WO2015065046A1 - 양극 활물질의 제조방법, 및 이에 의해 제조된 리튬 이차전지용 양극 활물질 - Google Patents
양극 활물질의 제조방법, 및 이에 의해 제조된 리튬 이차전지용 양극 활물질 Download PDFInfo
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- WO2015065046A1 WO2015065046A1 PCT/KR2014/010257 KR2014010257W WO2015065046A1 WO 2015065046 A1 WO2015065046 A1 WO 2015065046A1 KR 2014010257 W KR2014010257 W KR 2014010257W WO 2015065046 A1 WO2015065046 A1 WO 2015065046A1
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Definitions
- the present invention relates to a method for producing a cathode active material, and a cathode active material for a lithium secondary battery produced thereby.
- Lithium secondary batteries have been widely used as power sources for portable devices since they emerged in 1991 as small, light and large capacity batteries. Recently, with the rapid development of electronics, telecommunications, and computer industry, camcorders, mobile phones, notebook PCs, etc. have emerged and are developing remarkably, and the demand for lithium secondary battery is increasing day by day as a power source to drive these portable electronic information communication devices. Doing.
- Lithium secondary batteries have a problem in that their lifespan drops rapidly as they are repeatedly charged and discharged. In particular, this problem is more serious at high temperatures. This is due to the phenomenon that the electrolyte is decomposed or the active material is deteriorated due to moisture or other effects in the battery, and the internal resistance of the battery is increased.
- the first technical problem to be solved of the present invention is to provide a method for producing a positive electrode active material that can convert the lithium impurities present on the lithium transition metal oxide to structurally stable boron lithium oxide by heat treatment using a boron-containing compound.
- the second technical problem to be solved of the present invention is to provide a cathode active material including a coating layer containing boron lithium oxide on the surface of the lithium transition metal oxide by the method of manufacturing the cathode active material.
- the third technical problem to be solved of the present invention is to provide a positive electrode and a lithium secondary battery including the positive electrode active material.
- the present invention provides a method for producing a positive electrode active material comprising the step of dry mixing and heat treatment of the lithium transition metal oxide and boron-containing compounds to coat the lithium transition metal oxide surface with boron lithium oxide.
- the present invention is a lithium transition metal oxide; And it provides a cathode active material comprising a coating layer comprising a boron lithium oxide on the surface of the lithium transition metal oxide.
- the present invention provides a positive electrode including the positive electrode active material.
- the present invention provides a lithium secondary battery including the positive electrode.
- lithium impurities present on the lithium transition metal oxide can be easily converted into structurally stable boron lithium oxide.
- a coating layer in which boron lithium oxide is uniformly coated on the surface of the lithium transition metal oxide may be formed in an amount proportional to the amount of the boron-containing compound used.
- FIG. 1 is a schematic view of a method of manufacturing a positive electrode active material according to an embodiment of the present invention.
- Figure 2 is a graph showing the pH titration (titration) results for determining the amount of lithium impurities of the positive electrode active material prepared in Example 1, and Comparative Examples 1 and 2 of the present invention.
- FIG. 3 is a graph showing results of measuring capacity characteristics after high temperature storage (60 ° C.) of the lithium secondary batteries of Example 5 and Comparative Example 4, according to Experimental Example 3.
- FIG. 3 is a graph showing results of measuring capacity characteristics after high temperature storage (60 ° C.) of the lithium secondary batteries of Example 5 and Comparative Example 4, according to Experimental Example 3.
- FIG. 4 is a graph showing results of measuring high temperature (45 ° C) cycle characteristics of the lithium secondary batteries of Example 5 and Comparative Example 4 according to Experimental Example 4.
- FIG. 4 is a graph showing results of measuring high temperature (45 ° C) cycle characteristics of the lithium secondary batteries of Example 5 and Comparative Example 4 according to Experimental Example 4.
- a method of manufacturing a cathode active material dry mixing and heat treating a lithium transition metal oxide and a boron-containing compound to coat the lithium transition metal oxide surface with boron lithium oxide. It may include.
