KR101751009B1 - Mixture for Anode for Secondary Battery having irreversible Additives - Google Patents
Mixture for Anode for Secondary Battery having irreversible Additives Download PDFInfo
- Publication number
- KR101751009B1 KR101751009B1 KR1020160071549A KR20160071549A KR101751009B1 KR 101751009 B1 KR101751009 B1 KR 101751009B1 KR 1020160071549 A KR1020160071549 A KR 1020160071549A KR 20160071549 A KR20160071549 A KR 20160071549A KR 101751009 B1 KR101751009 B1 KR 101751009B1
- Authority
- KR
- South Korea
- Prior art keywords
- negative electrode
- secondary battery
- irreversible
- active material
- battery according
- Prior art date
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- 230000002427 irreversible effect Effects 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 239000000654 additive Substances 0.000 title claims abstract description 25
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- 230000000996 additive effect Effects 0.000 claims abstract description 24
- -1 CO 3 Inorganic materials 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
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- 239000011230 binding agent Substances 0.000 claims description 9
- 239000006182 cathode active material Substances 0.000 claims description 9
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 9
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
본 발명은 비가역 첨가제가 포함되어 있는 이차전지용 음극 합제에 관한 것으로서, 상세하게는, 음극 활물질 및 음극의 비가역 효율을 낮추는 비가역 첨가제가 포함되어 있는 것을 특징으로 하는 이차전지용 음극 합제를 제공한다.The present invention relates to a negative electrode mixture for a secondary battery comprising an irreversible additive, and more particularly, to a negative electrode mixture for a secondary battery comprising the negative electrode active material and an irreversible additive for lowering the irreversible efficiency of the negative electrode.
Description
본 발명은 비가역 첨가제가 포함되어 있는 이차전지용 음극 합제에 관한 것이다.The present invention relates to a negative electrode mixture for a secondary battery including an irreversible additive.
모바일 기기에 대한 기술 개발과 수요가 증가함에 따라 에너지원으로서의 이차전지의 수요가 급격히 증가하고 있고, 그러한 이차전지 중 높은 에너지 밀도와 전압을 가지고, 사이클 수명이 길며, 자기방전율이 낮은 리튬 이차전지가 상용화되어 널리 사용되고 있다.As technology development and demand for mobile devices are increasing, the demand for secondary batteries as energy sources is rapidly increasing. Among such secondary batteries, lithium secondary batteries having high energy density and voltage, long cycle life and low self- It has been commercialized and widely used.
이러한 리튬 이차전지의 양극 활물질로는 리튬 함유 코발트 산화물(LiCoO2)이 주로 사용되고 있고, 그 외에 스피넬 결정구조의 LiMn2O4 등과 같은 리튬 함유 망간 산화물과, 리튬 함유 니켈 산화물(LiNiO2) 등도 사용되고 있다. 특히, LiMnO2, LiMn2O4 등의 리튬 망간 함유 산화물은 원료로서 자원이 풍부하고 환경친화적인 망간을 사용한다는 장점 뿐만 아니라, 고용량의 리튬 이차전지 제조가 가능하여, 근래 리튬 이차전지의 양극 활물질로 주목 받고 있다. 음극 활물질로는 탄소재료가 주로 사용되고 있고, 리튬 금속, 황 화합물 등의 사용도 고려되고 있다.Lithium-containing cobalt oxide (LiCoO 2 ) is mainly used as a cathode active material of this lithium secondary battery, and lithium-containing manganese oxide such as LiMn 2 O 4 having a spinel crystal structure and lithium-containing nickel oxide (LiNiO 2 ) have. Particularly, lithium manganese-containing oxides such as LiMnO 2 and LiMn 2 O 4 have the advantage of using manganese which is rich in resources and environmentally friendly as a raw material and capable of producing a high capacity lithium secondary battery, . As the negative electrode active material, a carbon material is mainly used, and the use of lithium metal, a sulfur compound, etc. is also considered.
이러한 전극에 있어서, 양극과 음극의 효율을 비슷한 수준으로 조절하면 비효율적인 전극의 낭비를 최소화할 수 있다. 예를 들어, 대략 100%의 효율을 갖는 음극에 대하여 100%의 효율을 갖는 양극을 사용하는 경우, 전지는 100%의 효율을 발휘할 수 있는 반면, 100%의 효율을 갖는 음극에 대해 90%의 효율을 갖는 양극을 사용하는 경우, 전지는 90%의 효율만을 발휘할 수 있다. 결과적으로, 10%의 음극이 불필요하게 낭비되게 되는 문제가 있다. In such an electrode, it is possible to minimize the waste of the inefficient electrode by controlling the efficiency of the anode and the cathode at a similar level. For example, when a positive electrode having an efficiency of 100% is used for a negative electrode having an efficiency of about 100%, the battery can exhibit an efficiency of 100%, while a negative electrode having an efficiency of 90% When a positive electrode having an efficiency is used, the battery can exert only an efficiency of 90%. As a result, there is a problem that 10% of the cathode is unnecessarily wasted.
이와 관련하여, 일반적으로 탄소계 음극 활물질을 사용하고, 양극 활물질로서 고용량의 리튬 망간 함유 산화물을 사용하는 경우, 최초 충전을 포함한 초기 충방전시 음극의 비가역 효율은 90% 이상으로 매우 높은 반면, 양극의 초기 비가역 효율은 80 ~ 90% 정도에 머무른다. In this connection, when a carbonaceous anode active material is generally used and a high-capacity lithium manganese-containing oxide is used as the cathode active material, irreversible efficiency of the cathode during initial charging and discharging including initial charging is as high as 90% The initial irreversible efficiency of 80 ~ 90%.
