KR100351034B1 - Preparation of Li2OV2O5 glass for cathod materials of Li Secondary battery - Google Patents
Preparation of Li2OV2O5 glass for cathod materials of Li Secondary battery Download PDFInfo
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/14—Compositions for glass with special properties for electro-conductive glass
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- 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
Abstract
본 발명은 Li 2차 전지의 정극활물질로 사용가능한 Li2O-V2O5계 유리제조에 관한 것으로, 종래에는 리튬 2차 전지의 정극활물질로는 코발트산리튬(LiCoO2), 리켈산리튬(LiNiO2), 망간산리튬(LiMn2O4) 등의 결정성 전이금속 산화물이 실용화되어 있지만, LiCoO2의 경우 충방전 용량은 130∼140mAh/g 정도로 상당히 높지만 원료가격이 너무 높고 자원이 고갈되고 있는 상태라 지속적인 사용에 문제가 많다. 그리고, LiNiO2나 LiMn2O4등은 가격이 저렴하고 화학적으로 안정하지만 충방전 용량이 100mAh/g이하로 고용량을 요구하는 휴대용 전자기기등에는 문제가 많다. 그리고, 사이클 특성도 나쁘고, 제작에 비용이 많이드는 단점을 갖고 있다.The present invention relates to the production of Li 2 OV 2 O 5 -based glass that can be used as a positive electrode active material of a Li secondary battery. Conventionally, as a positive electrode active material of a lithium secondary battery, lithium cobaltate (LiCoO 2 ) and lithium chelate (LiNiO) are used. 2 ) Crystalline transition metal oxides such as lithium manganate (LiMn 2 O 4 ) have been put to practical use, but the charge and discharge capacity of LiCoO 2 is 130 ~ 140mAh / g, but the raw material price is too high and resources are exhausted. Because of the state, there are many problems with continuous use. LiNiO 2 and LiMn 2 O 4 are inexpensive and chemically stable, but there are many problems in portable electronic devices requiring high capacity with charge / discharge capacity of 100 mAh / g or less. In addition, the cycle characteristics are also poor and costly to produce.
이러한 제반 문제점을 개선하기 위하여 Li 전이금속 산화물계의 각종 결정성 물질들이 연구개발되고 있지만, 현재 LiCoO2보다 뚜렷한 성능이 우수한 정극재료등이 개발되지 못하고 있다.Various crystalline materials of Li transition metal oxides have been researched and developed in order to improve such various problems, but at present, no positive electrode material having better performance than LiCoO 2 has been developed.
이에 본 발명은, Li2O, P2O5, Bi2O3, V2O5의 산화물 조성범위(mol%)에서 Li2CO3, H3PO4, Bi2O3, V2O5등의 고순도 원료를 배합하여 균질하게 혼합시킨후 900∼1000℃에서 충분히 용융시켜 쌍Roller를 이용하여 박판으로 급냉시킨 시편을 200∼450℃의 결정화 영역에서 일정시간(보통 3∼8시간) 동안 열처리하여 화학적으로 안정되고 제조가격이 낮고 충방전 용량은 높고 제조가 간편하면서 성형의 자유도가 큰 LiVO2계의 미세 결정을 일부 함유한 V2O5계유리를 만들고, 급냉시킨 박판의 유리를 미분쇄한후 이에 결합제와 전도제를 일부섞으므로서, 충방전용량이 높은 정극활물질을 제조하는 정극재료용 Li2O-V2O5계 유리 제조방법을 제공한다.Thus, the present invention, Li 2 CO 3 , H 3 PO 4 , Bi 2 O 3 , V 2 O in the oxide composition range (mol%) of Li 2 O, P 2 O 5 , Bi 2 O 3 , V 2 O 5 High- purity raw materials such as 5 are mixed and homogeneously mixed, and then sufficiently melted at 900 to 1000 ° C. and rapidly quenched into thin plates using a double roller for a predetermined time (usually 3 to 8 hours) in a crystallization region of 200 to 450 ° C. Heat-treatment makes a V 2 O 5 type glass containing chemically stable, low manufacturing cost, high charge and discharge capacity, easy to manufacture, and some of the fine crystals of LiVO 2 type with high degree of freedom of molding. The present invention provides a method for producing a Li 2 OV 2 O 5 based glass for a positive electrode material, which manufactures a positive electrode active material having a high charge and discharge capacity by pulverizing a binder and a conductive agent thereafter after grinding.
