WO2021066229A1 - 리튬 이차 전지용 양극 활물질, 및 이를 포함하는 리튬 이차 전지 - Google Patents
리튬 이차 전지용 양극 활물질, 및 이를 포함하는 리튬 이차 전지 Download PDFInfo
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- WO2021066229A1 WO2021066229A1 PCT/KR2019/012962 KR2019012962W WO2021066229A1 WO 2021066229 A1 WO2021066229 A1 WO 2021066229A1 KR 2019012962 W KR2019012962 W KR 2019012962W WO 2021066229 A1 WO2021066229 A1 WO 2021066229A1
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- secondary battery
- active material
- lithium secondary
- positive electrode
- electrode active
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000006182 cathode active material Substances 0.000 title abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 32
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010937 tungsten Substances 0.000 claims abstract description 29
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 claims description 44
- 239000011164 primary particle Substances 0.000 claims description 32
- 229910052796 boron Inorganic materials 0.000 claims description 31
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 28
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 18
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Images
Classifications
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- H—ELECTRICITY
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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M10/052—Li-accumulators
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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- H—ELECTRICITY
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H—ELECTRICITY
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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
Definitions
- the present embodiment relates to a positive electrode active material for a lithium secondary battery, and a lithium secondary battery including the same.
- Lithium secondary batteries are manufactured in the form of high-performance small-sized batteries and are used as energy storage sources for mobile information and communication devices including smart phones, notebook computers, and computers. (Electric Vehicle), hybrid electric vehicle (Hybrid Electric Vehicle) research is also being conducted.
- a secondary battery having excellent charge/discharge characteristics, life characteristics, high rate characteristics, “G stability at high temperature, etc.” is required.
- a lithium secondary battery basically a high voltage is required. And because it has a high energy density, it satisfies the above requirements, but there are still problems that must be determined before being applied to a large field.
- a positive electrode active material among the main constituent elements of a lithium secondary battery has a higher production cost than other elements, and currently, a positive electrode active material mainly commercially available includes LiCoO 2 and the like.
- NCM which can be high-capacity as a cathode material to replace LCO
- LCO low-capacity carbonate
- Mn and Co the content of Mn and Co
- the safety and output characteristics are deteriorated, and the capacity deterioration proceeds relatively quickly. Attempts have been made to solve this problem through doping and coating processes of various elements.
- the present invention is to compensate the problem of life characteristics of the high-capacity cathode material High Nickel NCM. More specifically, it is intended to maintain a long life by maintaining the discharge capacity and rate characteristics and improving the capacity reduction problem of the life characteristics.
- it is in the form of secondary particles made of primary particles, and the primary particles have a rough surface structure, providing a positive electrode active material for a lithium secondary battery.
- the specific surface area of the secondary particles may be 0.19 m 2 /g or less. More specifically, it may be greater than 0 and less than or equal to 0.19 m 2 /g.
- the primary particle may have a grain size of 100 to 500 nm. More specifically, it may be 200 to 400nm.
- the primary particles may include both primary particles having a layered structure and primary particles having a Rocksalt structure.
- the positive active material for a lithium secondary battery may be a lithium metal oxide, and may be doped with tungsten (W) and boron (B).
- the positive electrode active material for a lithium secondary battery is a lithium metal oxide, and has a structure doped with tungsten (W) and boron (B), and, based on 1 mol% of metal in the lithium metal oxide, tungsten (W) is 0.0005 to 0.005 mol% Doped, boron (B) may be doped 0.0005 to 0.005 mol%.
- the positive electrode active material for a rechargeable lithium battery may be represented by Formula 1 below.
- the positive electrode active material for a lithium secondary battery is a lithium metal oxide, has a structure doped with tungsten (W) and boron (B), and the boron (B) is doped on the surface in the form of B 2 O 3 , and the tungsten (W ) Doped on the surface in the form of WO 3 , and may be doped inside in the form of WO 2.
- a positive electrode active material for a lithium secondary battery which is a lithium metal oxide and is doped with tungsten (W) and boron (B).
- the positive electrode active material for a lithium secondary battery is a lithium metal oxide, and has a structure doped with tungsten (W) and boron (B), and, based on 1 mol% of metal in the lithium metal oxide, tungsten (W) is 0.0005 to 0.005 mol% Doped, boron (B) may be doped 0.0005 to 0.005 mol%.
- the anode; cathode; And an electrolyte wherein the positive electrode provides a lithium secondary battery including the positive electrode active material for a lithium secondary battery according to an embodiment of the present invention.