또한, 이러한 양극과 음극의 비가역 효율의 차이로 인해, 비가역 효율이 높은 전극의 비가역 작용이 유발되며, 이러한 비가역 작용을 개선하기 위해 비가역 효율이 높은 음극의 활물질을 보다 많이 사용해야 한다.In addition, due to the difference in the irreversible efficiency between the anode and the cathode, irreversible action of the electrode having a high irreversible efficiency is caused. To improve such irreversible action, more active substance having a high irreversible efficiency should be used.
따라서, 상기 리튬 망간 함유 산화물의 양극과 함께 전지의 설계를 위해서는 음극 활물질을 과다하게 투입하게 되고, 본래의 목적인 리튬 망간 함유 산화물을 이용한 고에너지 밀도의 전지를 설계하기 위해, 탄소계 음극 활물질의 투입량이 과다해져, 효율적인 설계가 어려워지는 문제가 있다.Therefore, in order to design a battery together with the anode of the lithium manganese-containing oxide, an anode active material is excessively charged, and in order to design a battery having a high energy density using lithium manganese-containing oxide as its original purpose, And there is a problem that efficient design becomes difficult.
따라서, 이러한 문제점을 해결할 수 있는 기술에 대한 필요성이 높은 실정이다.Therefore, a need exists for a technique capable of solving such a problem.
본 발명은 상기와 같은 종래기술의 문제점과 과거로부터 요청되어온 기술적 과제를 해결하는 것을 목적으로 한다.SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art and the technical problems required from the past.
본 출원의 발명자들은 심도 있는 연구와 다양한 실험을 거듭한 끝에, 이후 설명하는 바와 같이, 비가역 효율 설계에 효과적으로 사용할 수 있고, 높은 도전성으로 인해 전극의 도전 네트워크 구성을 개선시킬 수 있는 이차전지용 음극 합제를 확인하고, 본 발명을 완성하기에 이르렀다.The inventors of the present application have conducted intensive studies and various experiments and, as described later, have found that a negative electrode mixture for a secondary battery, which can be effectively used for irreversible efficiency design and can improve the conductive network structure of the electrode due to high conductivity, And have completed the present invention.
따라서, 본 발명에 따른 이차전지용 음극 합제는 음극 활물질 및 음극의 비가역 효율을 낮추는 비가역 첨가제가 포함되어 있는 것을 특징으로 한다.Accordingly, the negative electrode material mixture for a secondary battery according to the present invention includes an anode active material and an irreversible additive for lowering the irreversible efficiency of the negative electrode.
하나의 구체적인 예에서, 상기 비가역 첨가제는 Li 대비 1.0V이상 내지 2.5V 이하의 작동전압을 가질 수 있다.In one specific example, the irreversible additive may have an operating voltage of 1.0 V to 2.5 V vs. Li.
따라서, 상기 비가역 첨가제는 보통 음극의 작동 전압인 0.05 내지 1.5V 보다 높아 초기의 충전시에만 반응에 참여하고 방전시에는 반응에 참여하지 않아, 전지의 비가역 효율을 효과적으로 설계할 수 있다.Therefore, the irreversible additive is usually higher than the operating voltage of the cathode of 0.05 to 1.5 V, so that the irreversible additive can participate in the reaction only at the initial charging time, and does not participate in the reaction at the time of discharging, thereby effectively designing the irreversible efficiency of the battery.
구체적으로, 본 발명에 따른 음극 합제는 비가역 첨가제를 포함함으로써, 음극의 비가역 효율을 낮출 수 있는 바, 양극에 비해 비가역 효율이 상대적으로 높은 음극을 포함하는 이차전지에 있어서, 음극 합제의 전체적인 사용량을 감소시킬 수 있으며, 이에 따라, 보다 용이하게 전지의 비가역 효율을 효과적으로 설계할 수 있다.Specifically, the negative electrode mixture according to the present invention can reduce the irreversible efficiency of the negative electrode by including an irreversible additive. In the secondary battery including the negative electrode having a relatively high irreversible efficiency as compared with the positive electrode, Therefore, it is possible to more effectively design the irreversible efficiency of the battery.
또한, 상기 비가역 첨가제는 높은 도전성을 나타낼 수 있는 바, 전극의 도전 네트워크 구성을 개선시킬 수 있다.In addition, the irreversible additive can exhibit high conductivity, which can improve the conductive network configuration of the electrode.
이러한 경우에, 상기 비가역 첨가제의 전기 저항값은 5 μΩm 이상 내지 10 μΩm 이하일 수 있다.In this case, the electrical resistance value of the irreversible additive may be not less than 5 μΩm and not more than 10 μΩm.
하나의 구체적인 예에서, 상기 비가역 첨가제는 몰리브덴 화합물일 수 있으며, 더욱 구체적으로, 하기 화학식 1로 표현되는 몰리브덴 황화물일 수 있다.In one specific example, the irreversible additive may be a molybdenum compound, and more specifically, a molybdenum sulfide expressed by the following general formula (1).
MoxSy (1)Mo x S y (1)
상기 식에서, y에 대한 x의 비율(x/y)은 1/2 이상 내지 1이하이다.In the above formula, the ratio (x / y) of x to y is not less than 1/2 and not more than 1.