Description
본 발명은 리튬(Li) 이차전지의 정극활 물질로서 사용가능한 산화리듐(Li2O)-산화바나듐(V2O5)계 유리제조에 관한 것으로서, 특히 결정화 열처리후 화학적으로 안정하고 제조가격이 낮고 충방전 용량이 기존 코발트산리튬(LiCoO3)의 2배 가까운 높은 용량을 갖는 산화리튬(Li2O)-산화비스무스(Bi2O3)-오산화인 (P2O5)-산화바나듐(V2O5)계 결정성 유리 정극재료를 제조하는 방법에 관한 것이다.The present invention relates to the production of lithium oxide (Li 2 O)-vanadium oxide (V 2 O 5 ) -based glass that can be used as a positive electrode active material of lithium (Li) secondary batteries, and is particularly chemically stable and crystallized after crystallization heat treatment. Lithium oxide (Li 2 O)-Bismuth oxide (Bi 2 O 3 )-Phosphorous pentoxide (P 2 O 5 )-Vanadium oxide (L 2 O) with a low charge and discharge capacity of about 2 times higher than that of conventional lithium cobalt (LiCoO 3 ) A method for producing a V 2 O 5 ) -based crystalline glass positive electrode material.
최근에 휴대용 전자기기등의 보급확대로 각종 전자기기의 소형화와 경량화, 고성능화가 수반되고, 그에 따른 전자기기의 전원으로서 특히, 고에너지 밀도를 갖는 긴 수명의 2차 전지 개발이 강하게 요망되고 있다.In recent years, with the expansion of portable electronic devices and the like, miniaturization, weight reduction, and high performance of various electronic devices have been accompanied, and as a power source for electronic devices, there is a strong demand for development of long-life secondary batteries having high energy density.
고성능 Li 이차전지의 성능은 정극 활물질에 크게 좌우된다.The performance of a high performance Li secondary battery largely depends on the positive electrode active material.
그런데, 최근 리듐2차 전지의 정극 활물질로서 코발트산리튬(LiCoO2), 리켈산리튬(LiNiO2), 망간산리튬(LiMn2O4) 등의 결정물질들이 일부 사용화되고 있다.However, recently, crystal materials such as lithium cobalt (LiCoO 2 ), lithium chelate (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ) and the like are used as positive electrode active materials of lithium secondary batteries.
그 중 LiCoO2의 경우 충방전용량은 다른 결정물에 비해 높지만 원료가격이 상당이 높고 Co자체의 자원이 고갈되고 있는 상태로 원가부담은 더욱 가중될 것이다.Among them, LiCoO 2 has higher charge and discharge capacity than other crystals, but the cost burden will be higher due to the high raw material price and the depletion of Co's own resources.
그 외 LiNiO2, LiMn2O4등이 대체 결정물질로 개발되고 있지만 충방전용량 및 전지전압이 낮고 사이클 특성이 나쁘다. 또한 제작에도 어려움이 많다.LiNiO 2 and LiMn 2 O 4 have been developed as alternative crystals, but the charge and discharge capacity, battery voltage are low, and cycle characteristics are poor. There are also many difficulties in production.
