형의 리튬 전지용 양극 활물질들은 공지되어 있고, 이들은 황-황 결합을 포함하는 황 함유 양극 활물질을 포함하며, 황-황 결합의 전기화학적 절단(환원) 및 재형성(산화)으로부터 고에너지 용량 및 재충전능이 달성된다.Cathode active materials for lithium batteries of this type are known and include sulfur-containing cathode active materials containing sulfur-sulfur bonds and are used for electrochemical cleavage (reduction) and reforming (oxidation) of sulfur- Rechargeability is achieved.
상기와 같이 음극 활물질로 리튬과 알칼리 금속을, 양극 활물질로 황을 사용하는 리튬-황 전지는 이론 에너지 밀도가 2,800 Wh/kg, 황의 이론 용량이 1,675 mAh/g으로, 다른 전지 시스템에 비하여 월등히 높고, 황은 자원이 풍부하여 값이 싸며, 환경친화적인 물질이라는 장점 때문에, 휴대 전자기기로 주목을 받고 있다As described above, the lithium-sulfur battery using lithium and alkali metal as the anode active material and sulfur as the cathode active material has a theoretical energy density of 2,800 Wh / kg and a theoretical capacity of sulfur of 1,675 mAh / g, which is much higher than other battery systems , Hwang has attracted attention as a portable electronic device because of its advantage that it is abundant in resources, cheaper, and environmentally friendly.
그러나, 리튬-황 전지의 양극 활물질로 사용되는 황은 부도체이므로 전기화학 반응으로 생성된 전자의 이동이 어렵고, 충방전 과정에서 발생되는 폴리 설파이드(Li2S8 ~ Li2S4) 용출 문제 및 황과 리튬 설파이드(Li2S2/Li2S) 의 낮은 전기 전도성으로 인한 전기화학 반응의 느린 kinetic으로 인하여 전지 수명 특성과 속도 특성이 저해되는 문제들이 있었다.However, since sulfur used as a cathode active material of a lithium-sulfur battery is an insulator, it is difficult to transfer electrons generated by an electrochemical reaction, and problems such as dissolution of polysulfide (Li 2 S 8 to Li 2 S 4 ) And slow kinetic of electrochemical reaction due to the low electrical conductivity of lithium sulfide (Li 2 S 2 / Li 2 S).
이와 관련하여, 최근에는 전기화학적 촉매로 많이 사용되었던 백금(Pt)을 사용하여 리튬-황 전지의 충방전 과정에서, 황의 산화환원 반응의 kinetic 을 향상시킴으로써 리튬-황 전지의 고성능화를 구현한 연구가 보고된 바 있다 (Hesham Al Salem et al.: "Polysulfide Traps for Controlling Redox Shuttle Process of Li-S Batteries": J.Am.Chem.Soc., 2015, 137, 11542).In this regard, recently, a study has been carried out to improve the performance of a lithium-sulfur battery by improving the kinetic of the redox reaction of sulfur in the course of charging and discharging lithium-sulfur batteries using platinum (Pt), which has been widely used as an electrochemical catalyst has been reported (Hesham Al Salem et al:. "Polysulfide Traps for Controlling Redox Shuttle Process of Li-S Batteries":. J.Am.Chem.Soc, 2015, 137, 11542).
그러나, 백금과 같은 귀금속 촉매는 고가이므로 상업화가 힘든 소재일 뿐만 아니라, 충방전 과정에서 황의 산화환원 반응에 의해 피독 가능성이 있어 리튬-황 전지의 양극소재로 활용하기가 쉽지 않은 문제가 있다.However, since noble metal catalysts such as platinum are expensive, they are not only difficult to commercialize, but also have potential to be poisoned by the redox reaction of sulfur in charge and discharge processes, making it difficult to utilize them as a cathode material for lithium-sulfur batteries.
이와 같이, 촉매를 이용한 리튬-황 전지의 성능을 향상시키는데 한계가 있었다. 이에, 전극의 형태 변경과 같은 다른 방식으로 리튬-황 전지를 비롯한 전지 성능을 향상시킬 수 있는 기술 개발이 요구되고 있다.As described above, there was a limit in improving the performance of the lithium-sulfur battery using the catalyst. Accordingly, development of a technique for improving the performance of a battery including a lithium-sulfur battery has been demanded in other ways such as changing the shape of an electrode.
[선행기술문헌][Prior Art Literature]
[특허문헌][Patent Literature]
대한민국 공개특허 제2015-0142832호, “리튬설퍼 전지용 양극조성물, 이를 포함하는 리튬설퍼 전지용 양극 및 이의 제조 방법”Korean Patent Laid-Open Publication No. 2015-0142832, " A cathode composition for a lithium sulfur battery, a cathode for a lithium sulfur battery including the same,
대한민국 공개특허 제2016-0118597호, “산화 그래핀이 적용된 전고체 리튬황 이차전지 양극 및 이의 제조방법”Korean Patent Laid-Open Publication No. 2016-0118597, " A Whole Solid Lithium Sulfide Secondary Battery Having Oxidized Graphene and Its Manufacturing Method "
본 발명자들은 상기 문제점을 해결하기 위해 다각적으로 연구를 수행한 결과, 전극 제조시 전극 활물질, 바인더 및 도전재 이외에 추가로, 마이크로 크기의 탄소재 다공성 입자를 첨가하여 전극을 제조한 결과, 전극의 기공도가 높아져 높은 로딩 하에서도 전극의 반응성과 초기 용량이 향상된 것을 확인하였다.As a result of various studies to solve the above problems, the inventors of the present invention have found that, in addition to the electrode active material, the binder and the conductive material, the microporous carbon particles are also added to the electrodes, It was confirmed that the reactivity and the initial capacity of the electrode were improved even under high loading.
따라서, 본 발명의 목적은 기공도가 향상된 전극을 제공하는 것이다.Accordingly, an object of the present invention is to provide an electrode having improved porosity.
또한, 본 발명의 다른 목적은 이와 같은 기공도가 향상된 전극을 포함하는 리튬 이차전지를 제공하는 것이다.Another object of the present invention is to provide a lithium secondary battery including the electrode having improved porosity.
상기 목적을 달성하기 위해, 본 발명은, 평균 입경(D50)이 1 ㎛ 이상의 다공성 입자인 기공 형성용 첨가제를 포함하는 전극을 제공한다.In order to achieve the above object, the present invention provides an electrode comprising a pore-forming additive which is porous particles having an average particle diameter (D50) of 1 탆 or more.
상기 다공성 입자에 포함된 기공의 기공율(porosity)는 50 내지 95% 일 수 있다.The porosity of the pores contained in the porous particles may be 50 to 95%.
또한, 상기 기공 형성용 첨가제는 탄소 또는 그라파이트를 포함할 수 있다.The pore-forming additive may include carbon or graphite.
또한, 상기 기공 형성용 첨가제의 함량은 상기 전극 전체 중량을 기준으로 0.5 내지 5 중량% 일 수 있다.The content of the pore-forming additive may be 0.5 to 5 wt% based on the total weight of the electrode.
또한, 상기 전극은 기공도가 64% 이상일 수 있다.The electrode may have a porosity of 64% or more.