- a lithium transition metal oxide and a boron-containing compound are dry mixed and heat-treated, in particular, in the vicinity of the melting point of the boron-containing compound, thereby being present on the lithium transition metal oxide.
- the lithium impurity can be easily converted into structurally stable boron lithium oxide.
- a coating layer in which boron lithium oxide is uniformly coated on the surface of the lithium transition metal oxide may be formed in an amount proportional to the amount of the boron-containing compound used.
- the boron-containing compound is H 3 BO 3 , B 2 O 3 , C 6 H 5 B (OH) 2 , (C 6 H 5 O) 3 B , [CH 3 (CH 2 ) 3 O] 3 B, C 13 H 19 BO 3 , C 3 H 9 B 3 O 6 and (C 3 H 7 O) 3 B, or any one selected from the group 2 It may be a mixture of species or more.
- the method of forming a coating layer on the surface of the lithium transition metal oxide generally includes a dry mixing method and a wet mixing method.
- a dry mixing method In the case of using the wet mixing method, there is an advantage that the coating layer formed on the surface of the lithium transition metal oxide can be more uniformly obtained.
- the boron-containing compound should be used in an aqueous solution, in which case the damage may occur to the lithium transition metal oxide due to the aqueous solution.
- the boron-containing compound is dry mixed with a lithium transition metal to perform a heat treatment near the melting point of the boron-containing compound, thereby melting the boron-containing compound
- the advantages of the wet mixing method that is, a uniform coating layer, without causing damage to the lithium transition metal oxide, which is a problem of the wet mixing method.
- H 3 BO 3 begins to melt while softening at a low temperature, for example, a temperature range of about 130 °C to 160 °C.
- the boron-containing compound is melted and flows by the heat treatment to react with at least some of the lithium impurities present on the lithium transition metal oxide, thereby easily converting the boron-containing compound into boron lithium oxide and coating the lithium metal oxide surface.
- the lithium impurities present in the lithium transition metal oxide may be reduced by the conversion of the lithium impurities into the boron lithium oxide.
- the heat treatment is performed at 130 ° C. to 300 ° C., preferably 130 ° C. to 200 ° C., which is near the melting point of the boron-containing compound. May be performed for a time.
- the heat treatment temperature is less than 130 ° C.
- the boron-containing compound is not sufficiently melted, and thus, the boron-containing compound remains on the lithium transition metal oxide, or even when converted to boron lithium oxide, a uniform coating layer cannot be formed and exceeds 300 ° C. Due to the high temperature, the reaction is too fast to form a uniform coating layer on the surface of the lithium transition metal oxide.
- a coating layer in which the boron lithium oxide is uniformly coated on the surface of the lithium transition metal oxide in an amount proportional to the amount of the boron-containing compound can be formed.
- the dry mixing method may be performed using a mortar grinder mixing method and a mixing method using a mechanical milling method, and preferably a mechanical milling method. It may be desirable to use a uniform coating layer formation.
- the lithium transition metal oxide and the boron-containing compound may be uniformly mixed using mortar, and then heat-treated at the heat treatment temperature range.
- the mechanical milling method is, for example, roll mill (ball-mill), ball mill (ball-mill), high energy ball mill (high energy ball mill), planetary mill (planetary mill), stirred ball mill (stirred ball mill, Using a vibrating mill or a jet-mill, the lithium transition metal oxide and the boron-containing compound may be mixed by mechanical friction, for example, by rotating at a rotational speed of 100 rpm to 1500 rpm Compressive stress can be applied.
- the mixture may be heat treated at the temperature range, or the mixing and heat treatment are simultaneously performed in the milling apparatus. can do.
- the amount of the boron-containing compound is 0.05 to 1% by weight, preferably 0.1 to 0.8% by weight based on the total weight of the lithium transition metal oxide. It may be the amount of.
- the content of element B included in the coating layer of the positive electrode active material may increase.
- some element B of the boron lithium oxide is doped into the lithium transition metal oxide, and the content of B decreases from the surface of the lithium transition metal oxide toward the inside. It can have a concentration gradient.
- the present invention is a lithium transition metal oxide; And it provides a positive electrode active material comprising a coating layer containing a boron lithium oxide on the surface of the lithium transition metal oxide.