이러한 제반 문제점을 개선하기 위하여 Li전이금속 산화물계의 각종 결정성 물질들이 연구 개발되고 있지만, 현재의 LiCoO2보다 뚜렷한 성능이 우수한 정극재료들이 개발되지 못하였다.In order to improve these problems, various crystalline materials of Li transition metal oxides have been researched and developed, but no positive electrode materials with superior performances over current LiCoO 2 have been developed.
따라서, 본 발명은 상기와 같은 종래의 문제점을 해결 하기위해 Li2O, Bi2O3,P2O5V2O5의 조성범위(mol%)에서 Li2CO3, H3PO4, Bi2O3, V2O5등의 원료를 배합하여 900∼1000℃에서 용융시킨후 쌍 Roller를 이용하여 준급냉시켜 성형하고 이를 200∼500℃의 결정화 영역에서 4∼10시간 동안 열처리하여 화학적으로 안정되고 제조가격이 낮고 충방전 용량이 높은 LiVO3계 미세결정을 함유한 Li2O -Bi2O3-P2O5-V2O5계 유리정극활물질을 만들고자 하는데 그 목적이 있다.Accordingly, the present invention is Li 2 O, Bi 2 O 3 , P 2 O 5 in the composition range (mol%) of V 2 O 5 Li 2 CO 3 , H 3 PO 4 in order to solve the conventional problems as described above, After mixing raw materials such as Bi 2 O 3 , V 2 O 5 , and melting them at 900∼1000 ℃, they are quenched using double rollers and molded and heat treated for 4-10 hours in the crystallization region at 200∼500 ℃. The purpose of this study is to make Li 2 O -Bi 2 O 3 -P 2 O 5 -V 2 O 5 -based glass positive electrode active materials containing LiVO 3 -based microcrystals that are stable, low in manufacturing price, and high in charge and discharge capacity.
더불어, 상기의 결정성 유리를 미분쇄한후 이에 결합제와 전도제를 일부 섞음으러서, 충방전 효율이 더 높은 정극을 제조할 수 있도록 하는데 있다.In addition, by pulverizing the crystalline glass and then mixing some of the binder and the conductive agent, it is possible to manufacture a positive electrode having a higher charge and discharge efficiency.
도 1은 본 발명의 일실시예로서 Li2O-Bi2O3-P2O5-V2O5계 유리 열분석 곡선도.1 is a glass thermal analysis curve of the Li 2 O-Bi 2 O 3 -P 2 O 5 -V 2 O 5 system as an embodiment of the present invention.
도 2는 본 발명의 제 3 실시예에 대한 cycle 횟수에 따른 충방전용량 변화도.2 is a charge and discharge capacity change according to the number of cycles for the third embodiment of the present invention.
상기 목적 달성을 위한 본 발명의 정극활물질용 Li2O-V2O5유리는,Li 2 OV 2 O 5 glass for the positive electrode active material of the present invention for achieving the above object,
Li2O 5∼50mol%, Bi2O32∼30mol%, P2O53∼40mol%, V2O530∼90mol% 의 조성범위를 설정하는 단계와;Setting a composition range of Li 2 O 5 to 50 mol%, Bi 2 O 3 2 to 30 mol%, P 2 O 5 3 to 40 mol%, and V 2 O 5 30 to 90 mol%;
상기 단계에 의해 설정된 유리조성범위에 Li2CO3, H3PO4, Bi2O3, V2O5등의 원료를 배합하여 용융시킨후 쌍Roller로 압형성형하는 단계와;Mixing and melting raw materials such as Li 2 CO 3 , H 3 PO 4 , Bi 2 O 3 , V 2 O 5 and the like into the glass composition range set by the above step and forming a pair of rollers;
상기 단계에 의한 성형물을 200∼500℃의 결정화 영역에서 일정시간(예:2∼10시간)동안 열처리하는 단계; 로 진행된다.Heat-treating the molded product according to the step for a predetermined time (for example, 2 to 10 hours) in a crystallization region of 200 to 500 ° C .; Proceeds.