또한, 상기 전극은 전극 활물질, 바인더, 도전재 및 상기 기공 형성용 첨가제를 포함할 수 있다.In addition, the electrode may include an electrode active material, a binder, a conductive material, and the pore-forming additive.
또한, 상기 전극 활물질은 황 원소(elemental sulfur, S8), 황 계열 화합물 또는 이들의 혼합물로 이루어진 군에서 선택되는 1종 이상일 수 있다.The electrode active material may be at least one selected from the group consisting of elemental sulfur (S8), sulfur-based compounds, and mixtures thereof.
또한, 상기 바인더는 SBR-CMC(styrene-butadiene rubber-carboxymethylcellulose), 폴리(비닐 아세테이트), 폴리비닐알코올, 폴리에틸렌옥사이드, 폴리비닐피롤리돈, 알킬레이티드 폴리에틸렌옥사이드, 가교결합된 폴리에틸렌옥사이드, 폴리비닐에테르, 폴리(메틸메타크릴레이트), 폴리 비닐리덴플루오라이드, 폴리헥사플루오로프로필렌과 폴리비닐리덴플루오라이드의 코폴리머, 폴리(에틸아크릴레이트), 폴리테트라플루오로에틸렌, 폴리비닐클로라이드, 폴리아크릴로니트릴, 폴리비닐피리딘, 폴리스티렌, 이들의 유도체, 이들의 블랜드 및 이들의 코폴리머로 이루어진 군에서 선택되는 1종 이상일 수 있다.Also, the binder may be selected from the group consisting of styrene-butadiene rubber-carboxymethylcellulose (SBR-CMC), polyvinyl acetate, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, crosslinked polyethylene oxide, Poly (ethyl acrylate), polytetrafluoroethylene, polyvinyl chloride, polyacrylic acid, polyvinylidene fluoride, polyvinylidene fluoride, polyvinylidene fluoride, polyvinylidene fluoride, Polyvinylpyridine, polystyrene, derivatives thereof, blends thereof, and copolymers thereof. It is also possible to use at least one of these compounds.
또한, 상기 도전재는 카본 블랙, 아세틸렌 블랙 및 케첸 블랙 중에서 선택되는 탄소계 물질; 및 폴리아닐린, 폴리티오펜, 폴리아세틸렌 및 폴리피롤 중에서 선택되는 전도성 고분자;로 이루어진 군에서 선택되는 1종 이상일 수 있다.Further, the conductive material may be a carbon-based material selected from carbon black, acetylene black, and ketjen black; And a conductive polymer selected from polyaniline, polythiophene, polyacetylene, and polypyrrole.
본 발명은 또한, 상기 전극을 포함하는 리튬 이차전지를 제공한다.The present invention also provides a lithium secondary battery comprising the electrode.
본 발명에 따르면, 기공 형성용 첨가제에 의해 전극의 기공도가 높아지고, 이에 따라 높은 로딩 하에서도 전극의 반응성이 우수하고 초기 용량도 향상되는 효과가 있다.According to the present invention, the porosity of the electrode is increased by the pore-forming additive, so that the reactivity of the electrode is excellent even under high loading and the initial capacity is improved.
또한, 본 발명의 기공 형성용 첨가제에 의해 기공도가 높아진 전극을 리튬-황 전지의 양극으로 적용할 경우, 상기 양극에 포함된 기공 내에 충분한 양의 전해액이 담지되어 리튬-황 전지의 방전 생성물인 폴리 설파이드를 효율적으로 제거할 수 있어, 리튬-황 전지를 비롯한 리튬 이차전지의 수명 특성을 향상시킬 수 있다.When an electrode having increased porosity by the pore-forming additive of the present invention is applied as a positive electrode of a lithium-sulfur battery, a sufficient amount of an electrolyte solution is supported in pores included in the positive electrode to produce a discharge product The polysulfide can be efficiently removed, and the lifetime characteristics of the lithium secondary battery including the lithium-sulfur battery can be improved.
도 1은 본 발명의 실시예 1 및 비교예 1,2에서 제조된 리튬-황 전지의 충방전 실험 결과를 나타내는 그래프이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the results of charging / discharging tests of the lithium-sulfur battery produced in Example 1 of the present invention and Comparative Examples 1 and 2. FIG.
도 2는 실시예 1,2 및 비교예 1에서 제조된 리튬-황 전지의 충방전 실험 결과를 나타내는 그래프이다.FIG. 2 is a graph showing the results of charge-discharge experiments of the lithium-sulfur battery produced in Examples 1 and 2 and Comparative Example 1. FIG.
이하, 본 발명에 대한 이해를 돕기 위하여 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.
본 명세서 및 청구범위에서 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms and words used in the present specification and claims should not be construed in an ordinary or dictionary sense and the inventor can properly define the concept of the term to describe its invention in the best possible way It should be construed as meaning and concept consistent with the technical idea of the present invention.
전극 electrode
본 발명은 높은 로딩 하에서도 전극의 반응성이 우수하고 초기 용량이 높은 전극에 관한 것이다.The present invention relates to an electrode having high reactivity and high initial capacity even under high loading.
본 발명의 전극은 평균 입경(D50)이 1 ㎛ 이상인 기공 형성용 첨가제를 포함한다.The electrode of the present invention includes a pore-forming additive having an average particle diameter (D50) of 1 占 퐉 or more.
상기 기공 형성용 첨가제의 형상은 특별히 제한되지 않으며, 다만 평균 입경(D50)이 1 ㎛ 이상, 바람직하게는 1 ㎛ 내지 20 ㎛ 일 수 있다. 상기 범위 미만이면 전극의 기공도 증가율이 미미하여 높은 로딩 하에서 전극의 반응성 향상 및 초기 용량 향상 효과를 기대할 수 없고, 특히, 리튬-황 전지의 양극으로 적용시 방전 생성물인 폴리 설파이드의 제거 효율이 저하되어 전지의 수명 특성이 저하될 수 있다. 상기 범위 초과이면 입자 크기가 과도하게 크므로 전극용 첨가제로 적절하지 않다.The shape of the pore-forming additive is not particularly limited, but may be an average particle diameter (D50) of 1 占 퐉 or more, preferably 1 占 퐉 to 20 占 퐉. If the amount is less than the above range, the rate of increase in the degree of porosity of the electrode is insignificant, so that it is not expected to improve the reactivity and initial capacity of the electrode under high loading. Particularly, as the anode of lithium- The lifetime characteristics of the battery may be deteriorated. If the amount is larger than the above range, the particle size is excessively large, which is not suitable as an additive for electrodes.
상기 기공 형성용 첨가제는 입자 내부 기공율(porosity)가 50% 내지 95%, 바람직하게는 50% 내지 90%, 보다 바람직하게는 50% 내지 85%일 수 있으며, 이와 같이 기공 형성용 첨가제 자체가 기공을 포함하고 있어 전극에 적용시 상기 기공 형성용 첨가제에 포함된 기공에 의해 전극의 기공도가 향상될 수 있다.The pore-forming additive may have an internal porosity of 50% to 95%, preferably 50% to 90%, more preferably 50% to 85%. In this way, the pore- The porosity of the electrode can be improved by the pores included in the pore-forming additive when applied to an electrode.