이러한 경우에, 상기 몰리브덴 황화물은 Mo6S8일 수 있다.In this case, the molybdenum sulfide may be Mo 6 S 8 .
한편, 상기 비가역 첨가제는 음극 합제 전체 중량을 기준으로 0.1 중량% 이상 내지 5 중량% 이하의 범위로 포함될 수 있다.On the other hand, the irreversible additive may be contained in an amount of 0.1 wt% or more to 5 wt% or less based on the total weight of the negative electrode material mixture.
만일, 상기 비가역 첨가제가 음극 합제 전체 중량을 기준으로 0.1 중량% 미만으로 포함될 경우, 본 발명에 따른 소정의 효과를 발휘할 수 없으며, 5 중량%를 초과하여 포함될 경우에는, 양극에 비해 음극의 비가역 효율을 지나치게 낮출 수 있다.If the irreversible additive is contained in an amount of less than 0.1% by weight based on the total weight of the negative electrode material mixture, the desired effect according to the present invention can not be exhibited. If the irreversible additive is contained in an amount exceeding 5% by weight, Can be excessively lowered.
하나의 구체적인 예에서, 상기 음극 활물질은 탄소계 물질을 포함할 수 있는 바, 상기 탄소계 물질은 결정질 인조 흑연, 결정질 천연 흑연, 비정질 하드카본, 저결정질 소프트카본, 카본 블랙, 아세틸렌 블랙, 케첸 블랙, 수퍼 P, 그래핀 (graphene), 및 섬유상 탄소로 이루어진 군으로부터 선택되는 하나 이상일 수 있으며, 상기 탄소계 물질은 결정질 인조 흑연, 및/또는 결정질 천연 흑연일 수 있다.In one specific example, the negative electrode active material may include a carbonaceous material, and the carbonaceous material may be selected from the group consisting of crystalline artificial graphite, crystalline natural graphite, amorphous hard carbon, low crystalline soft carbon, carbon black, acetylene black, , Super P, graphene, and fibrous carbon, and the carbon-based material may be crystalline artificial graphite, and / or crystalline natural graphite.
또한, 상기 음극 활물질은 Si를 더 포함하고, 상기 Si는 음극 활물질 전체 중량을 기준으로 0.1 중량% 이상 내지 30 중량% 이하로 포함될 수 있다.In addition, the negative electrode active material may further include Si, and the Si may be contained in an amount of 0.1 wt% or more to 30 wt% or less based on the total weight of the negative electrode active material.
하나의 구체적인 예에서, 상기 음극 합제는 바인더 및 도전재를 더 포함할 수 있다.In one specific example, the negative electrode material mixture may further include a binder and a conductive material.
본 발명은 상기 음극 합제를 전극집전체 상에 도포하여 제조되는 음극을 제공하는 바, 일반적으로, 상기 음극은 음극 집전체 상에 음극 활물질, 상기 도전재 및 바인더의 혼합물인 전극 합제를 도포한 후 건조하여 제조되며, 필요에 따라서는, 상기 혼합물에 충진제를 더 첨가하기도 한다.The present invention provides a negative electrode prepared by applying the negative electrode mixture onto an electrode current collector. In general, the negative electrode is formed by applying an electrode mixture, which is a mixture of an anode active material, the conductive material and a binder, Dried, and if necessary, a filler may be further added to the mixture.
상기 음극 활물질은, 상기 탄소계 물질, Si 외에, LixFe2O3(0≤x≤1), LixWO2(0≤x≤1), SnxMe1 - xMe'yOz (Me: Mn, Fe, Pb, Ge; Me': Al, B, P, Si, 주기율표의 1족, 2족, 3족 원소, 할로겐; 0<x≤1; 1≤y≤3; 1≤z≤8) 등의 금속 복합 산화물; 리튬 금속; 리튬 합금; 규소계 합금; 주석계 합금; SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, and Bi2O5 등의 금속 산화물; 폴리아세틸렌 등의 도전성 고분자; Li-Co-Ni 계 재료; 티타늄 산화물; 리튬 티타늄 산화물 등을 포함할 수 있지만, 이들만으로 한정되는 것은 아니다.The negative electrode active material may include Li x Fe 2 O 3 (0? X? 1), Li x WO 2 (0? X? 1), Sn x Me 1 - x Me y y O z (Me: Mn, Fe, Pb and Ge; Me ': Al, B, P, Si, Group 1, Group 2 and Group 3 elements of the periodic table, Halogen; z < / = 8); Lithium metal; Lithium alloy; Silicon-based alloys; Tin alloy; SnO, SnO 2, PbO, PbO 2, Pb 2 O 3, Pb 3 O 4, Sb 2 O 3, Sb 2 O 4, Sb 2 O 5, GeO, GeO 2, Bi 2 O 3, Bi 2 O 4, and Bi 2 O 5 ; Conductive polymers such as polyacetylene; Li-Co-Ni-based materials; Titanium oxide; Lithium titanium oxide, and the like, but the present invention is not limited thereto.