- 2A and 2B are results of XRD and XPS analysis after synthesis of the cathode material.
- 3A and 3B are initial charge/discharge curves and C-rate evaluation results during electrochemical evaluation.
- 4A and 4B are results of evaluation of room temperature/high temperature life characteristics during electrochemical evaluation.
- 5A and 5B are results of cyclic voltage scanning and differential capacity curve analysis.
- Figure 8 is the content of morphology analysis through FE-SEM.
- it is in the form of secondary particles made of primary particles, and the primary particles have a rough surface structure, providing a positive electrode active material for a lithium secondary battery.
- the primary particles mean changes in morphology during growth due to the doping effect of tungsten and boron. This will be sufficiently described in the embodiment to be described later.
- the primary particles may have an average grain size of 100 to 500 nm. This is a level showing a reduction rate of about 40-50% through the doping.
- it may have a structure (needle structure) in which an aspect ratio is increased compared to a pristine material that is not doped with tungsten and boron. This allows the primary particles to be formed more densely.
- the voids in the secondary particles may be 10 to 30% by volume or less than that of a Pristine material that is not doped with tungsten and boron.
- the specific surface area of the secondary particles may be 0.19 m 2 /g or less. More specifically, the specific surface area of the secondary particles rather decreases due to the denser primary particles. The decrease in the specific surface area of the secondary particles suppresses side reactions with the electrolyte, thereby improving the life performance and increasing the particle strength.
- the primary particles may include both primary particles having a layered structure and primary particles having a Rocksalt structure. More specifically, the layered structure and the Rocksalt structure may be mixed.
- the positive active material for a lithium secondary battery is a lithium metal oxide, and may be doped with tungsten (W) and boron (B).
- the positive electrode active material for a lithium secondary battery is a lithium metal oxide, has a structure doped with tungsten (W) and boron (B), and, based on 1 mol% of metal in the lithium metal oxide, tungsten (W) is 0.05 to 0.15 mol% Doped, boron (B) may be in the form of 0.05 to 0.15 mol% doped.
- tungsten boride may be used as the doping material, and in this case, tungsten and boron may be doped with the same mole %.
- the positive active material for a lithium secondary battery may be represented by Formula 1 below.
- the positive electrode active material for a lithium secondary battery is a lithium metal oxide, has a structure doped with tungsten (W) and boron (B), and the boron (B) is doped on the surface in the form of B 2 O 3 , and the tungsten (W ) It is doped on the surface in the form of WO 3 , and may be doped inside in the form of WO 2.
- boron is located outside the secondary particles and may substantially suppress the reaction with the electrolyte like a coating layer.
- the anode; cathode; And an electrolyte wherein the positive electrode includes a positive electrode active material for a lithium secondary battery according to any one of the foregoing, and provides a lithium secondary battery.
- the positive electrode includes a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector.
- the positive electrode active material layer includes the positive electrode active material described above, and optionally a binder, a conductive material, or a combination thereof.
- Aluminum may be used as the current collector, but is not limited thereto.
- the binder is, for example, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymer containing ethylene oxide, polyvinyl p Rolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, and the like.
- the conductive material is used to impart conductivity to the electrode, and any electronically conductive material may be used without causing chemical changes in the battery.
- the conductive material include natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powders such as copper, nickel, aluminum, silver, and metal fibers, and conductive materials such as polyphenylene derivatives Can be used alone or in combination of one or more.
- the negative electrode includes a current collector and a negative active material layer formed on the current collector.
- a copper foil, a nickel foil, a stainless steel foil, a titanium foil, a nickel foam, a copper foam, a polymer substrate coated with a conductive metal, or a combination thereof may be used.
- the negative active material layer includes a negative active material, a binder composition, and/or a conductive material.
- the negative active material includes a material capable of reversibly intercalating/deintercalating lithium ions, a lithium metal, an alloy of lithium metal, a material capable of doping and undoping lithium, or a transition metal oxide.
- the electrolyte includes a non-aqueous organic solvent and a lithium salt.
- the non-aqueous organic solvent and the lithium salt may be applied without limitation as long as they are compatible, so a detailed description thereof will be omitted.
- a nickel-based metal hydroxide precursor LiOH as a raw material for lithium, W, and WB (tungsten boride) as a B raw material were dryly mixed.
- Dry mixture A total of 100 g of a mixture was filled in a saggar, and in an oxygen (O 2 ) sintering furnace, the temperature was raised to 740° C. at 2.5° C./min and maintained for 13 hours.