상기 기공의 기공율이 상기 범위 미만이면 전극의 기공도 증가율이 미미하여 높은 로딩 하에서 전극의 반응성 향상 및 초기 용량 향상 효과를 기대할 수 없고, 특히, 리튬-황 전지의 양극으로 적용시 방전 생성물인 폴리 설파이드의 제거 효율이 저하되어 전지의 수명 특성이 저하될 수 있으며, 상기 범위 초과이면 전극의 내구성이 저하될 수 있다.If the porosity of the pores is less than the above range, the rate of increase in porosity of the electrode is insignificant, so that it is not expected to improve the reactivity and initial capacity of the electrode under high loading. Particularly, The removal efficiency may be lowered and the lifetime characteristics of the battery may be deteriorated. If the above range is exceeded, the durability of the electrode may be deteriorated.
상기 기공 형성용 첨가제는 다공성 탄소 또는 그라파이트일 수 있다.The pore-forming additive may be porous carbon or graphite.
상기 기공 형성용 첨가제의 함량은 상기 전극 전체 중량을 기준으로 0.5 내지 10 중량%, 바람직하게는 1 내지 10 중량%, 보다 바람직하게는 1.5 내지 10 중량% 일 수 있다. 상기 범위 미만이면 전극의 기공도 증가율이 미미하여 높은 로딩 하에서 전극의 반응성 향상 및 초기 용량 향상 효과를 기대할 수 없고, 특히, 리튬-황 전지의 양극으로 적용시 방전 생성물인 폴리 설파이드의 제거 효율이 저하되어 전지의 수명 특성이 저하될 수 있으며, 상기 범위 초과이면 전극의 기공률이 과도하게 높아져 전극의 내구성이 저하될 수 있다.The content of the pore-forming additive may be 0.5 to 10% by weight, preferably 1 to 10% by weight, more preferably 1.5 to 10% by weight based on the total weight of the electrode. If the amount is less than the above range, the rate of increase in the degree of porosity of the electrode is insignificant, so that it is not expected to improve the reactivity and initial capacity of the electrode under high loading. Particularly, as the anode of lithium- The life characteristics of the battery may be deteriorated. If the above range is exceeded, the porosity of the electrode becomes excessively high, and the durability of the electrode may be deteriorated.
상기 기공 형성용 첨가제는 당업계에서 다공성 탄소 생성물을 제조하는 공지의 방법에 의해 제조될 수 있으며, 예컨대, 상기 기공 형성용 첨가제는 하기 (S1) 내지 (S5) 단계를 포함하는 방법에 의해 다공성 탄소 생성물의 형태로 제조될 수 있다.The pore-forming additive may be produced by a known method for producing a porous carbon product in the art. For example, the pore-forming additive may be produced by a method comprising the following steps (S1) to (S5) Can be prepared in the form of a product.
(S1) 상호 연결된 기공들을 포함하는 무기 주형 재료의 주형을 제공하는 단계;(S1) providing a template of an inorganic mold material comprising interconnected pores;
(S2) 탄소 전구체 물질을 제공하는 단계;(S2) providing a carbon precursor material;
(S3) 상기 전구체 물질로 상기 주형의 기공들을 침투시키는 단계;(S3) infiltrating the pores of the mold with the precursor material;
(S4) 상기 전구체 물질을 탄화시키는 단계; 및(S4) carbonizing the precursor material; And
(S5) 상기 주형을 제거하여 다공성 탄소 생성물을 형성하는 단계.(S5) removing the template to form a porous carbon product.
이때, 상기 (S1) 단계에서 상기 주형 재료는 SiO2일 수 있다.At this time, the mold material at the (S1) step may be SiO 2.
또한, 상기 (S2) 단계에서 탄소 전구체 물질은 피치(pitch)일 수 있으며, 특히 “메소상 피치”는 규칙적인 액정 구조를 갖는 탄소질 재료일 수 있다.In addition, the carbon precursor material may be a pitch in the step (S2), and in particular, the " mesophase pitch " may be a carbonaceous material having a regular liquid crystal structure.
상기 (S5) 단계에서 주형을 제거하는 방법은 화학적 해리에 의해 일어날 수 있으며, 이때, 형성된 다공성 탄소 생성물이 본 발명에 따른 기공 형성용 첨가제일 수 있다.The method of removing the template in the step (S5) may be performed by chemical dissociation, wherein the formed porous carbon product may be a pore-forming additive according to the present invention.
또한, 상기 전극은 전극 활물질과 함께 전자가 전극 내에서 원활하게 이동하도록 하기 위한 도전재 및 전극 활물질간 또는 전극 활물질과 바인더 및 도전재를 더 포함할 수 있다.The electrode may further include an electrode active material and a conductive material and an electrode active material or an electrode active material, a binder, and a conductive material for allowing electrons to move smoothly in the electrode.
상기 전극 활물질은 전지에 사용되는 양극 활물질 또는 음극 활물질을 제한 없이 포함할 수 있다.The electrode active material may include, without limitation, a positive electrode active material or a negative electrode active material used in a battery.
예컨대, 상기 전극 활물질이 리튬-황 전지용 양극 활물질인 경우, 상기 양극 활물질은 황 원소(elemental sulfur, S8), 황 계열 화합물 또는 이들의 혼합물을 포함할 수 있다. 상기 황 계열 화합물은 구체적으로, Li2Sn(n≥1), 유기황 화합물 또는 탄소-황 폴리머((C2Sx)n: x=2.5∼50, n≥2) 등일 수 있다.For example, when the electrode active material is a cathode active material for a lithium-sulfur battery, the cathode active material may include elemental sulfur (S8), a sulfur-based compound, or a mixture thereof. Specifically, the sulfur-based compound may be Li 2 Sn (n? 1), an organic sulfur compound or a carbon-sulfur polymer ((C 2 S x ) n : x = 2.5 to 50, n?
또한, 상기 도전재는 카본 블랙, 아세틸렌 블랙, 케첸 블랙과 같은 탄소계 물질; 또는 폴리아닐린, 폴리티오펜, 폴리아세틸렌, 폴리피롤과 같은 전도성 고분자일 수 있으며, 상기 도전재는 전극 총 중량을 기준으로 5 내지 20 중량%, 바람직하게는 5 내지 15 중량%, 보다 바람직하게는 5 내지 10 중량%의 범위로 포함되는 것이 바람직할 수 있다. 상기 도전재의 함량이 상기 범위 미만이면 상기 도전재 사용에 따른 도전성 향상효과가 미미하고, 상기 범위 초과이면 전극 활물질의 함량이 상대적으로 적게 되어 용량 특성이 저하될 우려가 있다.Further, the conductive material may be a carbon-based material such as carbon black, acetylene black, and Ketjenblack; Or a conductive polymer such as polyaniline, polythiophene, polyacetylene, and polypyrrole, and the conductive material is used in an amount of 5 to 20% by weight, preferably 5 to 15% by weight, more preferably 5 to 10% By weight based on the total weight of the composition. If the content of the conductive material is less than the above range, the effect of improving the conductivity of the conductive material is insignificant. If the content of the conductive material exceeds the above range, the content of the electrode active material becomes relatively small.