상기 음극 집전체는 일반적으로 3 ~ 500 ㎛의 두께로 만들어진다. 이러한 음극 집전체는, 당해 전지에 화학적 변화를 유발하지 않으면서 도전성을 가진 것이라면 특별히 제한되는 것은 아니며, 예를 들어, 구리, 스테인레스 스틸, 알루미늄, 니켈, 티탄, 소성 탄소, 구리나 스테인레스 스틸의 표면에 카본, 니켈, 티탄, 은 등으로 표면처리한 것, 알루미늄-카드뮴 합금 등이 사용될 수 있다. 또한, 양극 집전체와 마찬가지로, 표면에 미세한 요철을 형성하여 음극 활물질의 결합력을 강화시킬 수도 있으며, 필름, 시트, 호일, 네트, 다공질체, 발포체, 부직포체 등 다양한 형태로 사용될 수 있다.The negative electrode current collector is generally made to have a thickness of 3 to 500 mu m. Such an anode current collector is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, and examples of the anode current collector include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, a surface of copper or stainless steel A surface treated with carbon, nickel, titanium, silver or the like, an aluminum-cadmium alloy, or the like can be used. In addition, like the positive electrode collector, fine unevenness can be formed on the surface to enhance the bonding force of the negative electrode active material, and it can be used in various forms such as films, sheets, foils, nets, porous bodies, foams and nonwoven fabrics.
상기 도전재는 통상적으로 양극 활물질을 포함한 혼합물 전체 중량을 기준으로 1 내지 50 중량%로 첨가된다. 이러한 도전재는 당해 전지에 화학적 변화를 유발하지 않으면서 도전성을 가진 것이라면 특별히 제한되는 것은 아니며, 예를 들어, 천연 흑연이나 인조 흑연 등의 흑연; 카본블랙, 아세틸렌 블랙, 케첸 블랙, 채널 블랙, 퍼네이스 블랙, 램프 블랙, 서머 블랙 등의 카본블랙; 탄소 섬유나 금속 섬유 등의 도전성 섬유; 불화 카본, 알루미늄, 니켈 분말 등의 금속 분말; 산화아연, 티탄산 칼륨 등의 도전성 위스키; 산화 티탄 등의 도전성 금속 산화물; 폴리페닐렌 유도체 등의 도전성 소재 등이 사용될 수 있다.The conductive material is usually added in an amount of 1 to 50% by weight based on the total weight of the mixture including the cathode active material. Such a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, for example, graphite such as natural graphite or artificial graphite; Carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
한편, 상기 탄성을 갖는 흑연계 물질이 도전재로 사용될 수 있고, 상기 물질들과 함께 사용될 수도 있다.On the other hand, the graphite-based material having elasticity may be used as a conductive material, and may be used together with the materials.
상기 바인더는 활물질과 도전재 등의 결합과 집전체에 대한 결합에 조력하는 성분으로서, 통상적으로 양극 활물질을 포함하는 혼합물 전체 중량을 기준으로 1 내지 50 중량%로 첨가된다. 이러한 바인더의 예로는, 폴리불화비닐리덴, 폴리비닐알코올, 카르복시메틸셀룰로우즈(CMC), 전분, 히드록시프로필셀룰로우즈, 재생 셀룰로우즈, 폴리비닐피롤리돈, 테트라플루오로에틸렌, 폴리에틸렌, 폴리프로필렌, 에틸렌-프로필렌-디엔 테르 폴리머(EPDM), 술폰화 EPDM, 스티렌 브티렌 고무, 불소 고무, 다양한 공중합체 등을 들 수 있다.The binder is a component that assists in bonding of the active material and the conductive material and bonding to the current collector, and is usually added in an amount of 1 to 50 wt% based on the total weight of the mixture containing the cathode active material. Examples of such binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.
상기 충진제는 양극의 팽창을 억제하는 성분으로서 선택적으로 사용되며, 당해 전지에 화학적 변화를 유발하지 않으면서 섬유상 재료라면 특별히 제한되는 것은 아니며, 예를 들어, 폴리에틸렌, 폴리프로필렌 등의 올리핀계 중합체; 유리섬유, 탄소섬유 등의 섬유상 물질이 사용된다.The filler is optionally used as a component for suppressing the expansion of the anode, and is not particularly limited as long as it is a fibrous material without causing a chemical change in the battery. Examples of the filler include olefin polymers such as polyethylene and polypropylene; Fibrous materials such as glass fibers and carbon fibers are used.
본 발명은 또한, 상기 전극을 포함하는 이차전지를 제공하고, 상기 이차전지는 리튬 이온 전지, 리튬 이온 폴리머 전지, 또는 리튬 폴리머 전지일 수 있다.The present invention also provides a secondary battery comprising the electrode, wherein the secondary battery may be a lithium ion battery, a lithium ion polymer battery, or a lithium polymer battery.
본 발명은, 상기 음극, 양극 및 상기 음극과 양극 사이에 개재되는 분리막을 포함하는 전극조립체에 전해액이 함침되어 있는 구조로 이루어진 이차전지를 제공하는 바, 상기 양극은 양극 활물질로서 하기 화학식 2 또는 3으로 표현되는 리튬 전이금속 산화물을 포함할 수 있다.The present invention provides a secondary battery having a structure in which an electrolyte solution is impregnated in an electrode assembly including the negative electrode, the positive electrode, and the separator interposed between the negative electrode and the positive electrode, wherein the positive electrode includes: Lt; RTI ID = 0.0 > transition metal oxide. ≪ / RTI >
LixMyMn2-yO4-zAz (2) Li x M y Mn 2 - y O 4 - z z (2)
상기 식에서, In this formula,
M은 Al, Mg, Ni, Co, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Ti 및 Bi로 이루어진 군에서 선택되는 하나 이상의 원소이며; M is at least one element selected from the group consisting of Al, Mg, Ni, Co, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, ;
A는 -1 또는 -2가의 하나 이상의 음이온이고; A is one or more anions of -1 or -2;
0.9≤x≤1.2, 0<y<2, 0≤z<0.2이다. 0.9? X? 1.2, 0 <y <2, 0? Z <0.2.