- the coating layer may contain element B in an amount of 100 ppm to 2000 ppm, preferably 250 ppm to 1100 ppm.
- the boron lithium oxide contained in the coating layer is an amount of 0.05% to 1% by weight, preferably 0.1% to 0.8% by weight relative to the total weight of the positive electrode active material. It may be included as.
- the coating layer formed on the surface of the lithium transition metal oxide becomes thin, the effect of suppressing side reactions between the electrolyte during charging and discharging may be insignificant, and when it exceeds 1% by weight, lithium boron Due to the excessive content of the oxide, the thickness of the coating layer is thickened, thereby increasing resistance, which may cause deterioration of the electrochemical properties of the lithium secondary battery.
- the boron lithium oxide may be LiBO 2 , Li 2 B 4 O 7 , or a mixture thereof.
- the thickness of the coating layer may be 10 nm to 1000 nm.
- the lithium transition metal oxide may be a lithium transition metal oxide that is commonly used, for example lithium-cobalt oxide, lithium-manganese oxide, lithium- It may be any one selected from the group consisting of nickel-manganese oxide, lithium-manganese-cobalt oxide and lithium-nickel-manganese-cobalt oxide, or a mixture of two or more thereof.
- a lithium transition metal oxide having a layered structure having high capacity characteristics is preferable, and may be represented by the following Chemical Formula 1:
- M is any one selected from the group consisting of Al, Zr, Zn, Ti, Mg, Ga and In, or two or more elements thereof;
- the lithium impurity that may be present on the surface of the lithium transition metal oxide may include at least one of LiOH and Li 2 CO 3 .
- the lithium impurity may be included in the lithium transition metal oxide, for example, in the form of Formula 2:
- the lithium impurities present on the lithium transition metal oxide may be 0.1 wt% to 0.6 wt% based on the total weight of the lithium transition metal oxide.
- At least some of the lithium impurities on the lithium transition metal oxide react and are converted to the boron lithium oxide so that the amount of lithium impurities is about 30% to 70% compared to before the conversion to the boron lithium oxide, preferably Preferably 40% to 70%.
- the amount of lithium impurities present in the cathode active material according to the present invention is preferably present in less than 0.3% by weight relative to the total weight of the cathode active material.
- Lithium impurities such as LiOH or Li 2 CO 3 have a high reactivity with the electrolyte, so when the amount of lithium impurities present on the surface of the lithium transition metal oxide is 0.3% by weight or more, excessive swelling may occur. Because there is.
- some elements B of the boron lithium oxide may be further doped into the lithium transition metal oxide.
- the lithium transition metal oxide is represented by the following Chemical Formula 3,
- M is any one selected from the group consisting of Al, Zr, Zn, Ti, Mg, Ga and In, or two or more elements thereof;
- w may have a concentration gradient that decreases toward the inside from the surface of the lithium transition metal oxide.
- the present invention provides a cathode including the cathode active material.
- the present invention provides a cathode including the cathode active material.
- the positive electrode can be prepared by conventional methods known in the art.
- a positive electrode may be prepared by mixing and stirring a solvent, a binder, a conductive agent, and a dispersant in a positive electrode active material, if necessary, and then applying the coating (coating) to a current collector of a metal material, compressing it, and drying the same. have.
- the current collector of the metal material is a metal having high conductivity, and any metal can be used as long as the slurry of the positive electrode active material is a metal that can be easily adhered.
- Non-limiting examples of the positive electrode current collector include a foil made of aluminum, nickel, or a combination thereof.
- the solvent for forming the positive electrode includes an organic solvent such as NMP (N-methyl pyrrolidone), DMF (dimethyl formamide), acetone, dimethyl acetamide or water, and these solvents alone or in combination of two or more. Can be mixed and used. The amount of the solvent used is sufficient to dissolve and disperse the positive electrode active material, the binder, and the conductive agent in consideration of the coating thickness of the slurry and the production yield.