또한, 상기 바인더는 폴리(비닐 아세테이트), 폴리비닐알코올, 폴리에틸렌옥사이드, 폴리비닐피롤리돈, 알킬레이티드 폴리에틸렌옥사이드, 가교결합된 폴리에틸렌옥사이드, 폴리비닐에테르, 폴리(메틸메타크릴레이트), 폴리 비닐리덴플루오라이드, 폴리헥사플루오로프로필렌과 폴리비닐리덴플루오라이드의 코폴리머(상품명: Kynar), 폴리(에틸아크릴레이트), 폴리테트라플루오로에틸렌, 폴리비닐클로라이드, 폴리아크릴로니트릴, 폴리비닐피리딘, 폴리스티렌, 이들의 유도체, 블랜드, 코폴리머 등이 사용될 수 있다. 또 상기 바인더는 상기 전극 총 중량을 기준으로 5 내지 20 중량%, 바람직하게는 5 내지 15 중량%, 보다 바람직하게는 5 내지 10 중량%의 범위로 포함되는 것이 바람직할 수 있다. 상기 바인더의 함량이 상기 범위 미만이면 상기 바인더 사용에 따른 전극 활물질간 또는 전극 활물질과 집전체간 결착력 개선효과가 미미하고, 반면 상기 범위 초과이면 상기 전극 활물질의 함량이 상대적으로 적게 되어 용량 특성이 저하될 우려가 있다.The binder may be selected from the group consisting of poly (vinyl acetate), polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, alkylated polyethylene oxide, crosslinked polyethylene oxide, polyvinyl ether, poly (methyl methacrylate) (Trade name: Kynar), poly (ethyl acrylate), polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyvinylpyridine, polyvinylidene fluoride, polyvinylidene fluoride, Polystyrene, derivatives thereof, blends, copolymers and the like can be used. The binder may be contained in an amount of 5 to 20 wt%, preferably 5 to 15 wt%, more preferably 5 to 10 wt% based on the total weight of the electrode. If the content of the binder is less than the above range, the effect of improving the adhesion between the electrode active material or between the electrode active material and the current collector may be insufficient. On the other hand, if the content of the electrode active material is less than the above range, There is a concern.
상기와 같은 전극은 통상의 방법에 따라 제조될 수 있으며, 구체적으로는 상기 전극 활물질과 도전재 및 바인더를 유기용매 상에서 혼합하여 제조한 전극 활물질층 형성용 조성물을, 전극 집전체 위에 도포한 후 건조 및 선택적으로 압연하여 제조될 수 있다. 이때, 상기 기공 형성용 조성물은 상기 전극 활물질과, 도전재 및 바인더와 함께 유기용매 상에서 혼합할 수 있다.The electrode may be prepared by a conventional method. Specifically, a composition for forming an electrode active material layer, which is prepared by mixing the electrode active material, the conductive material, and the binder in an organic solvent, is coated on the electrode current collector, And optionally rolled. At this time, the pore-forming composition may be mixed with the electrode active material, the conductive material, and the binder in an organic solvent.
이때 상기 유기용매로는 상기 양극활물질, 바인더 및 도전재를 균일하게 분산시킬 수 있으며, 쉽게 증발되는 것을 사용하는 것이 바람직하다. 구체적으로는 NMP(N-methyl-2-pyrrolidone), 아세토니트릴, 메탄올, 에탄올, 테트라하이드로퓨란, 물, 이소프로필알코올 등을 들 수 있다.At this time, it is preferable to use the organic solvent which can uniformly disperse the cathode active material, the binder and the conductive material, and is easily evaporated. Specific examples thereof include N-methyl-2-pyrrolidone (NMP), acetonitrile, methanol, ethanol, tetrahydrofuran, water and isopropyl alcohol.
본 발명에 따른 기공 형성용 첨가제를 포함하는 전극은 기공도가 50% 이상, 바람직하게는 55% 이상, 보다 바람직하게는 64% 이상일 수 있다. 또는 상기 기공도는 64% 내지 80% 일 수 있다.The electrode comprising the pore-forming additive according to the present invention may have a porosity of 50% or more, preferably 55% or more, and more preferably 64% or more. Or the porosity may be 64% to 80%.
상기 전극의 기공도가 상기 범위 미만이면 전극의 반응성 및 초기 용량 향상 효과가 미미하고 상기 범위 초과이면 전극의 내구성이 저하될 수 있다.If the porosity of the electrode is less than the above range, the effect of improving the reactivity and initial capacity of the electrode is insignificant. If the porosity is more than the above range, the durability of the electrode may be deteriorated.
리튬 이차전지Lithium secondary battery
본 발명은 또한, 전술한 바와 같은 기공 형성용 첨가제를 포함하는 전극을 포함하는 리튬 이차전지에 관한 것이다.The present invention also relates to a lithium secondary battery comprising an electrode comprising the pore-forming additive as described above.
상기 전극은 리튬 이차전지의 양극 또는 음극 모두에 사용될 수 있으나, 특히, 리튬-황 전지의 양극으로 사용될 경우, 방전 생성물인 폴리 설파이드를 제거하는 효과가 있어 전지의 수명 특성 향상에 유리할 수 있다.The electrode can be used for both the positive electrode and the negative electrode of the lithium secondary battery. However, when used as the positive electrode of the lithium-sulfur battery, the electrode has an effect of removing the polysulfide as a discharge product.
구체적으로, 상기 기공 형성용 첨가제는 기공율이 50 내지 95%가 되도록 기공을 포함하고 있어, 상기 기공 내에 전해액이 담지 되며 상기 기공 내에서 전해액에 의해 폴리 설파이드가 제거될 수 있다.Specifically, the pore-forming additive includes pores such that the porosity is 50 to 95%, and the electrolyte is supported in the pores, and the polysulfide can be removed by the electrolyte in the pores.
본 발명은 또한, 해중합 반응형 고분자(unzipping polymer)의 모노머, 가소제, 유기 주형 및 이들의 혼합물로 이루어진 군에서 선택되는 기공 형성제를 포함하는 전극에 관한 것이다.The present invention also relates to an electrode comprising a pore-forming agent selected from the group consisting of monomers of an unzipping polymer, a plasticizer, an organic template, and mixtures thereof.
상기 기공 형성제는 전극의 활물질층에 포함되어 화학적 반응에 의해 가스를 발생시키는 동시에 기공을 형성하여 전극의 기공도를 향상시킬 수 있다.The pore-forming agent may be included in the active material layer of the electrode to generate a gas by a chemical reaction and simultaneously form pores to improve porosity of the electrode.
상기 전극은 리튬 이차전지, 특히, 리튬 황-전지에 적용되어 충방전에 따른 활물질의 체적 변화에 대하여 완충 작용을 나타내어 리튬-황 전지의 수명 특성을 향상시킬 수 있다.The electrode is applied to a lithium secondary battery, particularly, a lithium sulfur battery, and exhibits a buffering effect against a change in volume of an active material due to charge and discharge, thereby improving lifetime characteristics of the lithium-sulfur battery.