- SPL.1 to SPL.3 are indicated. (WB 1,000ppm-SPL.1, WB 2,000ppm-SPL.2, WB 3,000ppm-SPL.3)
- Tungsten and boron were not added as a comparative example.
- the material thus obtained was pulverized and classified to obtain a positive electrode active material.
- the mass ratio of the positive electrode active material of Examples 1-3 and Comparative Examples, the conductive material (Super-P), and the binder (PVDF) is 96.5:1.5:2 (active material: conductive material: binder) N-methyl-2 pyrrolidone ( NMP) was uniformly mixed in a solvent.
- NMP was evaporated through hot air drying, pressed in a roll press, and vacuum dried in a vacuum oven at 100 to 120° C. for 12 hours to prepare a positive electrode.
- EC ethylene carbonate
- DMC dimethyl carbonate
- the electrochemical evaluation was conducted by sequentially applying a constant current and a constant voltage. Rate characteristic evaluation was measured from 0.1C to 2C, and life characteristic evaluation was measured at room temperature and high temperature up to 30 times at 0.3C and compared. At this time, the increase rate was confirmed by calculating the DC resistance value generated in 10s.
- the degree of shift of the oxidation-reduction peak was measured through the differential capacity curve, and the phase change was observed using a cyclic voltage scanning method that scans a constant voltage per unit time.
- the resistance increase rate according to the cycle progress was compared with the impedance.
- the change of the primary particles was confirmed through FE-SEM, and the specific shape of the primary particles was observed through the low-voltage SEM.
- the surface and internal primary particle shape of the specimen thinly processed with FIB was confirmed by FE-TEM, and the average particle size was compared. In addition, by analyzing the diffraction pattern of each grain, it was confirmed whether the crystal structure was distributed in a specific pattern.
- the internal voids and specific surface areas were confirmed by BET, and the form of the doping element was observed by etching through XPS.
- the sample was mixed at an approximate weight ratio of 1:1 and observed at a heating rate of 10°C per minute from 50°C to 800°C in order to confirm a distinct change.
- TGA analysis can determine the phenomenon at that temperature by weight change occurring in each temperature section.
- WB a doping material
- WB a doping material
- oxides of WO 3 and B 2 O 3 in the range of 550 to 730°C during O 2 firing, and it can be seen that the weight increases.
- the weight decreases after passing the LiOH melting point, and then changes to the oxide form again, and the weight increases.
- the precursor in the form of Me(OH) 2 and WB When the precursor in the form of Me(OH) 2 and WB are mixed, the precursor changes to an oxide form around 250°C, and after a certain amount of weight decreases, the behavior of the graph is similar to that of WB.
- the firing temperature of the precursor was set to 740°C, and it can be expected that WB exists in the form of oxide in the temperature range.
- 2A and 2B are results of XRD and XPS analysis after synthesis of the cathode material.
- the impurity peak was not confirmed by the addition of a small amount of WB, and a typical layered structure pattern was confirmed.
- the XPS was subjected to 1hr, 2hr etching including the surface part to analyze the inside of the particle. Compared with pristine, in SPL.3, element B was identified in the form of B 2 O 3 oxide in trace amounts only on the surface, and element W was identified in the form of WO 3 on the surface and in a complex form such as WO 2 and W-Cl inside. . Through XPS analysis, the expected result from TGA was confirmed.
- 3A and 3B are initial charge/discharge curves and C-rate evaluation results during electrochemical evaluation.
- the evaluation was conducted at room temperature 25°C, and the initial dose was compared to 0.2C.
- the reference capacity was 200mAh/g and the electrode loading density was 16.5mg/cm 2 .
- C-rate was compared relative to the capacity retention rate according to each rate.
- 4A and 4B are results of evaluation of room temperature/high temperature life characteristics during electrochemical evaluation.
- the increment was plotted by measuring the DCR value at 10 seconds of discharge in each cycle.
- 5A is a cyclic voltage scanning analysis result.
- Figure 5b is a differential capacity curve analysis result. More specifically, the differential capacity curve was checked to confirm the degree of phase shift when an overvoltage occurred.
- the reason for the high-capacity expression of the high nickel NCM cathode material is the difference in the oxidation number of Ni ions due to the phase transition of H2 ⁇ H3 expressed above 4.1V.
- the peak of SPL.3 maintains sharply high intensity up to 100 cycles and exists.
- the impedance was measured at 100% SOC in 1 st , 10 th , and 30 th cycles.
- the initial interfacial resistance is similarly confirmed, but it is measured that the increase rate of the resistance (R ct) of SPL.3 decreases as the cycle progresses. This result becomes a factor of maintaining high capacity by WB doping.