- NMP N-methyl pyrrolidone
- DMF dimethyl formamide
- acetone dimethyl acetamide or water
- the binder may be polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (polyvinylidenefluoride), polyacrylonitrile, polymethylmethacrylate, Polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), Sulfonated EPDM, styrene butadiene rubber (SBR), fluorine rubber, poly acrylic acid and polymers in which hydrogen thereof is replaced with Li, Na or Ca, or the like, or Various kinds of binder polymers such as various copolymers can be used.
- PVDF-co-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
- the conductive agent is not particularly limited as long as it has conductivity without causing chemical change in the battery.
- Examples of the conductive agent include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, farnes black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Conductive tubes such as carbon nanotubes; Metal powders such as fluorocarbon, aluminum and nickel powders; Conductive whiskers 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.
- the present invention provides a lithium secondary battery including a separator interposed between the positive electrode, the negative electrode, the positive electrode and the negative electrode.
- a carbon material, lithium metal, silicon, tin, or the like, in which lithium ions may be occluded and released may be used.
- the negative electrode current collector is generally made to a thickness of 3 ⁇ m to 500 ⁇ m.
- a negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
- the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like, aluminum-cadmium alloy, and the like can be used.
- the binder and the conductive agent used in the negative electrode can be used as can be commonly used in the art as the positive electrode.
- the negative electrode may prepare a negative electrode by mixing and stirring the negative electrode active material and the additives to prepare a negative electrode active material composition, and then applying the same to a current collector and compressing the negative electrode.
- the separator is interposed between the cathode and the anode, and an insulating thin film having high ion permeability and mechanical strength may be used, and since it is known in the art, a detailed description thereof will be omitted herein.
- the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be cylindrical, square, pouch type, or coin type using a can.
- the lithium secondary battery according to the present invention may not only be used in a battery cell used as a power source for a small device, but also preferably used as a unit battery in a medium-large battery module including a plurality of battery cells.
- Preferred examples of the medium-to-large device include, but are not limited to, electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, and electric power storage systems.
- MOOH Ni 0.78 Mn 0.11 Co 0.11
- Li 2 CO 3 Li 2 CO 3
- LiNi 0.78 Mn 0.11 Co 0.11 O 2 and H 3 BO 3 were quantified in a weight ratio of 100: 0.17, and mixed with a dry mixer (CYCLOMIX, HOSOKAWA Micron Coorporation) to obtain a mixed powder.
- the obtained powder was heat-treated at 150 ° C. for 5 hours in an oxygen atmosphere.
- the positive electrode active material containing LiBO 2 and Li 2 B 4 O 7 on the surface of LiNi 0.78 Mn 0.11 Co 0.11 O 2 was obtained by the above method.
- the thickness of the coating layer was 150 nm.
- a positive electrode active material was manufactured in the same manner as in Example 1, except that LiNi 0.78 Mn 0.11 Co 0.11 O 2 and H 3 BO 3 were used in a weight ratio of 100: 0.34.
- the thickness of the coating layer was 230 nm.
- a positive electrode active material was manufactured in the same manner as in Example 1, except that LiNi 0.78 Mn 0.11 Co 0.11 O 2 and H 3 BO 3 were used in a weight ratio of 100: 0.68.
- the thickness of the coating layer was 300 nm.
- a positive electrode active material was manufactured in the same manner as in Example 1, except that LiNi 0.78 Mn 0.11 Co 0.11 O 2 and H 3 BO 3 were used in a weight ratio of 100: 0.09, and the heat treatment was not performed.
- the thickness of the coating layer was 100 nm.
- a positive electrode active material was manufactured in the same manner as in Comparative Example 1, except that LiNi 0.78 Mn 0.11 Co 0.11 O 2 and H 3 BO 3 were used in a weight ratio of 100: 0.17.
- the thickness of the coating layer was 150 nm.
- a positive electrode active material was manufactured in the same manner as in Comparative Example 1, except that LiNi 0.78 Mn 0.11 Co 0.11 O 2 and H 3 BO 3 were used in a weight ratio of 100: 0.34.
- the thickness of the coating layer was 160 nm.
- a cathode active material including a coating layer containing LiBO 2 and Li 2 B 4 O 7 on the surface of LiNi 0.78 Mn 0.11 Co 0.11 O 2 prepared in Example 1 was used.
