KR20000020531A - Electrode activate material slurry of secondary battery - Google Patents

Electrode activate material slurry of secondary battery Download PDF

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Publication number
KR20000020531A
KR20000020531A KR1019980039174A KR19980039174A KR20000020531A KR 20000020531 A KR20000020531 A KR 20000020531A KR 1019980039174 A KR1019980039174 A KR 1019980039174A KR 19980039174 A KR19980039174 A KR 19980039174A KR 20000020531 A KR20000020531 A KR 20000020531A
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South Korea
Prior art keywords
active material
electrode
slurry
binder
material slurry
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KR1019980039174A
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Korean (ko)
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문기병
송수안
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손욱
삼성에스디아이 주식회사
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Priority to KR1019980039174A priority Critical patent/KR20000020531A/en
Publication of KR20000020531A publication Critical patent/KR20000020531A/en

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    • 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
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

PURPOSE: An electrode activate material slurry of secondary battery is provided to increase capacity of a battery. CONSTITUTION: An electrode activate material, a conduction material and binder are inputted in an instrument. A slurry is made by adding a poly vinyl pyrrolidone polymers(PVP) to the mixture. The poly vinyl pyrrolindone polymers is added 1-50 % of the binder. The activate material is constituted by lithium-transient metal oxide. An air bladder of activate material slurry is removed at a vacuum atmosphere and coated by an aluminum or a cooper foil.

Description

이차전지의 전극 활물질 슬러리Electrode Active Material Slurry of Secondary Battery

본 발명은 이차전지의 전극 활물질 슬러리에 관한 것으로, 특히 활물질 슬러리의 분산성을 향상시켜 전지의 생산성 및 용량을 향상시킬수 있는 분산제를 첨가 한 이차전지의 전극 활물질 슬러리에 관한 것이다.The present invention relates to an electrode active material slurry of a secondary battery, and more particularly, to an electrode active material slurry of a secondary battery containing a dispersant capable of improving dispersibility of an active material slurry to improve battery productivity and capacity.

이차전지는 재충전이 가능하고 소형 및 대용량화가 용이한 것으로, 대표적으로 니켈수소(Ni-MH)전지, 리튬(Li)전지 및 리튬이온(Li-ion)전지가 사용되고 있다.Secondary batteries are rechargeable, easy to compact and large in capacity, and typically include nickel-hydrogen (Ni-MH) batteries, lithium (Li) batteries, and lithium ion (Li-ion) batteries.

여기서 리튬이온전지는 정극 활물질로 리튬-천이금속산화물을 사용하고, 부극활물질로는 카본 혹은 카본복합체를 사용한다. 여기에 산소기, 질소기, 황산기 등을 포함하는 한 개 이상의 유기용매에 리튬염을 녹인 액체 전해질이 사용되어서, 정극과 부극간에 리튬 이온이 이동될 때 발생되는 기전력을 이용하여 충·방전이 이루어지도록 한다.In this case, the lithium ion battery uses lithium-transition metal oxide as the positive electrode active material, and carbon or carbon composite material as the negative electrode active material. A liquid electrolyte in which lithium salt is dissolved in one or more organic solvents including an oxygen group, a nitrogen group, a sulfuric acid group, and the like is charged and discharged by using electromotive force generated when lithium ions are transferred between the positive electrode and the negative electrode. do.

이러한 리튬이온전지에서 정극 및 부극과 같은 전극(電極)의 제조는, 전지의 종류에 따라 활물질의 차이는 있지만, 리튬-천이금속 산화물 또는 카본으로 된 활물질과, 카본으로 된 도전제(정극의 경우) 및 NMP(N-methyl pyrrolidone)와 같은 유기 용매에 녹인 PVDF(polyvinylidene fluoride)로 된 바인더를 혼합한 활물질 슬러리를 제조한 다음, 이것을 진공 분리 후 알루미늄이나 쿠퍼 호일로 된 전극 기재에 코팅하고, 다시 건조 및 롤 프레스한 다음 소정의 크기로 절단하는 공정에 의해 제조되고 있다.In such a lithium ion battery, the production of electrodes such as a positive electrode and a negative electrode differs depending on the type of battery, but the active material is lithium-transition metal oxide or carbon, and a carbon conductive agent (in the case of a positive electrode). ) And an active material slurry prepared by mixing a binder of polyvinylidene fluoride (PVDF) dissolved in an organic solvent such as N-methyl pyrrolidone (NMP), and then vacuum-separating and coating the electrode substrate of aluminum or cooper foil and then again. It is manufactured by the process of drying and roll pressing, and then cutting | disconnection to predetermined size.