여기서, 상기 열처리된 LiVO3계 결정을 갖는 Li2O -Bi2O3-P2O5-V2O5유리를 미분쇄한후 이에 일정비율의 결합제와 전도제를 혼합하면, 충방전 효율이 높은 정극활물질이 제조된다.Here, the finely pulverized Li 2 O -Bi 2 O 3 -P 2 O 5 -V 2 O 5 glass having the heat-treated LiVO 3 system crystals and then mixing a certain ratio of the binder and the conductive agent, charge and discharge efficiency This high positive electrode active material is produced.
상기 구성에 의하여 Li2O, Bi2O3, P2O5, V2O5의 유리조성범위에 대해서 살펴보면 다음과 같다.Looking at the glass composition range of Li 2 O, Bi 2 O 3 , P 2 O 5 , V 2 O 5 by the above configuration.
[1]. Li2O[One]. Li 2 O
Li ion의 전도성을 증대시키고 유리의 융제로서 들어가며, 5mol% 이하에서는 LiVO3결정 형성에 영향을 주지 못하고, 50mol% 이상에서는 LiVO3결정형성에 Li2O의 함량이 너무 증가되어 몰비(mol%)가 맞지 않다.It increases the conductivity of Li ion and enters the flux of glass, and it does not affect the formation of LiVO 3 crystals at 5 mol% or less, and the content of Li 2 O is increased too much for the formation of LiVO 3 crystals at 50 mol% or more (mol%). Is not correct.
또한, Li2O의 함량이 너무 많으면 흡수성이 증가하여 정극을 제조할 때 가용성으로 알카리 용출을 야기시키므로, 적정한 범위는 Li2O 10∼40mol%이다.In addition, when the content of Li 2 O is too high, the absorbency increases, causing alkali elution with solubility when preparing the positive electrode, and therefore, a suitable range is 10 to 40 mol% of Li 2 O.
[2]. Bi2O3 [2]. Bi 2 O 3
일부 유리형성 산화물 및 결정화시 고점성의 결정화 촉진제로 들어가며, 2mol% 이하에서는 결정화 촉진제로서의 영향을 주지 못하고, 30mol% 이상에서는 너무 고점성의 유리가되어 냉각시 실투가 심하여 glass matrix(유리질)로 부터 균일한 미세 결정석출을 얻기가 힘들다.In some glass forming oxides and crystallization, it enters a high-viscosity crystallization accelerator, and below 2 mol%, it does not affect as a crystallization accelerator, and in 30 mol% or more, it becomes too highly viscous glass, so that the devitrification is severe during cooling and uniform from the glass matrix. It is difficult to obtain fine crystal precipitation.
또한, 점성이 너무 높으면 Liion의 전도에 문제가 되므로, 그 적정범위는 Bi2O33∼25mol%이다.In addition, if the viscosity is too high, it will be a problem in the conduction of Li ion , the appropriate range is Bi 2 O 3 3-25 mol%.
[3]. P2O5 [3]. P 2 O 5
유리형성 산화물로 들어가고 결정화에도 상당한 도움을 주는 것으로, 3mol% 이하에서는 유리형성제로서의 영향을 주지 못하고, 40mol% 이상에서는 유리질이 너무 많이 형성되어 LiVO3결정형성에 너무 점성이 떨어져서 어려움이 많고 생성되는 LiVO3의 량도 적어서 Li ion의 전도에 문제가 되므로 그 적정범위는 P2O54∼35mol% 이다.It enters the glass-forming oxide and contributes to the crystallization, and it has no effect as the glass-forming agent at 3 mol% or less, and too much glass is formed at 40 mol% or more, so that it is too viscous to form the LiVO 3 crystal, which is difficult and produced. Since the amount of LiVO 3 is also low, it is a problem in the conduction of Li ions, so the appropriate range is 4 to 35 mol% of P 2 O 5 .