(1-x)LiM'O2-yAy -xLi2MnO3-y'Ay' (3) (1-x) LiM'O 2-y A y -xLi 2 MnO 3 -y ' A y' (3)
상기 식에서, In this formula,
M'은 MnaMb이고; M 'is Mn a M b ;
M은 Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn 및 2주기 전이금속들로 이루어진 군에서 선택되는 하나 이상이며; M is one or more selected from the group consisting of Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn and two period transition metals;
A는 PO4, BO3, CO3, F 및 NO3의 음이온으로 이루어진 군에서 선택되는 하나 이상이고; A is at least one selected from the group consisting of anions of PO 4 , BO 3 , CO 3 , F and NO 3 ;
0<x<1, 0<y≤0.02, 0<y'≤0.02, 0.5≤a≤1.0, 0≤b≤0.5, a + b = 1이다. 0 <x <1, 0 <y? 0.02, 0 <y? 0.02, 0.5? A? 1.0, 0 b? 0.5, a + b =
상기 양극은 양극 집전체 상에 양극 활물질을 도포, 건조 및 프레싱하여 제조되며, 필요에 따라 상기에서와 같은 도전재, 바인더, 충진제 등이 선택적으로 더 포함될 수 있다.The positive electrode is prepared by applying, drying and pressing a positive electrode active material on a positive electrode current collector, and may optionally further include a conductive material, a binder, a filler, and the like as described above.
상기 양극 활물질은, 상기 화학식 2 또는 3으로 표현되는 리튬 전이금속 산화물 외에, 상세하게는, 과량의 리튬을 포함하는 층상 복합 산화물일 수 있으며, 더욱 상세하게는, 음극에 비해 비가역 효율이 낮은 양극 활물질이라면, 이들만으로 한정되는 것은 아니다.The cathode active material may be a layered composite oxide containing an excessive amount of lithium in addition to the lithium transition metal oxide represented by the chemical formula 2 or 3 in detail. More specifically, the cathode active material may be a cathode active material having a lower irreversible efficiency It is not limited to these.
상기 양극 집전체는 일반적으로 3 ~ 500 ㎛의 두께로 만든다. 이러한 양극 집전체는, 당해 전지에 화학적 변화를 유발하지 않으면서 높은 도전성을 가지는 것이라면 특별히 제한되는 것은 아니며, 예를 들어, 스테인레스 스틸, 알루미늄, 니켈, 티탄, 소성 탄소, 또는 알루미늄이나 스테리인레스 스틸의 표면에 카본, 니켈, 티탄, 은 등으로 표면처리한 것 등이 사용될 수 있다. 집전체는 그것의 표면에 미세한 요철을 형성하여 양극 활물질의 접착력을 높일 수도 있으며, 필름, 시트, 호일, 네트, 다공질체, 발포체, 부직포체 등 다양한 형태가 가능하다.The cathode current collector generally has a thickness of 3 to 500 mu m. Such a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery. Examples of the positive electrode current collector include stainless steel, aluminum, nickel, titanium, sintered carbon, aluminum or stainless steel A surface treated with carbon, nickel, titanium, silver or the like may be used. The current collector may have fine irregularities on the surface thereof to increase the adhesive force of the cathode active material, and various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric are possible.
상기 이차전지는 리튬 이온 전지, 리튬 이온 폴리머 전지, 또는 리튬 폴리머 전지일 수 있다.The secondary battery may be a lithium ion battery, a lithium ion polymer battery, or a lithium polymer battery.
상기 리튬 이차전지들은 일반적으로 양극, 음극, 및 상기 양극과 음극에 개재되는 분리막 및 리튬염 함유 비수 전해질로 구성되어 있으며, 리튬 이차전지의 기타 성분들에 대해 이하에서 설명한다. The lithium secondary batteries generally include an anode, a cathode, a separator interposed between the anode and the cathode, and a non-aqueous electrolyte containing a lithium salt. Other components of the lithium secondary battery will be described below.
상기 분리막은 양극과 음극 사이에 개재되며, 높은 이온 투과도와 기계적 강도를 가지는 절연성의 얇은 박막이 사용된다. 분리막의 기공 직경은 일반적으로 0.01 ~ 10 ㎛이고, 두께는 일반적으로 5 ~ 300 ㎛이다. 이러한 분리막으로는, 예를 들어, 내화학성 및 소수성의 폴리프로필렌 등의 올레핀계 폴리머; 유리섬유 또는 폴리에틸렌 등으로 만들어진 시트나 부직포 등이 사용된다. 전해질로서 폴리머 등의 고체 전해질이 사용되는 경우에는 고체 전해질이 분리막을 겸할 수도 있다.The separation membrane is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used. The pore diameter of the separator is generally 0.01 to 10 mu m and the thickness is generally 5 to 300 mu m. Such separation membranes include, for example, olefinic polymers such as polypropylene, which are chemically resistant and hydrophobic; A sheet or nonwoven fabric made of glass fiber, polyethylene or the like is used. When a solid electrolyte such as a polymer is used as an electrolyte, the solid electrolyte may also serve as a separation membrane.