- Figure 8 is the content of morphology analysis through FE-SEM.
- the morphology was observed by selecting spherical particles within 15 ⁇ m at the same 5k magnification. It can be seen that the primary particles have changed despite the addition of a trace amount of doping element to the same precursor. Compared to pristine, the primary particles of SPL.3 have a thin shape like needle-like. This part was confirmed in detail through the low voltage SEM.
- the shape of the primary particles was observed as a special shape of the Churros type by the addition of a trace amount of WB doping element.
- the specimen was thinly processed with FIB to observe the cross section of the particles. It can be seen that the primary particles are formed in a thin shape not only on the surface but also on the inner core. Like the BET result, internal voids are relatively more observed in pristine than in SPL.3. As confirmed by XPS, this is the influence of the doping element W, which is also measured inside the particle. It was confirmed that grain growth was suppressed by the addition of a small amount of W doping element, resulting in thinner primary particles as well as dense rearrangement. It was confirmed that the average grain size decreased from 538 ⁇ 64nm (Pristine) to 229 ⁇ 20nm (SPL.3) by the Astm e112 method.
- the present invention is judged not to be the effect of the crystal structure according to the doping element, but the effect of the peculiar morphology.
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Abstract
Description
Claims (11)
- 일차 입자로 이루어진 이차 입자 형태이며,상기 일차 입자는 표면이 거친 구조인 것인 리튬 이차 전지용 양극 활물질.
- 제1항에 있어서,상기 이차 입자의 비표면적은 0.19 m2/g 이하인 것인 리튬 이차 전지용 양극 활물질.
- 제1항에 있어서,상기 일차 입자의 결정립(grain) 크기는 100 내지 500nm인 것인 리튬 이차 전지용 양극 활물질.
- 제1항에 있어서,상기 일차 입자는 layered 구조인 일차 입자 및 Rocksalt 구조인 일차 입자를 모두 포함하는 것인 리튬 이차 전지용 양극 활물질.
- 제1항에 있어서,상기 리튬 이차 전지용 양극 활물질은,리튬 금속 산화물이며, 텅스텐(W) 및 붕소(B)가 도핑된 것인 리튬 이차 전지용 양극 활물질.
- 제1항에 있어서,상기 리튬 이차 전지용 양극 활물질은,리튬 금속 산화물이며, 텅스텐(W) 및 붕소(B)가 도핑된 구조이며,상기 리튬 금속 산화물 내 금속 1몰%에 대해,텅스텐(W)은 0.0005 내지 0.005몰% 도핑되고,붕소(B)는 0.0005 내지 0.005몰% 도핑된 것인 리튬 이차 전지용 양극 활물질.
- 제1항에 있어서,상기 리튬 이차 전지용 양극 활물질은,리튬 금속 산화물이며, 텅스텐(W) 및 붕소(B)가 도핑된 구조이며,상기 붕소(B)는 B2O3 형태로 표면부에 도핑되고,상기 텅스텐(W) WO3 형태로 표면부에 도핑되며, WO2 형태로 내부에 도핑된 것인 리튬 이차 전지용 양극 활물질.
- 리튬 금속 산화물이며, 텅스텐(W) 및 붕소(B)가 도핑된 것인 리튬 이차 전지용 양극 활물질.
- 제9항에 있어서,상기 리튬 이차 전지용 양극 활물질은,리튬 금속 산화물이며, 텅스텐(W) 및 붕소(B)가 도핑된 구조이며,상기 리튬 금속 산화물 내 금속 1몰%에 대해,텅스텐(W)은 0.0005 내지 0.005몰% 도핑되고,붕소(B)는 0.0005 내지 0.005몰% 도핑된 것인 리튬 이차 전지용 양극 활물질.
- 양극;음극; 및전해질;을 포함하며,상기 양극은, 제1항 내지 제10항 중 어느 한 항에 따른 리튬 이차 전지용 양극 활물질을 포함하는 리튬 이차 전지.
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PCT/KR2019/012962 WO2021066229A1 (ko) | 2019-10-02 | 2019-10-02 | 리튬 이차 전지용 양극 활물질, 및 이를 포함하는 리튬 이차 전지 |
EP19947944.5A EP4040542A4 (en) | 2019-10-02 | 2019-10-02 | ACTIVE CATHODE MATERIAL FOR LITHIUM BATTERY AND LITHIUM BATTERY COMPRISING IT |
US17/766,342 US20240055592A1 (en) | 2019-10-02 | 2019-10-02 | Cathode active material for lithium secondary battery, and lithium secondary battery including same |
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