여기서 활물질 슬러리는 전극의 활물질, 도전제와 바인더를 혼합한 물질로서, 상기 전극(정극) 활물질은 기본적으로 전도성이 없는 것이므로 그 전도도를 높이기 위해 구(球)형으로 된 활물질 입자의 표면에 도전제가 코팅되게 하여 도전 네트워크를 형성하고, 분말상인 활물질과 도전제를 전극 기재에 용이하게 접착하여 전극형태로 성형하기 위하여 바인더를 혼합하는 것이다.The active material slurry is a material in which an active material, a conductive agent, and a binder of an electrode are mixed, and the electrode (positive electrode) active material is basically non-conductive, so that a conductive agent is formed on the surface of the spherical active material particles to increase its conductivity. The coating is formed to form a conductive network, and the binder is mixed in order to easily bond the powdered active material and the conductive agent to the electrode substrate to form an electrode.

그러나 앞서 설명된 종래의 전극 활물질은 첨가되는 도전제, 바인더 및 유기 용매에 비해 비중이 크기 때문에, 균일 분포의 슬러리 혼합이 이루어지지 못하고 시간이 지남에 따라 점도가 낮아지는 문제점이 있다. 또 도전제의 확산 효과가 저조하여 활물질과의 혼합이 잘 이루어지지 못하기 때문에, 결과적으로 기재의 코팅이 어려운 문제점을 수반하게 된다.However, the above-described conventional electrode active material has a problem that the specific gravity is greater than that of the conductive agent, the binder, and the organic solvent to be added, and thus the slurry is not uniformly distributed and the viscosity decreases over time. In addition, since the diffusion effect of the conductive agent is poor and the mixing with the active material is difficult, the coating of the substrate is difficult.

상술한 종래 기술의 문제점을 해소하기 위한 것으로서, 본 발명은 슬러리 특히 활물질과 도전제, 바인더의 혼합이 잘 이루어지도록 하는 방안으로, 점도를 안정화하고 슬러리 내의 고형분 비율을 높여 전지의 고용량화를 실현할 수 있도록 한 이차전지의 전극 활물질 슬러리를 제공함에 그 목적을 두고 있다.In order to solve the problems of the prior art described above, the present invention is to improve the mixing of the slurry, in particular the active material, the conductive agent, and the binder, so as to achieve high capacity of the battery by stabilizing the viscosity and increasing the solid content ratio in the slurry An object of the present invention is to provide an electrode active material slurry of a secondary battery.

이를 위하여, 본 발명은 용기에 전극 활물질과 도전제 및 바인더를 함께 투입 및 교반하고, 여기에 폴리 비닐 피롤리돈 폴리머(PVP; poly vinyl pyrrolidone polymers)를 소량 첨가하되 상기 바인더의 1∼50%의 양을 첨가하여 얻어짐을 특징으로 하는 슬러리를 제안한다.To this end, in the present invention, the electrode active material, the conductive agent and the binder are added and stirred together with a container, and a small amount of polyvinyl pyrrolidone polymers (PVP) is added thereto, and the amount of 1-50% of the binder A slurry is characterized which is obtained by adding an amount.

여기서 상기 PVP는 분자량이 커 분산제로 사용되는 것이며, 비중이 큰 전극 활물질의 고른 분산을 도와 바인더 및 도전제와의 혼합이 잘 이루어지도록 한다. 따라서, 본 발명에 의하면 활물질 슬러리의 점도가 안정화되고 고형분의 비율이 향상되며, 코팅 작업이 용이하게 이루어지게 되어 고용량의 전극을 제조할 수 있게 된다.Here, the PVP is used as a dispersant due to its high molecular weight, and helps to evenly disperse the electrode active material having a high specific gravity so as to be well mixed with the binder and the conductive agent. Therefore, according to the present invention, the viscosity of the active material slurry is stabilized, the ratio of solid content is improved, and the coating operation is easily performed, thereby making it possible to manufacture a high capacity electrode.

이하, 본 발명의 바람직한 실시예를 보다 상세하게 설명한다.Hereinafter, preferred embodiments of the present invention will be described in more detail.

본 발명에서는 이차전지의 일 예로서 리튬이온전지에 사용되는 전극에 대하여 설명하기로 한다.In the present invention, an electrode used in a lithium ion battery as an example of a secondary battery will be described.