[4]. V2O5 [4]. V 2 O 5
유리형성 산화물의 역할도 하지만 LiVO3결정의 주성분이며, 전도제로서의 중요한 역할을 한다.It also acts as a glass-forming oxide but is the main component of LiVO 3 crystals and plays an important role as a conducting agent.
30mol% 이하에서는 LiVO3결정을 얻기 힘들고, 90mol% 이상에서는 실투가 심하여 균질한 유리를 얻기가 어렵다. 최적범위는 35∼85mol%이다.At 30 mol% or less, it is difficult to obtain LiVO 3 crystals, and at 90 mol% or more, devitrification is severe and it is difficult to obtain a homogeneous glass. The optimum range is 35 to 85 mol%.
따라서, 상기[1]∼[4]에 의한 유리조성범위에서 Li2CO3, H3PO4, Bi2O3, V2O5등의 원료를 배합한 후 상기의 배합물에 대한 분말 20∼30g 정도를 백금도가니에 담는다.Therefore, after blending raw materials such as Li 2 CO 3 , H 3 PO 4 , Bi 2 O 3 , V 2 O 5 in the glass composition range according to the above [1] to [4], the powders 20 to the above formulations Put about 30g in platinum crucible.
이후, 상기 원료분말이 담긴 백금도가니를 전기로에 넣어 900∼1000℃에서 1시간 이상 충분히 용융시킨후, 쌍 Roller 법으로 준급냉시켜 성형한다.Thereafter, the platinum crucible containing the raw material powder is put into an electric furnace and sufficiently melted at 900 to 1000 ° C. for at least 1 hour, and then quenched and molded by a pair roller method.
그리고, 상기의 성형물을 다시 130∼170℃의 건조기에 넣어 2시간 이상 서냉시켜 시편을 얻도록 하였다.Then, the molded product was placed in a dryer at 130 to 170 ° C and slowly cooled for 2 hours or longer to obtain a specimen.
여기서, 상기 얻어진 시편에 대한 열분석 및 충방전 특성변화는 도 1 및 도 2에 도시된 바와같이 나타나게 된다.Here, the thermal analysis and the charge / discharge characteristic change of the obtained specimen is shown as shown in Figs.
도 1의 경우 첫 피크 온도 250∼300℃와 두 번째 피크온도 350∼370℃ 부근에서 열처리시켜 LiVO3결정을 갖는 Li2O-Bi2O3-P2O5-V2O5계 결정화 유리를 얻었다.In the case of Figure 1 Li 2 O-Bi 2 O 3 -P 2 O 5 -V 2 O 5 type crystallized glass having LiVO 3 crystals by heat treatment at the first peak temperature of 250 ~ 300 ℃ and the second peak temperature of 350 ~ 370 ℃ Got.
그리고, 도 2에 도시된 바와같이, 충방전 특성 변화는 cycle 횟수에 따라 약간 감소하나 거의 200mAh/g의 높은 용량을 갖고 있었다.And, as shown in Figure 2, the charge and discharge characteristics change slightly decreased with the number of cycles, but had a high capacity of almost 200mAh / g.
한편, 상기 열처리된 Li2O-Bi2O3-P2O5-V2O5계 결정화유리를 미분쇄한 후 이에 일정비율의 결합제와 전도제를 혼합하면 충방전 효율이 높은 정극재료를 사용할 수 있게 되는 것이다.On the other hand, the finely pulverized Li 2 O-Bi 2 O 3 -P 2 O 5 -V 2 O 5- based crystallized glass, and then mixed with a certain ratio of the binder and the conductive agent to obtain a positive electrode material with high charge and discharge efficiency It will be available.