리튬-황 전지에 있어서, 전극에서의 활물질들은 충방전이 진행됨에 따라 수축 팽창하게 된다. 이에 본 발명에서는 전술한 바와 같은 기공 형성제를 전극에 도입하여 활물질의 체적 변화에 대한 완충 작용 및 전해액 담지 효과를 나타내도록 한다.In the lithium-sulfur battery, the active material in the electrode shrinks and expands as the charge and discharge proceeds. In the present invention, the pore-forming agent as described above is introduced into the electrode to exhibit the buffering effect and the electrolyte-supporting effect on the volume change of the active material.
구체적으로는, 상기 전극은 집전체; 및 상기 집전체 상에 형성되며, 활물질을 포함하는 활물질층;을 포함하며, 상기 활물질층은 S와 C을 이용하는 활물질; 및 해중합 반응형 고분자(unzipping polymer)의 모노머, 가소제, 유기 주형 및 이들의 혼합물로 이루어진 군에서 선택되는 기공 형성제;를 포함할 수 있으며, 상기 활물질층은 추가로 바인더, 도전재와 같은 활물질층의 일반적인 첨가제를 더 포함할 수 있다.Specifically, the electrode includes a current collector; And an active material layer formed on the current collector and including an active material, wherein the active material layer comprises S and C; And a pore-forming agent selected from the group consisting of a monomer, a plasticizer, an organic template, and a mixture thereof, of an unzipping polymer, and the active material layer may further include an active material layer such as a binder, , ≪ / RTI >
상기 기공 형성제는 활물질층내에 10 중량% 이하의 함량으로 포함되는 것이 바람직하고, 바람직하게는 0.1 내지 5 중량%, 보다 바람직하게는 0.1 내지 2 중량%의 함량으로 포함될 수 있다. The pore-forming agent is contained in the active material layer in an amount of 10 wt% or less, preferably 0.1 to 5 wt%, more preferably 0.1 to 2 wt%.
또한, 상기 활물질층은 0.8 g/cc 내지 2.0 g/cc의 합제밀도를 가질 수 있고, 바람직하게 0.9 내지 1.6 g/cc, 보다 바람직하게는 1.19 내지 1.3 g/cc의 합제밀도를 가질 수 있다. 활물질층의 합제 밀도가 상기 범위 미만이면 부피당 용량 감소로 인하여 바람직하지 않고,상기 범위를 초과하면 활물질층의 부피팽창이 증가하여 바람직하지 않다.In addition, the active material layer may have an additive density of 0.8 g / cc to 2.0 g / cc, preferably 0.9 to 1.6 g / cc, more preferably 1.19 to 1.3 g / cc. If the mixing density of the active material layer is less than the above range, it is not preferable due to the decrease in capacity per volume, and if it exceeds this range, the volume expansion of the active material layer increases, which is not preferable.
상기와 같은 활물질층을 포함하는 리튬-황 전지용 전극은 활물질 및 기공 형성용 첨가제를 포함하는 활물질층 형성용 조성물을 제조하고, 상기 활물질층 형성용 조성물을 집전체에 도포한 후 건조 또는 열처리하여 활물질층을 형성하는 단계를 포함하는 리튬 황 전지용 전극의 제조방법에 의해 제조될 수 있다.The electrode for a lithium-sulfur battery including the above-described active material layer may be produced by preparing a composition for forming an active material layer containing an active material and an additive for forming pores, applying the composition for forming the active material layer to a current collector, And a step of forming an electrode for a lithium-sulfur battery.
또한, 활물질층 형성시 사용되는 기공 형성용 첨가제의 크기, 형태 및 함량에 따라 활물질층에 형성되는 기공의 크기, 형태 및 기공도를 조절할 수 있는데, 바람직하게는 상기 활물질층은 50 부피% 초과 70 부피% 이하, 바람직하게는 55 부피% 내지 70 부피%, 보다 바람직하게는 60 부피% 내지 70 부피%의 기공도를 가질 수 있다.The size, shape, and porosity of the pores formed in the active material layer can be controlled according to the size, shape, and content of the pore-forming additive used in forming the active material layer. Preferably, And may have a porosity of not more than 5% by volume, preferably 55% by volume to 70% by volume, more preferably 60% by volume to 70% by volume.
상기 활물질층내 기공도가 상기 범위 이하이면 활물질의 체적 변화에 따른 완충 효과가 미미하여 바람직하지 않고, 상기 범위를 초과하면 전극 전도성 감소와 부피당 용량 감소의 단점이 발생하여 바람직하지 않다.If the porosity in the active material layer is less than the above range, the buffering effect due to a change in the volume of the active material is insufficient, which is undesirable. If the porosity is above the above range, electrodeconductivity decreases and capacity per volume decreases.
이와 같은 기공 형성용 첨가제를 포함하는 전극을 포함하는 리튬 이차전지는 기공도 향상에 따라 충방전에 따른 활물질의 체적 변화에 대하여 완충 작용을 나타내어 리튬 이차전지의 수명 특성을 향상시킬 수 있다.The lithium secondary battery including the electrode including the pore-forming additive exhibits a buffering effect against the volume change of the active material according to the improvement of the porosity to improve the life characteristic of the lithium secondary battery.
이하 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변경 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.
제조예 1: 기공 형성용 첨가제 합성Production Example 1: Synthesis of Additive for Pore Formation
상호 연결된 기공들을 포함하는 비-구형의 SiO2 주형의 기공에 탄소 전구체 물질로서 피치를 침투시킨 후, 700 ℃의 온도로 상기 피치를 탄화시켜 다공성 복합체를 형성하였다. After penetrating the pitch as a carbon precursor material into the pores of the non-spherical SiO 2 mold including interconnected pores, the pitch was carbonized at a temperature of 700 ° C to form a porous composite.
그 후, 상기 다공성 복합체를 불산 조 내에 담지하여 SiO2 주형을 제거하여, 다공성 탄소 생성물 형태의 기공 형성용 첨가제를 합성하였다. Thereafter, the porous composite was supported in a hydrofluoric acid bath to remove the SiO 2 template to synthesize a pore-forming additive in the form of a porous carbon product.
합성된 다공성 탄소 생성물의 기공율(porosity)는 50% 이상이고, 평균 입경(D50)은 4 ㎛ 이다.The porosity of the synthesized porous carbon product is 50% or more, and the average particle diameter (D50) is 4 占 퐉.
실시예 1: 양극 및 이를 포함하는 리튬-황 전지 제조Example 1: Preparation of a positive electrode and a lithium-sulfur battery containing the same
양극 활물질인 황-탄소 복합체는 7:3의 비율로 제조되며, 황-탄소 복합체를 88 중량%, 도전재인 카본 블랙 5 중량%, 바인더인 SBR-CMC(styrene-butadiene rubber-carboxymethylcellulose) 5 중량% 및 제조예 1의 기공 형성용 첨가제 2 중량%를 포함하는 양극 합제를 용제인 물에 첨가하여 양극 슬러리를 제조한 후, 알루미늄 호일 집전체상에 코팅하여, 5 mAh/㎠ 의 로딩으로 양극을 제조하였다. The SBR-CMC (styrene-butadiene rubber-carboxymethylcellulose) 5 weight%, the carbon black 5 weight% as a conductive material, and the sulfur-carbon composite as a cathode active material were prepared in a ratio of 7: And 2% by weight of the pore-forming additive of Production Example 1 were added to water as a solvent to prepare a positive electrode slurry and then coated on an aluminum foil current collector to prepare a positive electrode by loading at 5 mAh / Respectively.