상기 리튬염 함유 비수 전해질은, 비수 전해질과 리튬으로 이루어져 있고, 비수 전해질로는 비수계 유기용매, 유기 고체 전해질, 무기 고체 전해질 등이 사용되지만 이들만으로 한정되는 것은 아니다.The lithium salt-containing nonaqueous electrolyte is composed of a nonaqueous electrolyte and lithium. Nonaqueous organic solvents, organic solid electrolytes, inorganic solid electrolytes, and the like are used as the nonaqueous electrolyte, but the present invention is not limited thereto.
상기 비수계 유기용매로는, 예를 들어, N-메틸-2-피롤리디논, 프로필렌 카르보네이트, 에틸렌 카르보네이트, 부틸렌 카르보네이트, 디메틸 카르보네이트, 디에틸 카르보네이트, 감마-부틸로 락톤, 1,2-디메톡시 에탄, 테트라히드록시 프랑(franc), 2-메틸 테트라하이드로푸란, 디메틸술폭시드, 1,3-디옥소런, 포름아미드, 디메틸포름아미드, 디옥소런, 아세토니트릴, 니트로메탄, 포름산 메틸, 초산메틸, 인산 트리에스테르, 트리메톡시 메탄, 디옥소런 유도체, 설포란, 메틸 설포란, 1,3-디메틸-2-이미다졸리디논, 프로필렌 카르보네이트 유도체, 테트라하이드로푸란 유도체, 에테르, 피로피온산 메틸, 프로피온산 에틸 등의 비양자성 유기용매가 사용될 수 있다.Examples of the non-aqueous organic solvent include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma -Butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane , Acetonitrile, nitromethane, methyl formate, methyl acetate, triester phosphate, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate Nonionic organic solvents such as tetrahydrofuran derivatives, ethers, methyl pyrophosphate, ethyl propionate and the like can be used.
상기 유기 고체 전해질로는, 예를 들어, 폴리에틸렌 유도체, 폴리에틸렌 옥사이드 유도체, 폴리프로필렌 옥사이드 유도체, 인산 에스테르 폴리머, 폴리 에지테이션 리신(agitation lysine), 폴리에스테르 술파이드, 폴리비닐 알코올, 폴리 불화 비닐리덴, 이온성 해리기를 포함하는 중합제 등이 사용될 수 있다.Examples of the organic solid electrolyte include a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, A polymer containing an ionic dissociation group and the like may be used.
상기 무기 고체 전해질로는, 예를 들어, Li3N, LiI, Li5NI2, Li3N-LiI-LiOH, LiSiO4, LiSiO4-LiI-LiOH, Li2SiS3, Li4SiO4, Li4SiO4-LiI-LiOH, Li3PO4-Li2S-SiS2 등의 Li의 질화물, 할로겐화물, 황산염 등이 사용될 수 있다.Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides and sulfates of Li such as Li 4 SiO 4 -LiI-LiOH and Li 3 PO 4 -Li 2 S-SiS 2 can be used.
상기 리튬염은 상기 비수계 전해질에 용해되기 좋은 물질로서, 예를 들어, LiCl, LiBr, LiI, LiClO4, LiBF4, LiB10Cl10, LiPF6, LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, (CF3SO2)2NLi, 클로로 보란 리튬, 저급 지방족 카르본산 리튬, 4 페닐 붕산 리튬, 이미드 등이 사용될 수 있다.The lithium salt is a material that is readily soluble in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10 Cl 10, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide.
또한, 상기 리튬염 함유 비수 전해질에는 충방전 특성, 난연성 등의 개선을 목적으로, 예를 들어, 피리딘, 트리에틸포스파이트, 트리에탄올아민, 환상 에테르, 에틸렌 디아민, n-글라임(glyme), 헥사 인산 트리 아미드, 니트로벤젠 유도체, 유황, 퀴논 이민 염료, N-치환 옥사졸리디논, N,N-치환 이미다졸리딘, 에틸렌 글리콜 디알킬 에테르, 암모늄염, 피롤, 2-메톡시 에탄올, 삼염화 알루미늄 등이 첨가될 수도 있다. 경우에 따라서는, 불연성을 부여하기 위하여, 사염화탄소, 삼불화에틸렌 등의 할로겐 함유 용매를 더 포함시킬 수도 있고, 고온 보존 특성을 향상시키기 위하여 이산화탄산 가스를 더 포함시킬 수도 있으며, FEC(Fluoro-Ethylene Carbonate), PRS(Propene sultone) 등을 더 포함시킬 수 있다.The lithium salt-containing non-aqueous electrolyte may further contain, for the purpose of improving charge / discharge characteristics, flame retardancy, etc., for example, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, glyme, N, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol, aluminum trichloride, etc. May be added. In some cases, halogen-containing solvents such as carbon tetrachloride and ethylene trifluoride may be further added to impart nonflammability. In order to improve the high-temperature storage characteristics, carbon dioxide gas may be further added. FEC (Fluoro-Ethylene Carbonate, PRS (Propene sultone), and the like.