즉, 본 발명에서 얻은 Li2O-Bi2O3-P2O5-V2O5계 유리의 정극재료를 전극으로 만들어 충방전 용량을 측정해본 결과 표1에서와 같이 얻어진 Li2O-V2O5계 유리에 Teflon(불소화합물; 불소가 들어간 유기물) 및 전도재(유기물 전도성 물질을 말함)를 소량 첨가시킨 경우 210mAh/g의 높은 충방전 용량을 나타내었으며, 이는 기존 수입되고 있는 LiCoO2결정물질의 2배에 가까운 용량을 보이고 있다. 그리고 증류수에 24시간 이상 침적시킨 결과 내수성(耐水性)이 우수하였다.That is, the charge and discharge capacity of the Li 2 O-Bi 2 O 3 -P 2 O 5 -V 2 O 5 glass obtained in the present invention as an electrode was measured and the Li 2 OV 2 obtained as shown in Table 1 O 5 based Teflon on glass (fluorine compound, organic fluorine-containing), and the conductive material, if that amount is added to (referring to organic conductive material) showed a higher charge-discharge capacity of 210mAh / g, which LiCoO 2 crystals that are existing income It is nearly twice the capacity of the material. Subsequent to immersion in distilled water for 24 hours or more, the water resistance was excellent.
-내수성은 열처리 온도에서 결정화시킨 시편을 증류수중에 담그고 24시간 방 치 시킨후 침식정도를 분석한 결과.-Water resistance is the result of analyzing the degree of erosion after immersing the specimen crystallized at the heat treatment temperature in distilled water and left for 24 hours.
-충방전용은 60cycle 까지 값이 거의 일정함.본 발명의 일실시예를 단계별로 설명면 다음과 같다.[1단계]출발물질은 유리화가 가능한 Li2O, P2O5, V2O5(Li2CO3, 인산염, V2O5등)조성범위를 설정하는 단계이다.[2단계]900 ∼ 1000℃에서의 열처리로 완전 용융시킨 후 준 냉각시켜서 일단비성질의 Li2O, P2O5, V2O5의 새 유리를 만드는 단계이다.[3단계]상기에서 만든 유리를 250 ∼ 350℃의 결정화 영역에서 열처리하는 단계로서, 상기의 단계를 거쳐 안정한 LiV3O8결정을 갖는 결정유리를 형성하여, 이를 분쇄시켜서 정극재료로 사용하게 된다.-The charge and discharge is almost constant up to 60 cycles. When explaining one embodiment of the present invention step by step. [Step 1] Starting material is vitrified Li 2 O, P 2 O 5 , V 2 O 5 (Li 2 CO 3 , Phosphate, V 2 O 5, etc.) This step is to set the composition range. [Step 2] After complete melting by heat treatment at 900 ~ 1000 ℃, semi-cooling to make Li 2 O, P This step is to make a new glass of 2 O 5 , V 2 O 5. [Step 3] The above-mentioned glass is heat-treated in a crystallization region of 250 to 350 ° C., and stable LiV 3 O 8 crystals are formed through the above steps. It forms a crystal glass which has it, and it grind | pulverizes and uses it as a positive electrode material.
이하, 상기 표1을 참조하여 Li2O-Bi2O3-P2O5-V2O5계 유리의 조성비율에 따른 본 발명의 제 1 내지 제 4 실시예를 보다 구체적으로 설명하면 다음과 같다.Hereinafter, referring to Table 1, the first to fourth embodiments of the present invention according to the composition ratio of Li 2 O—Bi 2 O 3 -P 2 O 5 -V 2 O 5 -based glass will be described in detail. Same as
[제 1 및 제 2 실시예][First and Second Embodiment]
Li2O 5∼50mol%, Bi2O315∼20mol%, P2O520mol%, V2O550∼60mol%의 조성범위에서 원료를 혼합한 후 이를 50cc의 백금도가니에 담아 전기로에서 900∼1000℃로 1시간 이상 용융시킨후, 상기의 용융물을 쌍 Roller법으로 준급냉시킨다. 5 to 50 mol% of Li 2 O, 15 to 20 mol% of Bi 2 O 3 , 20 mol% of P 2 O 5 , and 50 to 60 mol% of V 2 O 5, and then mixed in a 50 cc platinum crucible After melt | dissolving at 900-1000 degreeC for 1 hour or more, the said melt is quenched by the twin roller method.