음극으로 200 ㎛ 두께를 갖는 리튬 호일을, 전해액은 1M LiTFSI (DME/DOL, 1:1 volumae ratio)에 2 중량%의 LiNO3 첨가제를 용해시킨 유기용액을, 분리막은 폴리프로필렌 필름을 사용하여 리튬-황 전지를 제조하였다.A lithium foil having a thickness of 200 μm as a cathode and an electrolyte solution containing 2 wt% of a LiNO 3 additive dissolved in 1 M LiTFSI (DME / DOL, 1: 1 volumer ratio) - Sulfur batteries were prepared.
-LiTFSI: bis(trifluoromethane) sulfonamide lithium salt -LiTFSI: bis (trifluoromethane) sulfonamide lithium salt
-DME: dimethoxymethane-DME: dimethoxyethane
-DOL: 1,3-dioxolane-DOL: 1,3-dioxolane
실시예 2: 양극 및 이를 포함하는 리튬-황 전지 제조Example 2: Preparation of positive electrode and lithium-sulfur battery containing same
양극 활물질인 황-탄소 복합체는 7:3의 비율로 제조되며, 황-탄소 복합체를 88 중량%, 도전재인 카본 블랙 5 중량%, 바인더인 SBR-CMC(styrene-butadiene rubber-carboxymethylcellulose) 5 중량% 및 제조예 1의 기공 형성용 첨가제 5 중량%를 포함하는 양극 합제를 용제인 물에 첨가하여 양극 슬러리를 제조한 후, 알루미늄 호일 집전체상에 코팅하여, 5 mAh/㎠ 의 로딩으로 양극을 제조하였다. The SBR-CMC (styrene-butadiene rubber-carboxymethylcellulose) 5 weight%, the carbon black 5 weight% as a conductive material, and the sulfur-carbon composite as a cathode active material were prepared in a ratio of 7: And 5% by weight of the pore-forming additive of Production Example 1 were added to water as a solvent to prepare a positive electrode slurry and then coated on an aluminum foil current collector to prepare a positive electrode by loading at 5 mAh / Respectively.
음극으로 200 ㎛ 두께를 갖는 리튬 호일을, 전해액은 1M LiTFSI (DME/DOL, 1:1 volumae ratio)에 2 중량%의 LiNO3 첨가제를 용해시킨 유기용액을, 분리막은 폴리프로필렌 필름을 사용하여 리튬-황 전지를 제조하였다.A lithium foil having a thickness of 200 μm as a cathode and an electrolyte solution containing 2 wt% of a LiNO 3 additive dissolved in 1 M LiTFSI (DME / DOL, 1: 1 volumer ratio) - Sulfur batteries were prepared.
-LiTFSI: bis(trifluoromethane) sulfonamide lithium salt -LiTFSI: bis (trifluoromethane) sulfonamide lithium salt
-DME: dimethoxymethane-DME: dimethoxyethane
-DOL: 1,3-dioxolane-DOL: 1,3-dioxolane
비교예 1Comparative Example 1
실시예 1과 동일하게 실시하되, 기공 형성용 첨가제를 사용하지 않고 양극 및 리튬-황 전지를 제조하였다.A positive electrode and a lithium-sulfur battery were prepared in the same manner as in Example 1 except that no pore-forming additive was used.
비교예 2Comparative Example 2
실시예 1과 동일하게 실시하되, 기공 형성용 첨가제 대신, 평균 입경(D50) 1㎛ 미만인 다공성 탄소를 사용하였으나 기공의 크기가 충분하지 않아 전극의 porosity 향상 효과가 나타나지 않은 양극 및 리튬-황 전지를 제조하였다.Except that porous carbon having an average particle diameter (D50) of less than 1 μm was used in place of the pore-forming additive, but a positive electrode and a lithium-sulfur battery in which porosity improvement effect of the electrode was not obtained due to insufficient pore size .
단위:중량%Unit: wt% 양극 활물질Cathode active material 도전재Conductive material 바인더bookbinder 기공 형성용 첨가제Additive for pore formation 다공성 탄소Porous carbon
황sulfur 카본블랙Carbon black SBR-CMCSBR-CMC 제조예 1Production Example 1
실시예 1Example 1 8888 55 55 22 00
실시예 2Example 2 8585 55 55 55 00
비교예 1Comparative Example 1 9090 55 55 00 00
비교예 2Comparative Example 2 8888 55 55 00 22
실험예Experimental Example 1 One
실시예 1 및 비교예 1에서 제조된 각각 제조된 양극에 대하여 기공도를 측정하였으며, 그 결과, 기공 형성용 첨가제를 포함하지 않는 양극인 비교예 1의 기공도는 56% 인 반면, 기공 형성용 첨가제를 포함하는 양극인 실시예 1의 기공도는 64%로 향상된 것으로 나타났다.The porosity of each of the prepared positive electrode prepared in Example 1 and Comparative Example 1 was measured. As a result, the porosity of Comparative Example 1, which is a positive electrode containing no pore forming additive, was 56% The porosity of Example 1, which is an anode containing additives, was improved to 64%.
실험예 2Experimental Example 2
실시예 1,2 및 비교예 1,2의 리튬-황 전지에 대하여 충방전 실험을 실시하였다.The lithium-sulfur batteries of Examples 1 and 2 and Comparative Examples 1 and 2 were subjected to charge-discharge experiments.
도 1은 본 발명의 실시예 1 및 비교예 1,2에서 제조된 리튬-황 전지의 충방전 실험 결과를 나타내는 그래프이고, 도 2는 실시예 1,2 및 비교예 1에서 제조된 리튬-황 전지의 충방전 실험 결과를 나타내는 그래프이다.FIG. 1 is a graph showing the results of charge and discharge tests of the lithium-sulfur battery prepared in Example 1 of the present invention and Comparative Examples 1 and 2, and FIG. 2 is a graph showing the results of charge- A graph showing the charge / discharge test results of the battery.
도 1 및 2를 참조하면, 1.5-2.8V 전압 범위에서 0.1C 조건으로 충전 및 방전 실험을 실시하여 1 사이클에서의 실험 결과를 관찰한 바, 기공도가 향상된 양극으로 인하여 실시예 1, 2의 리튬-황 전지가 쿨롱 효율(Coulombic efficiency), 초기 방전 용량, 재현성(Cyclability)이 향상된 것을 알 수 있다.Referring to FIGS. 1 and 2, the charging and discharging tests were performed under the condition of the voltage of 1.5-2.8 V and the condition of 0.1 C, and the experimental results in one cycle were observed. As a result, It can be seen that the lithium-sulfur battery has improved Coulombic efficiency, initial discharge capacity, and reproducibility.
이상에서 본 발명은 비록 한정된 실시예와 도면에 의해 설명되었으나, 본 발명은 이것에 의해 한정되지 않으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 본 발명의 기술사상과 아래에 기재될 특허청구범위의 균등범위 내에서 다양한 수정 및 변형이 가능함은 물론이다. While the present invention has been described in connection with certain exemplary embodiments and drawings, it is to be understood that the present invention is not limited thereto and that various changes and modifications will be apparent to those skilled in the art. And various modifications and variations are possible within the scope of the appended claims.