- a positive electrode mixture slurry was prepared.
- the positive electrode mixture slurry was applied to a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of about 20 ⁇ m, dried to prepare a positive electrode, and then subjected to roll press to prepare a positive electrode.
- Al aluminum
- a negative electrode active material slurry 96.3% by weight of carbon powder as a negative electrode active material, 1.0% by weight of super-p as a conductive material, and 1.5% by weight and 1.2% by weight of styrene butadiene rubber (SBR) and carboxymethylcellulose (CMC) as a binder were added to NMP as a solvent.
- SBR styrene butadiene rubber
- CMC carboxymethylcellulose
- LiPF 6 was added to a nonaqueous electrolyte solvent prepared by mixing ethylene carbonate and diethyl carbonate in a volume ratio of 30:70 as an electrolyte to prepare a 1 M LiPF 6 nonaqueous electrolyte.
- the positive electrode and the negative electrode thus prepared were interposed with a mixed separator of polyethylene and polypropylene, followed by fabrication of a polymer battery in a conventional manner, followed by pouring the prepared non-aqueous electrolyte to complete the production of a lithium secondary battery.
- a lithium secondary battery was manufactured in the same manner as in Example 4, except that each cathode active material prepared in Examples 2 and 3 was used.
- a lithium secondary battery was manufactured in the same manner as in Example 4, except that each cathode active material prepared in Comparative Examples 1 to 3 was used.
- ICPAES Inductively Coupled Plasma-Atomic Emission Spectroscometer
- ICP-AES (ICP 5300DV, Perkinelemer) was operated under the following conditions: Forward Power 1300 W; Torch Height 15 mm; Plasma gas flow 15.00 L / min; Sample gas flow 0.8 L / min; Assist gas flow 0.20 L / min and pump speed 1.5 mL / min.
- Forward Power 1300 W
- Torch Height 15 mm
- Plasma gas flow 15.00 L / min
- Sample gas flow 0.8 L / min
- Assist gas flow 0.20 L / min
- pump speed 1.5 mL / min the content of the element B included in the coating layer of the positive electrode active material prepared in Examples 1 to 3, and Comparative Examples 1 to 3 is shown in Table 1 below.
- the amount of H 3 BO 3 the positive electrode active material according to the use of the 0.17% to 0.68% by weight
- the content of element B included also increased from 275 ppm to 1110 ppm similarly to the theoretical value.
- PH titration was performed to determine the amount of lithium impurities for the positive electrode active materials prepared in Example 1 and Comparative Examples 1 and 2, and the results are shown in FIG. 2.
- a pH meter metrohm 794 was used and the pH was recorded by titration of 0.02 ml.
- FIG. 2 is a graph comparing the amount of reduction of the lithium impurities with respect to each of the positive electrode active materials of Example 1 and Comparative Examples 1 and 2.
- FIG. 2 is a graph comparing the amount of reduction of the lithium impurities with respect to each of the positive electrode active materials of Example 1 and Comparative Examples 1 and 2.
- Example 1 is about 11.6 ml
- Comparative Example 1 is 15ml
- Comparative Example 2 is about 14.2 ml
- Example 1 is reduced by about 20% or more compared to Comparative Examples 1 and 2.
- FIG. 3 is a graph showing results of measuring capacity characteristics after high temperature storage (60 ° C.) of the lithium secondary batteries of Example 5 and Comparative Example 4, according to Experimental Example 3.
- FIG. 3 is a graph showing results of measuring capacity characteristics after high temperature storage (60 ° C.) of the lithium secondary batteries of Example 5 and Comparative Example 4, according to Experimental Example 3.
- Example 5 the positive electrode active material of Example 2
- Comparative Example 4 the positive electrode active material of Comparative Example 1
- the slope of the capacity retention rate of the lithium secondary battery of Example 5 of the present invention was slower than that of the lithium secondary battery of Comparative Example 4 until the storage period of 4 weeks. Specifically, it can be seen that the lithium secondary battery of Example 5 of the present invention is increased by about 3% in 4 weeks of storage period compared to the lithium secondary battery of Comparative Example 4.