급냉시킨 유리를 건조기에 넣어 130∼170℃에서 2시간 정도 충분히 서냉 시켜서 균질한 유리를 얻었다. 이렇게 얻어진 균질한 유리를 열처리하고 미분쇄하여 용매와 섞어서 정극재료로 사용하게 된다.The quenched glass was placed in a drier and slowly cooled at 130 to 170 ° C. for about 2 hours to obtain a homogeneous glass. The homogeneous glass thus obtained is heat treated, pulverized and mixed with a solvent to be used as a positive electrode material.
이렇게 하여, 정극활 물질을 만들어 충방전 용량을 측정한 결과 110mAh/g정도의 값을 얻었으며, 기존에 시판되고 있는 LiCoO2와 거의 비슷한 값이며, 제조비는 훨씬 낮고 화학적으로 안정하다.In this way, the charge and discharge capacity of the positive electrode active material was measured to obtain a value of about 110 mAh / g, the value is almost similar to the commercially available LiCoO 2 , the manufacturing cost is much lower and chemically stable.
[제 3 및 제 4 실시예][Third and Fourth Embodiment]
제 1 및 제 2 실시예에서와 같이 배합된 원료를 900∼1000℃에서 용융시키고 성형하여 완전히 서냉시켜 얻은 Li2O-Bi2O3-P2O5-V2O5계 유리를 300∼370℃에서 각각 열처리 결정화시킨 후 미분쇄한 유리분말에 Teflon과 전도재를 각 10mol%씩 첨가시켜 정극을 만들면, 그 충방전 용량은 제 3 실시예에서는 210mAh/g, 제 4 실시예에서는 140mAh/g 의 높은값이 나타났으며, 100cycle까지 안정화되었으며 耐水性도 우수하다.The Li 2 O—Bi 2 O 3 —P 2 O 5 —V 2 O 5 based glass obtained by melting and molding the blended raw materials at 900 to 1000 ° C. as in the first and second embodiments and completely slow cooling was formed. After heat-treatment crystallization at 370 ° C., respectively, 10 mol% of Teflon and a conductive material were added to the pulverized glass powder to make a positive electrode. The charge / discharge capacity was 210mAh / g in the third embodiment and 140mAh / in the fourth embodiment. The high value of g appeared, stabilized up to 100 cycles and the water resistance was excellent.
이상에서 설명한 바와같이 본 발명은 Li2O-Bi2O3-P2O5-V2O5계 결정화유리를 Li 2차 전지용 정극활물질로 사용하는 경우 기존의 일본에서 수입되고 있는 LiCoO2,LiMn2O4등의 정극활물질의 거의 2배가 되는 210mAh/g의 높은 충방전 용량을 가질 뿐만아니라 100cycle까지 안정하였으며, 耐水性도 우수하였다. 특히, 유리로 만드는 경우 조성의 자유도가 크고, 성형의 방법이 다양하고 제조비가 아주 저렴하며 최근의 증가하고 있는 휴대용 각종전자기기의 고성능, 대용량화에 적합하게 적용할 수 있을 것이다.As described above, in the present invention, when Li 2 O—Bi 2 O 3 —P 2 O 5 —V 2 O 5 based crystallized glass is used as a cathode active material for a Li secondary battery, LiCoO 2 , In addition to having a high charge / discharge capacity of 210 mAh / g, which is almost twice that of a positive electrode active material such as LiMn 2 O 4 , it is stable up to 100 cycles and has excellent water resistance. In particular, when made of glass has a large degree of freedom of composition, a variety of molding methods, manufacturing cost is very low and will be applicable to the high-performance, high-capacity of various portable electronic devices recently increased.
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