Claims (13)

  1. 평균 입경(D50) 1 ㎛ 이상의 다공성 입자인 기공 형성용 첨가제를 포함하는 전극.An electrode comprising a pore-forming additive which is porous particles having an average particle diameter (D50) of 1 占 퐉 or more.
  2. 제1항에 있어서,The method according to claim 1,
    상기 다공성 입자에 포함된 기공의 기공율(porosity)은 50 내지 95%인, 전극.Wherein the porosity of the pores contained in the porous particles is 50 to 95%.
  3. 제1항에 있어서,The method according to claim 1,
    상기 기공 형성용 첨가제는 탄소 또는 그라파이트를 포함하는, 전극.Wherein the pore-forming additive comprises carbon or graphite.
  4. 제1항에 있어서,The method according to claim 1,
    상기 기공 형성용 첨가제의 함량은 상기 전극 전체 중량을 기준으로 0.5 내지 5 중량%인, 전극.Wherein the content of the pore-forming additive is 0.5 to 5 wt% based on the total weight of the electrode.
  5. 제1항에 있어서,The method according to claim 1,
    상기 전극은 기공도가 64% 이상인, 전극.Wherein the electrode has a porosity of at least 64%.
  6. 제1항에 있어서,The method according to claim 1,
    상기 전극은 전극 활물질, 바인더, 도전재 및 상기 기공 형성용 첨가제를 포함하는, 전극.Wherein the electrode comprises an electrode active material, a binder, a conductive material, and the pore-forming additive.
  7. 제6항에 있어서,The method according to claim 6,
    상기 전극 활물질은 황 원소(elemental sulfur, S8), 황 계열 화합물 또는 이들의 혼합물로 이루어진 군에서 선택되는 1종 이상의 양극 활물질인, 전극.Wherein the electrode active material is at least one cathode active material selected from the group consisting of elemental sulfur (S8), a sulfur-based compound, and a mixture thereof.
  8. 제6항에 있어서,The method according to claim 6,
    상기 바인더는 SBR-CMC(styrene-butadiene rubber-carboxymethylcellulose), 폴리(비닐 아세테이트), 폴리비닐알코올, 폴리에틸렌옥사이드, 폴리비닐피롤리돈, 알킬레이티드 폴리에틸렌옥사이드, 가교결합된 폴리에틸렌옥사이드, 폴리비닐에테르, 폴리(메틸메타크릴레이트), 폴리 비닐리덴플루오라이드, 폴리헥사플루오로프로필렌과 폴리비닐리덴플루오라이드의 코폴리머, 폴리(에틸아크릴레이트), 폴리테트라플루오로에틸렌, 폴리비닐클로라이드, 폴리아크릴로니트릴, 폴리비닐피리딘, 폴리스티렌, 이들의 유도체, 이들의 블랜드 및 이들의 코폴리머로 이루어진 군에서 선택되는 1종 이상인, 전극.The binder may be selected from the group consisting of styrene-butadiene rubber-carboxymethylcellulose (SBR-CMC), polyvinyl acetate, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, crosslinked polyethylene oxide, Polyvinylidene fluoride, copolymers of polyhexafluoropropylene and polyvinylidene fluoride, poly (ethyl acrylate), polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile , Polyvinylpyridine, polystyrene, derivatives thereof, blends thereof, and copolymers thereof.
  9. 제6항에 있어서,The method according to claim 6,
    상기 도전재는 카본 블랙, 아세틸렌 블랙 및 케첸 블랙 중에서 선택되는 탄소계 물질; 및 폴리아닐린, 폴리티오펜, 폴리아세틸렌 및 폴리피롤 중에서 선택되는 전도성 고분자;로 이루어진 군에서 선택되는 1종 이상인, 전극.The conductive material may be a carbon-based material selected from carbon black, acetylene black, and ketjen black; And a conductive polymer selected from the group consisting of polyaniline, polythiophene, polyacetylene, and polypyrrole.
  10. 제1항 내지 제9항 중 어느 한 항의 전극을 포함하는 리튬 이차전지.A lithium secondary battery comprising the electrode according to any one of claims 1 to 9.
  11. 제10항에 있어서,11. The method of claim 10,
    상기 전극은 양극인, 리튬 이차전지.Wherein the electrode is a positive electrode.
  12. 제10항에 있어서,11. The method of claim 10,
    상기 리튬 이차전지는 리튬-황 전지인, 리튬 이차전지.Wherein the lithium secondary battery is a lithium-sulfur battery.
  13. 해중합 반응형 고분자(unzipping polymer)의 모노머, 가소제, 유기 주형 및 이들의 혼합물로 이루어진 군에서 선택되는 기공 형성제를 포함하는 전극.A pore-forming agent selected from the group consisting of monomers of an unzipping polymer, a plasticizer, an organic template, and mixtures thereof.
PCT/KR2018/007263 2017-07-04 2018-06-27 Electrode and lithium secondary battery comprising same WO2019009560A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/623,844 US11424441B2 (en) 2017-07-04 2018-06-27 Electrode and lithium secondary battery comprising same
JP2020518382A JP6918224B2 (en) 2017-07-04 2018-06-27 Electrodes and lithium secondary batteries containing them
EP18828210.7A EP3627593A4 (en) 2017-07-04 2018-06-27 Electrode and lithium secondary battery comprising same
CN201880039648.6A CN110800135B (en) 2017-07-04 2018-06-27 Electrode and lithium secondary battery comprising the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170084684 2017-07-04
KR10-2017-0084684 2017-07-04
KR1020180073277A KR102160710B1 (en) 2017-07-04 2018-06-26 Electrode and Lithium Secondary Battery Comprising the Same
KR10-2018-0073277 2018-06-26