리튬이온전지에 사용되는 정극 및 부극과 같은 전극은 활물질로 리튬-천이금속산화물 및 카본, 카본복합체가 사용되고, 도전제(정극의 경우)로 카본이 사용되며, 바인더로 PVDF가 사용되어서, 이들을 혼합하므로 슬러리를 제조할 수 있다.Electrodes such as positive and negative electrodes used in lithium ion batteries are lithium-transition metal oxides, carbon, and carbon composites as active materials, carbon is used as a conductive agent (in the case of positive electrodes), and PVDF is used as a binder. Therefore, a slurry can be prepared.

여기서 본 발명은 비중이 큰 전극 활물질과 도전제 및 바인더의 혼합이 잘 이루어지도록 하기 위해, 슬러리의 교반 단계에서 PVP(1-ethenyl-2-pyrrolidone polymers)를 소량 첨가하여 전극 활물질의 분산에 기여토록 하고 있다. PVP는 바인더의 첨가량에 대해 1∼50%의 양을 첨가하는 것이 바람직하며, 그 미만의 경우에는 효과가 미미하고, 50％를 초과할 경우에는 바인더의 접착력이 오히려 감소하게 되는 문제점이 있다.Herein, the present invention contributes to the dispersion of the electrode active material by adding a small amount of PVP (1-ethenyl-2-pyrrolidone polymers) in the stirring step of the slurry, so that the specific gravity of the electrode active material, the conductive agent and the binder are well mixed. Doing. PVP is preferably added in an amount of 1 to 50% with respect to the amount of the binder added. If the amount is less than 50%, the effect of the binder is reduced.

PVP는 비닐 피롤리돈의 수용액에 소량의 암모니아를 가하고 과산화수소 용매에 의해 중합되어 얻어지는 백색 분말로, 다음의 화학식 1로 표시할 수 있다.PVP is a white powder obtained by adding a small amount of ammonia to an aqueous solution of vinyl pyrrolidone and polymerizing with a hydrogen peroxide solvent, which can be represented by the following formula (1).

여기서 PVP의 치환기를 구성하는 피롤리돈은 C4NOH7 로 표시될 수 있으며 그 분자량이 78이고, 바인더로 사용하는 PVDF의 치환기의 분자량 9 보다 8.67배에 해당하는 것이므로, 전극 활물질, 도전제 및 바인더와의 혼합시 특히 비중이 큰 전극 활물질의 분산을 도와 고른 분포의 혼합이 이루어지도록 하고, 시간이 지남에 따라 점도가 낮아지는 현상을 방지할 수 있다. 또 본 발명에 의하면 슬러리 내의 고형분 비율이 증대되므로 코팅 작업이 용이하게 실현될 수 있다.Wherein the pyrrolidone constituting the substituent of PVP C 4 NOH 7 Since the molecular weight is 78 and corresponds to 8.67 times the molecular weight of the substituent of the PVDF used as the binder, it helps to disperse the electrode active material having a specific gravity, especially when mixed with the electrode active material, the conductive agent and the binder. Evenly distributed mixing can be achieved, and the viscosity can be prevented from decreasing over time. In addition, according to the present invention, since the solid content ratio in the slurry is increased, the coating operation can be easily realized.

이렇게 제조된 전극의 활물질 슬러리는 진공 분위기에서 기포가 제거되고, 알루미늄 또는 쿠퍼 호일로 된 기재에 코팅되는 것이며, 건조 및 롤 프레스하고 소정의 크기로 절단하는 공정에 의해 극판으로 제조되어 진다.The active material slurry of the electrode thus prepared is one in which a bubble is removed in a vacuum atmosphere, coated on a substrate made of aluminum or cooper foil, and manufactured into an electrode plate by a process of drying, roll pressing and cutting to a predetermined size.

이상에서 설명된 본 발명의 전극은 종래와 달리 10∼15％까지 양품률이 향상됨을 알 수 있었다. 이것은 본 출원인에 의한 다수의 실험의 결과로서 얻어진 것이며, 그 작용은 슬러리의 점도가 향상되고 고형분의 비율이 향상됨에 의한 것이다. 또 본 발명에 의하면 25~30％의 생산성이 향상되는 것으로 나타나고 있다.Unlike the conventional electrode of the present invention described above it was found that the yield is improved by 10 to 15%. This is obtained as a result of a number of experiments by the applicant, the action of which is due to the improved viscosity of the slurry and the proportion of solids. Moreover, according to this invention, it turns out that productivity of 25 to 30% improves.