- the lithium secondary battery of Example 5 is about 25% reduced compared to the lithium secondary battery of Comparative Example 4. It can be seen that the decrease in storage growth rate of about 25% may also affect the output characteristics. That is, it can be seen that excellent output characteristics can be exhibited as the resistance increase rate of the lithium secondary battery of Example 5 decreases.
- Example 5 The lithium secondary batteries of Example 5 and Comparative Example 4 were charged at 1C to 4.15V / 30mA at constant current / constant voltage (CC / CV) conditions at 45 ° C, and then discharged at 2C to 2.5V under constant current (CC) conditions, The discharge capacity was measured. This was repeated 1 to 400 cycles, the measured discharge capacity is shown in FIG.
- the slope of the capacity retention rate of the lithium secondary battery of Example 5 of the present invention was similar to that of the lithium secondary battery of Comparative Example 4 until 400 cycles.
- the lithium secondary battery of Example 5 is reduced by about 7% in 400 cycles compared to the lithium secondary battery of Comparative Example 4. It can be seen that the decrease in storage growth rate can also affect the output characteristics. That is, it can be seen that excellent output characteristics can be exhibited as the resistance increase rate of the lithium secondary battery of Example 5 decreases.
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Abstract
Description
예 | H3BO3 사용량(중량%) | B 함량(ICP) | |
B(실험치, ppm) | B(이론치, ppm) | ||
실시예 1 | 0.17 | 275 | 290 |
실시예 2 | 0.34 | 575 | 585 |
실시예 3 | 0.68 | 1110 | 1170 |
비교예 1 | 0.09 | 145 | 145 |
비교예 2 | 0.17 | 290 | 290 |
비교예 3 | 0.34 | 290 | 585 |
Claims (22)
- 리튬 전이금속 산화물 및 보론 함유 화합물을 건식 혼합하고 열처리하여 리튬 전이금속 산화물 표면을 붕소 리튬 산화물로 코팅하는 단계를 포함하는 양극 활물질의 제조방법.
- 제 1 항에 있어서,상기 열처리는 130 ℃ 내지 300 ℃의 온도 범위에서 수행되는 것을 특징으로 하는 양극 활물질의 제조방법.
- 제 2 항에 있어서,상기 열처리는 130 ℃ 내지 200 ℃의 온도 범위에서 수행되는 것을 특징으로 하는 양극 활물질의 제조방법.
- 제 2 항에 있어서,상기 열처리에 의해 보론 함유 화합물이 상기 리튬 전이금속 산화물 상의 리튬 불순물 중 적어도 일부와 반응하여 붕소 리튬 산화물로 전환되는 것을 특징으로 하는 양극 활물질의 제조방법.
- 제 2 항에 있어서,상기 열처리에 의해 붕소 리튬 산화물 중 일부 원소 B가 리튬 전이금속 산화물의 내부에 도핑되고, 상기 B의 함량은 상기 리튬 전이금속 산화물의 표면에서 내부로 갈수록 감소하는 농도구배를 갖는 것을 특징으로 하는 양극 활물질의 제조방법.
- 제 4 항에 있어서,상기 리튬 불순물은 LiOH, Li2CO3 또는 이들의 혼합물인 것을 특징으로 하는 양극 활물질의 제조방법.
- 제 1 항에 있어서,상기 혼합은 몰타르 그라인더 혼합(mortar grinder mixing)법 또는 기계적 밀링법에 의해 수행되는 것을 특징으로 하는 양극 활물질의 제조방법.
- 제 7 항에 있어서,상기 기계적 밀링법에 의한 혼합은 롤밀 (roll-mill), 볼밀 (ball-mill), 고에너지 볼밀(high energy ball mill), 유성 밀(planetary mill), 교반 볼밀(stirred ball mill), 진동밀(vibrating mill) 또는 제트 밀 (jet-mill)을 이용하여 수행되는 것을 특징으로 하는 양극 활물질의 제조방법.