Publications (1)

Publication Number Publication Date
WO2019009560A1 true WO2019009560A1 (en) 2019-01-10

Family

ID=64951157

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/007263 WO2019009560A1 (en) 2017-07-04 2018-06-27 Electrode and lithium secondary battery comprising same

Country Status (1)

Country Link
WO (1) WO2019009560A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022528136A (en) * 2019-07-18 2022-06-08 エルジー エナジー ソリューション リミテッド Lithium-sulfur secondary battery
JP2022528412A (en) * 2019-07-18 2022-06-10 エルジー エナジー ソリューション リミテッド Lithium-sulfur secondary battery
JP2022538822A (en) * 2019-09-24 2022-09-06 エルジー エナジー ソリューション リミテッド Patterned positive electrode for lithium-sulfur secondary battery, manufacturing method thereof, and lithium-sulfur secondary battery including the same

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086404A (en) * 1976-01-27 1978-04-25 The United States Of America As Represented By The United States Department Of Energy Electrode including porous particles with embedded active material for use in a secondary electrochemical cell
KR20090020933A (en) * 2007-08-24 2009-02-27 삼성에스디아이 주식회사 Electrode for rechargeable lithium battery and rechargeable lithium battery including same
JP2011204571A (en) * 2010-03-26 2011-10-13 Panasonic Corp Electrode for lithium ion battery, its manufacturing method, and lithium ion battery using the electrode
KR20130093740A (en) * 2011-12-26 2013-08-23 재단법인 포항산업과학연구원 Carbon material for supercapacitor electrode and method for manufactoring the same
KR20150142832A (en) 2014-06-11 2015-12-23 (주)오렌지파워 Cathod materials for lithium sulfur batteries, cathod electrode comprising the same, and manufacturing method of the same
KR20160031293A (en) * 2014-09-12 2016-03-22 주식회사 엘지화학 Cathode for lithium-sulfur battery and method for preparing the same
KR20160118597A (en) 2015-04-02 2016-10-12 현대자동차주식회사 An anode of all-solid state lithium-sulfur battery using graphene oxide and a method for production thereof
KR20170084684A (en) 2016-01-12 2017-07-20 이브라힘 한나 Synergic method for hydradynamic energy generation with neutralized head pressure pump
KR20180073277A (en) 2016-12-22 2018-07-02 주식회사 성우하이텍 Active hood pop-up system

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086404A (en) * 1976-01-27 1978-04-25 The United States Of America As Represented By The United States Department Of Energy Electrode including porous particles with embedded active material for use in a secondary electrochemical cell
KR20090020933A (en) * 2007-08-24 2009-02-27 삼성에스디아이 주식회사 Electrode for rechargeable lithium battery and rechargeable lithium battery including same
JP2011204571A (en) * 2010-03-26 2011-10-13 Panasonic Corp Electrode for lithium ion battery, its manufacturing method, and lithium ion battery using the electrode
KR20130093740A (en) * 2011-12-26 2013-08-23 재단법인 포항산업과학연구원 Carbon material for supercapacitor electrode and method for manufactoring the same
KR20150142832A (en) 2014-06-11 2015-12-23 (주)오렌지파워 Cathod materials for lithium sulfur batteries, cathod electrode comprising the same, and manufacturing method of the same
KR20160031293A (en) * 2014-09-12 2016-03-22 주식회사 엘지화학 Cathode for lithium-sulfur battery and method for preparing the same
KR20160118597A (en) 2015-04-02 2016-10-12 현대자동차주식회사 An anode of all-solid state lithium-sulfur battery using graphene oxide and a method for production thereof
KR20170084684A (en) 2016-01-12 2017-07-20 이브라힘 한나 Synergic method for hydradynamic energy generation with neutralized head pressure pump
KR20180073277A (en) 2016-12-22 2018-07-02 주식회사 성우하이텍 Active hood pop-up system

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HESHAM AL SALEM ET AL.: "Polysulfide Traps for Controlling Redox Shuttle Process of Li-S Batteries", J.AM.CHEM.SOC., vol. 137, 2015, pages 11542, XP055539851, DOI: 10.1021/jacs.5b04472
See also references of EP3627593A4 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022528136A (en) * 2019-07-18 2022-06-08 エルジー エナジー ソリューション リミテッド Lithium-sulfur secondary battery
JP2022528412A (en) * 2019-07-18 2022-06-10 エルジー エナジー ソリューション リミテッド Lithium-sulfur secondary battery
JP7469325B2 (en) 2019-07-18 2024-04-16 エルジー エナジー ソリューション リミテッド Lithium-sulfur secondary battery
JP7469327B2 (en) 2019-07-18 2024-04-16 エルジー エナジー ソリューション リミテッド Lithium-sulfur secondary battery
JP2022538822A (en) * 2019-09-24 2022-09-06 エルジー エナジー ソリューション リミテッド Patterned positive electrode for lithium-sulfur secondary battery, manufacturing method thereof, and lithium-sulfur secondary battery including the same
JP7315726B2 (en) 2019-09-24 2023-07-26 エルジー エナジー ソリューション リミテッド Patterned positive electrode for lithium-sulfur secondary battery, manufacturing method thereof, and lithium-sulfur secondary battery including the same

Similar Documents

Publication Publication Date Title
WO2015041450A1 (en) Porous silicon-based anode active material, and lithium secondary battery containing same
WO2014014274A1 (en) Carbon-silicon composite, method for preparing same, and cathode active material comprising carbon-silicon composite
WO2015016496A1 (en) Anode for lithium-sulfur battery and manufacturing method therefor
WO2014109523A1 (en) Cathode active material for lithium-sulfur battery and manufacturing method therefor
WO2019182364A1 (en) Separator having a coating layer of lithium-containing composite, lithium secondary battery comprising same, and method for manufacturing same secondary battery
WO2015023154A1 (en) Anode for lithium-sulfur battery and preparation method therefor
WO2020055183A1 (en) Anode for lithium secondary battery and method for manufacturing lithium secondary battery
WO2019078544A1 (en) Negative electrode for lithium secondary battery, and lithium secondary battery comprising same
WO2019088475A1 (en) Sulfur-carbon composite and lithium-sulfur battery including same
WO2019013557A2 (en) Negative electrode for lithium secondary battery, lithium secondary battery comprising same, and method for manufacturing same
WO2018217071A1 (en) Fabrication method of cathode for secondary battery, cathode for secondary battery fabricated thereby, and lithium secondary battery comprising same cathode
WO2019103311A1 (en) Positive electrode for all-solid state lithium-polymer secondary battery, method for manufacturing same, and secondary battery comprising same
WO2019093709A1 (en) Electrolyte composite for lithium-sulfur battery, electrochemical device comprising same, and preparation method therefor
WO2019013525A2 (en) Negative electrode active material for lithium secondary battery, preparation method therefor, and lithium secondary battery comprising same
JP6918224B2 (en) Electrodes and lithium secondary batteries containing them
WO2019009560A1 (en) Electrode and lithium secondary battery comprising same
WO2019088628A2 (en) Sulfur-carbon composite, method for preparing same and lithium secondary battery comprising same
WO2018194345A1 (en) Anode for lithium secondary battery, lithium secondary battery comprising same, and manufacturing method therefor
WO2019078505A1 (en) Binder, and electrode and lithium secondary battery comprising same
WO2022164107A1 (en) Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising same
WO2020122459A1 (en) Anode active material for lithium secondary battery and secondary battery comprising same
WO2014027841A1 (en) Method for manufacturing positive electrode for lithium-sulfur battery and lithium-sulfur battery
WO2014193187A1 (en) Conductive material for secondary battery and electrode for lithium secondary battery comprising same
WO2016122196A1 (en) Electrode, and method for producing battery and electrode
WO2019059662A2 (en) Metal secondary battery having metal electrode

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18828210

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020518382

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018828210

Country of ref document: EP

Effective date: 20191219