하나의 구체적인 예에서, LiPF6, LiClO4, LiBF4, LiN(SO2CF3)2 등의 리튬염을, 고유전성 용매인 EC 또는 PC의 환형 카보네이트와 저점도 용매인 DEC, DMC 또는 EMC의 선형 카보네이트의 혼합 용매에 첨가하여 리튬염 함유 비수계 전해질을 제조할 수 있다.In one specific example, LiPF 6, LiClO 4, LiBF 4, LiN (SO 2 CF 3) 2 , such as a lithium salt, a highly dielectric solvent of DEC, DMC or EMC Fig solvent cyclic carbonate and a low viscosity of the EC or PC of And then adding it to a mixed solvent of linear carbonate to prepare a lithium salt-containing non-aqueous electrolyte.
본 발명은, 상기 이차전지를 단위전지로 포함하는 전지모듈, 상기 전지모듈을 포함하는 전지팩, 및 상기 전지팩을 전원으로 포함하는 디바이스를 제공한다.The present invention provides a battery module including the secondary battery as a unit cell, a battery pack including the battery module, and a device including the battery pack as a power source.
이 때, 상기 디바이스의 구체적인 예로는, 전기자동차, 하이브리드 전기자동차, 플러그-인 하이브리드 전기자동차, 또는 전력저장용 시스템일 수 있으나, 이에 한정되는 것은 아니다.At this time, specific examples of the device may be, but not limited to, an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or a power storage system.
상기에서 설명한 바와 같이, 본 발명에 따른 이차전지용 음극 합제는, 음극 활물질 및 음극의 비가역 효율을 낮추는 비가역 첨가제가 포함되어 있어, 전지의 비가역 효율을 효과적으로 설계할 수 있으며, 전극의 도전 네트워크 구성을 개선시킬 수 있다.As described above, the negative electrode material mixture for a secondary battery according to the present invention includes an irreversible additive for lowering the irreversible efficiency of the negative electrode active material and the negative electrode, thereby effectively designing the irreversible efficiency of the battery, .
이하, 실시예를 통해 본 발명을 더욱 상술하지만, 하기 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범주가 이들만으로 한정되는 것은 아니다.Hereinafter, the present invention will be described in further detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
<실시예 1>≪ Example 1 >
음극 활물질로서 인조 흑연을 포함하는 음극 활물질 92.2 중량%, Super-P(도전재) 3 중량%, PVdF(결합제) 3 중량% 및 비가역 첨가제로서 몰리브덴 황화물(Mo6S8) 1.8 중량%를 용제인 NMP(N-methyl-2-pyrrolidone)에 첨가하여 음극 합제를 제조하였다.A negative electrode active material including artificial graphite as a negative electrode active material, 92% by weight of an anode active material, 3% by weight of Super-P (conductive material), 3% by weight of PVdF (binder) and 1.8% by weight of molybdenum sulfide (Mo 6 S 8 ) N-methyl-2-pyrrolidone (NMP) to prepare an anode mixture.
<실시예 2>≪ Example 2 >
음극 활물질로서 인조 흑연을 포함하는 음극 활물질 89.7 중량%, Super-P(도전재) 3 중량%, PVdF(결합제) 3 중량% 및 비가역 첨가제로서 몰리브덴 황화물(Mo6S8) 4.3 중량%를 용제인 NMP(N-methyl-2-pyrrolidone)에 첨가하여 음극 합제를 제조하였다.A negative electrode active material containing artificial graphite as an anode active material, 89.7 wt% of an anode active material, 3 wt% of super-P (conductive material), 3 wt% of PVdF (binder) and 4.3 wt% of molybdenum sulfide (Mo 6 S 8 ) N-methyl-2-pyrrolidone (NMP) to prepare an anode mixture.
<비교예 1>≪ Comparative Example 1 &
몰리브덴 황화물(Mo6S8)을 첨가하지 않은 점을 제외하고, 음극 활물질로서 Si와 인조 흑연을 20:80의 비율로 포함하는 음극 활물질 94 중량%, Super-P(도전재) 3 중량%, PVdF(결합제) 3 중량%를 용제인 NMP(N-methyl-2-pyrrolidone)에 첨가하여 음극 합제를 제조하였으며, 실시예 1과 동일한 방법으로 음극을 제조하였다., 94% by weight of an anode active material containing Si and artificial graphite in a ratio of 20:80 as the negative electrode active material, 3% by weight of Super-P (conductive material), and a molybdenum sulfide (Mo 6 S 8 ) 3% by weight of PVdF (binder) was added to NMP (N-methyl-2-pyrrolidone) as a solvent to prepare a negative electrode mixture, and a negative electrode was prepared in the same manner as in Example 1.
<실험예 1><Experimental Example 1>
양극 활물질로 리튬 망간계 복합 산화물을 포함하는 양극으로서, 비가역 효율이 85%인 양극을 제조하고, 상기 실시예 1 및 비교예 1에서 각각 제조한 음극 합제를 두께 15 ㎛의 구리 호일에 도포하여 음극을 제조하였다. 상기 양극과 음극을 포함하는 전지를 제조하고, 각각의 전지의 양극과 음극의 비가역 효율 및 비교예 1에 대한 음극 활물질의 투입 비율을 측정하여, 그 결과를 각각 표 1에 나타내었다.A positive electrode having an irreversible efficiency of 85% as a positive electrode containing a lithium manganese composite oxide as a positive electrode active material was prepared. The negative electrode mixture prepared in each of Example 1 and Comparative Example 1 was applied to a copper foil having a thickness of 15 탆, . The batteries including the positive electrode and the negative electrode were manufactured and the irreversible efficiency of the positive electrode and the negative electrode of each battery and the charging ratio of the negative electrode active material to the comparative example 1 were measured and the results are shown in Table 1, respectively.