이상에서 설명된 구성 및 작용을 통하여 알 수 있는 바와 같이, 본 발명에 의한 이차전지의 전극 활물질 슬러리는 전극 활물질의 혼합이 잘 이루어지도록 하고, 점도가 향상되게 하는 효과를 갖는 것이다.As can be seen through the configuration and operation described above, the electrode active material slurry of the secondary battery according to the present invention has an effect of making the mixing of the electrode active material well, and improve the viscosity.

즉, 본 발명은 분산제로서 PVP를 첨가하여 비중이 큰 전극 활물질의 고른 확산에 기여토폭 함으로써, 종래 기술에서 문제시되었던 점도가 낮아지는 현상을 해소할 수 있다.That is, the present invention contributes to the even diffusion of the electrode active material having a specific gravity by adding PVP as a dispersant, thereby eliminating the phenomenon of low viscosity, which has been a problem in the prior art.

또 본 발명에 의하면 슬러리의 점도 및 고형분 비율의 증대로 코팅 작업이 용이하게 되므로 생산성이 향상되는 것이며, 그 양품률 또한 향상되고, 궁극적으로 슬러리의 충진량이 증대되어 고용량의 전지를 실현할 수 있게 된다.In addition, according to the present invention, since the coating operation is facilitated by increasing the viscosity and solid content ratio of the slurry, the productivity is improved, the yield rate is also improved, and ultimately the filling amount of the slurry is increased, thereby realizing a high capacity battery.

Claims (4)

카본으로 된 활물질과 폴리비닐리덴 플로라이드로 된 바인더를 혼합하여 교반하되, 여기에 폴리 비닐 피롤리돈 폴리머를 소량 첨가하여 얻어짐을 특징으로 하는 이차전지의 전극 활물질 슬러리.An electrode active material slurry of a secondary battery, which is obtained by mixing and stirring a carbon active material and a binder made of polyvinylidene fluoride, and adding a small amount of polyvinyl pyrrolidone polymer thereto. 제 1 항에 있어서, 폴리 비닐 피롤리돈 폴리머는 바인더의 첨가량에 대해 1∼50%의 양이 첨가됨을 특징으로 하는 이차전지의 전극 활물질 슬러리.The electrode active material slurry of claim 1, wherein the polyvinyl pyrrolidone polymer is added in an amount of 1 to 50% based on the amount of the binder added. 리튬-천이금속산화물로 된 활물질과 카본으로 된 도전제 및 폴리비닐리덴 플로라이드로 된 바인더를 혼합하여 교반하되, 여기에 폴리 비닐 피롤리돈 폴리머를 소량 첨가하여 얻어짐을 특징으로 하는 이차전지의 전극 활물질 슬러리.An electrode of a secondary battery, which is obtained by mixing and stirring an active material made of lithium-transition metal oxide, a conductive material made of carbon and a binder made of polyvinylidene fluoride, and adding a small amount of polyvinyl pyrrolidone polymer thereto. Active material slurry. 제 1 항에 있어서, 폴리 비닐 피롤리돈 폴리머는 바인더의 첨가량에 대해 1∼50%의 양이 첨가됨을 특징으로 하는 이차전지의 전극 활물질 슬러리.The electrode active material slurry of claim 1, wherein the polyvinyl pyrrolidone polymer is added in an amount of 1 to 50% based on the amount of the binder added.
KR1019980039174A 1998-09-22 1998-09-22 Electrode activate material slurry of secondary battery KR20000020531A (en)

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KR1019980039174A KR20000020531A (en) 1998-09-22 1998-09-22 Electrode activate material slurry of secondary battery

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0878001A (en) * 1994-09-02 1996-03-22 Kanebo Ltd Electrode for organic electrolyte battery
JPH0878057A (en) * 1994-09-02 1996-03-22 Kanebo Ltd Organic electrolytic battery
JPH08203529A (en) * 1995-01-26 1996-08-09 Matsushita Electric Ind Co Ltd Combined electrode, manufacture thereof and lithium secondary battery
JPH08203530A (en) * 1995-01-26 1996-08-09 Matsushita Electric Ind Co Ltd Combined electrode, manufacture thereof and lithium secondary battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0878001A (en) * 1994-09-02 1996-03-22 Kanebo Ltd Electrode for organic electrolyte battery
JPH0878057A (en) * 1994-09-02 1996-03-22 Kanebo Ltd Organic electrolytic battery
JPH08203529A (en) * 1995-01-26 1996-08-09 Matsushita Electric Ind Co Ltd Combined electrode, manufacture thereof and lithium secondary battery
JPH08203530A (en) * 1995-01-26 1996-08-09 Matsushita Electric Ind Co Ltd Combined electrode, manufacture thereof and lithium secondary battery

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