- 제 1 항에 있어서,상기 보론 함유 화합물은 H3BO3, B2O3, C6H5B(OH)2, (C6H5O)3B, [CH3(CH2)3O]3B, C13H19BO3, C3H9B3O6 및 (C3H7O)3B로 이루어진 군으로부터 선택된 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 양극 활물질의 제조방법.
- 제 1 항에 있어서,상기 보론 함유 화합물은 상기 리튬 전이금속 산화물 총 중량에 대해 0.05 중량% 내지 1 중량%의 양으로 사용되는 것을 특징으로 하는 양극 활물질의 제조방법.
- 제 1 항에 있어서,상기 붕소 리튬 산화물은 LiBO2, Li2B4O7, 또는 이들의 혼합물인 것을 특징으로 하는 양극 활물질의 제조방법.
- 제 1 항에 있어서,리튬 전이금속 산화물은 하기 화학식 1로 표시되는 것을 특징으로 하는 양극 활물질의 제조방법:<화학식 1>Li1+a[NixMnyCozMv]O2-cAc상기 식에서, M은 Al, Zr, Zn, Ti, Mg, Ga 및 In으로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 원소이고; A는 P, F, S 및 N로 이루어진 군에서 선택되는 1종 이상이며, 0≤x≤1.0, 0≤y<0.6, 0≤z<0.6, 0≤v≤0.1, 0≤a<0.3, 0≤c≤0.2, a+x+y+z+v=1이다.
- 리튬 전이금속 산화물; 및상기 리튬 전이금속 산화물의 표면에 붕소 리튬 산화물을 포함하는 코팅층을 포함하는 것을 특징으로 하는 양극 활물질.
- 제 13 항에 있어서,상기 코팅층은 원소 B를 100 ppm 내지 2000 ppm의 양으로 포함하는 것을 특징으로 하는 양극 활물질.
- 제 13 항에 있어서,상기 코팅층은 원소 B를 250 ppm 내지 1100 ppm의 양으로 포함하는 것을 특징으로 하는 양극 활물질.
- 제 13 항에 있어서,상기 코팅층의 두께는 10 nm 내지 1000 nm인 것을 특징으로 하는 양극 활물질.
- 제 13 항에 있어서,상기 리튬 전이금속 산화물의 내부에 붕소 리튬 산화물의 일부 원소 B가 더 포함되는 것을 특징으로 하는 양극 활물질.
- 제 17 항에 있어서,상기 리튬 전이금속 산화물은 하기 화학식 3으로 표시되고, 하기 화학식 3에서 w는 리튬 전이금속 산화물의 표면에서 내부로 갈수록 감소하는 농도구배를 갖는 것을 특징으로 하는 양극 활물질:<화학식 3>Li1+a[NixMnyCozBwMv]O2-cAc상기 식에서, M은 Al, Zr, Zn, Ti, Mg, Ga 및 In으로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 원소이고; A는 P, F, S 및 N로 이루어진 군에서 선택되는 1종 이상이며, 0≤x≤1.0, 0≤y<0.6, 0≤z<0.6, 0≤v≤0.1, 0≤a<0.3, 0≤c≤0.2, a+x+y+z+v=1, 0≤w≤0.1이다.
- 제 13 항에 있어서,상기 양극 활물질은 리튬 불순물을 양극 활물질 총 중량 대비 0.3 중량% 미만으로 포함하는 것을 특징으로 하는 양극 활물질.
- 제 13 항에 있어서,상기 붕소 리튬 산화물은 LiBO2, Li2B4O7, 또는 이들의 혼합물인 것을 특징으로 하는 양극 활물질.
- 제 13 항의 양극 활물질을 포함하는 것을 특징으로 하는 양극.
- 제 21 항의 양극을 포함하는 것을 특징으로 하는 리튬 이차전지.
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TWI609519B (zh) | 2017-12-21 |
US10529985B2 (en) | 2020-01-07 |
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CN104781960A (zh) | 2015-07-15 |
EP3065207A4 (en) | 2016-10-26 |
EP3065207A1 (en) | 2016-09-07 |
JP2015536558A (ja) | 2015-12-21 |
KR101651338B1 (ko) | 2016-08-25 |
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