상기 표 1에서 보는 바와 같이, 본 발명의 실시예 1 및 2와 같이 비가역 첨가제로서 몰리브덴 황화물을 포함하는 음극 합제를 사용해 제조한 음극의 경우, 상기 비가역 첨가제를 포함하고 있지 않은 비교예 1의 음극 합제를 사용해 제조한 음극에 비해, 양극과의 비가역 효율의 차이가 적음에도 불구하고, 음극 활물질의 투입량이 적음을 확인할 수 있다. As shown in Table 1, in the case of the negative electrode prepared using the negative electrode mixture containing molybdenum sulfide as the irreversible additive as in Examples 1 and 2 of the present invention, the negative electrode mixture of Comparative Example 1 containing no irreversible additive It can be confirmed that the amount of the negative electrode active material input is small although the difference in irreversible efficiency between the negative electrode and the negative electrode is small.
다시 말해, 상기 몰리브덴 황화물이 비가역 첨가제로서 음극 합제에 첨가될 경우, 음극의 초기 비가역 효율을 양극과 유사한 범위로 맞춤으로써, 음극의 과도한 투입을 방지하고, 이에 따라, 전지의 비가역 효율을 효과적으로 설계할 수 있으며, 나아가 전지셀의 전체적인 용량 및 부피당 에너지 밀도를 최대화할 수 있다.In other words, when the molybdenum sulfide is added to the negative electrode mixture as an irreversible additive, the initial irreversible efficiency of the negative electrode is adjusted to a range similar to that of the positive electrode, thereby preventing an excessive introduction of the negative electrode, thereby effectively designing the irreversible efficiency of the battery. And can further maximize the energy density per unit capacity and volume of the battery cell.
본 발명이 속한 분야에서 통상의 지식을 가진 자라면, 상기 내용을 바탕을 본 발명의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다.It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (19)
상기 탄소계 물질은 결정질 인조 흑연, 또는 결정질 천연 흑연, 또는 결정질 인조 흑연 및 결정질 천연 흑연인 것을 특징으로 하는 이차전지용 음극 합제:
MoxSy (1)
상기 식에서, y에 대한 x의 비율(x/y)은 1/2 이상 내지 1이하이다.An irreversible additive for lowering the irreversible efficiency of the negative electrode active material and the negative electrode, wherein the negative active material is made of a carbon-based material, and the irreversible additive is a molybdenum sulfide expressed by the following formula (1)
Wherein the carbon-based material is crystalline artificial graphite, crystalline natural graphite, or crystalline artificial graphite and crystalline natural graphite.
Mo x S y (1)
In the above formula, the ratio (x / y) of x to y is not less than 1/2 and not more than 1.
LixMyMn2-yO4-zAz (2)
상기 식에서,
M은 Al, Mg, Ni, Co, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Ti 및 Bi로 이루어진 군에서 선택되는 하나 이상의 원소이며;
A는 -1 또는 -2가의 하나 이상의 음이온이고;
0.9≤x≤1.2, 0<y<2, 0≤z<0.2이다.
(1-x)LiM'O2-yAy -xLi2MnO3-y'Ay' (3)
상기 식에서,
M'은 MnaMb이고;
M은 Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn 및 2주기 전이금속들로 이루어진 군에서 선택되는 하나 이상이며;
A는 PO4, BO3, CO3, F 및 NO3의 음이온으로 이루어진 군에서 선택되는 하나 이상이고;
0<x<1, 0<y≤0.02, 0<y'≤0.02, 0.5≤a≤1.0, 0≤b≤0.5, a + b = 1이다. 14. The secondary battery according to claim 13, wherein the cathode comprises a lithium transition metal oxide represented by the following general formula (2) or (3) as a cathode active material:
Li x M y Mn 2 - y O 4 - z z (2)
In this formula,
M is at least one element selected from the group consisting of Al, Mg, Ni, Co, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, ;
A is one or more anions of -1 or -2;
0.9? X? 1.2, 0 <y <2, 0? Z <0.2.
(1-x) LiM'O 2-y A y -xLi 2 MnO 3 -y ' A y' (3)
In this formula,
M 'is Mn a M b ;
M is one or more selected from the group consisting of Ni, Ti, Co, Al, Cu, Fe, Mg, B, Cr, Zr, Zn and two period transition metals;
A is at least one selected from the group consisting of anions of PO 4 , BO 3 , CO 3 , F and NO 3 ;
0 <x <1, 0 <y? 0.02, 0 <y? 0.02, 0.5? A? 1.0, 0 b? 0.5, a + b = 1.
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KR102024687B1 (en) | 2017-12-07 | 2019-09-24 | 충북대학교 산학협력단 | Electrolyte composition for ultra battery and ultra battery comprising the same |
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JP2000251895A (en) * | 1999-02-24 | 2000-09-14 | Samsung Sdi Co Ltd | Negative electrode active material for lithium secondary battery and its manufacture |
JP2010067508A (en) * | 2008-09-11 | 2010-03-25 | Nissan Motor Co Ltd | Negative electrode protective agent for lithium ion secondary battery, and negative electrode for lithium ion secondary battery including the same |
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JP2010067508A (en) * | 2008-09-11 | 2010-03-25 | Nissan Motor Co Ltd | Negative electrode protective agent for lithium ion secondary battery, and negative electrode for lithium ion secondary battery including the same |
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