CN105938901B - Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery - Google Patents
Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery Download PDFInfo
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- 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
- H01M4/50—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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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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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Abstract
The invention provides a positive electrode active material for a lithium ion battery, a positive electrode for a lithium ion battery, and a lithium ion battery having excellent battery characteristics. The positive electrode active material for a lithium ion battery comprises a Li-containing transition metal composite oxide and an inorganic ceramic having an average particle diameter of 0.02 to 1 μm and 10 to 1000 wtppm.
Description
Technical Field
The present invention relates to a positive electrode active material for a lithium ion battery, a positive electrode for a lithium ion battery, and a lithium ion battery.
Background
Lithium-containing transition metal oxides are generally used in positive electrode active materials of lithium ion batteries. Specifically, there are lithium cobaltate (LiCoO)2) Lithium nickelate (LiNiO)2) Lithium manganate (LiMn)2O4) For example, a combination of these materials has been advanced for the purpose of improving characteristics (high capacity, cycle characteristics, storage characteristics, internal resistance reduction, rate characteristics) and safety. Lithium ion batteries for large-scale applications such as vehicle-mounted applications and load balancing applications are required to have characteristics different from those of conventional lithium ion batteries for mobile phones and personal computers.
Conventionally, various studies and developments have been made to improve battery characteristics required for such a lithium ion battery. As a means for improving battery characteristics, for example, a material in which large and small particles are mixed while increasing the electrode density of a positive electrode material has been proposed. In this material, the gaps between the large particles of the Li-containing transition metal composite oxide are filled with small particles of the same material.
As such a technique, for example, patent document 1 discloses a positive electrode active material characterized in that the average particle diameter of lithium composite oxide particles is in the range of 0.1 to 50 μm, and 2 or more peaks are present in the particle size distribution of the lithium composite oxide particles. Further, it is described that a positive electrode active material capable of providing a nonaqueous electrolyte secondary battery having excellent initial capacity and capacity retention rate can be obtained.
Patent document 2 discloses a positive electrode active material for a nonaqueous electrolyte secondary battery, which is characterized by constituting lithiumThe particles of the metal composite oxide powder are mainly composed of secondary particles formed by gathering a plurality of primary particles of the lithium metal composite oxide, the secondary particles are spherical or elliptical, and are composed of mixed particles obtained by mixing particles with the particle diameter of less than 1 [ mu ] m at a ratio of 0.5-3.5 volume% in particles with the particle diameter of substantially 1-40 [ mu ] m, the average particle diameter of 5-11 [ mu ] m and the particle diameter distribution of normal distribution, and the specific surface area of the powder is at most 0.3m larger than that of the powder formed by removing the particles with the particle diameter of less than 1 [ mu ] m from the powder2(ii)/g, the tap density of the powder is at most 0.2g/cm, based on the tap density of the powder excluding the particles having a particle diameter of 1 μm or less3. Further, the following is hereby described: when all the powders constituting the positive electrode active material for a nonaqueous electrolyte secondary battery are pulverized, production troubles such as generation of dust are not caused, capacity reduction due to reduction of packing density is not caused, a contact area between an electrolyte solution and the positive electrode active material is increased, and a place where Li ions are diffused is increased, thereby providing a secondary battery capable of realizing high output.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2000-82466
Patent document 2: japanese patent No. 4766840
Disclosure of Invention
However, when a positive electrode active material is produced by mixing Li-containing transition metal composite oxides having a large particle diameter and a small particle diameter, the following problems arise. In general, a Li-containing transition metal composite oxide having a small particle diameter is rapidly deteriorated because the surface-modified portion formed by a reaction of an electrolyte solution or the like under the charge and discharge action has a large area relative to the volume, and thus the charge and discharge characteristics are greatly deteriorated. Therefore, when a positive electrode active material in which a large-particle-diameter Li-containing transition metal composite oxide and a small-particle-diameter Li-containing transition metal composite oxide are mixed is used, the charge/discharge function of the battery may be deteriorated. Further, since the Li-containing transition metal composite oxide having a small particle size changes the electrolyte in the vicinity thereof, the surface activity of the adjacent Li-containing transition metal composite oxide having a large particle size is lowered, and as a result, the charge and discharge characteristics as a whole may be lowered.
In view of such problems, an object of the present invention is to provide a positive electrode active material for a lithium ion battery having excellent battery characteristics.
The present inventors have conducted various studies to solve such problems, and as a result, have found that: by mixing the Li-containing transition metal composite oxide with a predetermined amount of inorganic ceramic as particles having a small particle diameter, a positive electrode active material for a lithium ion battery having excellent battery characteristics can be obtained.
One aspect of the present invention completed based on the above-described findings is a positive electrode active material for a lithium ion battery, which contains a Li-containing transition metal composite oxide and an inorganic ceramic having an average particle diameter of 0.02 to 1 μm and 10 to 1000 wtppm.
In one embodiment of the positive electrode active material for a lithium ion battery of the present invention, the inorganic ceramic is an oxide, nitride, carbide, or a combination thereof of 1 or more elements selected from Al, Si, Mg, Zr, and Y.
In another embodiment of the positive electrode active material for a lithium ion battery according to the present invention, the inorganic ceramic is Al2O3、SiO2、MgO、ZrO2And SiC and YSZ (yttria-stabilized zirconia).
In still another embodiment of the positive electrode active material for a lithium ion battery according to the present invention, the Li-containing transition metal composite oxide has an average particle diameter of 4 to 12 μm.
In still another embodiment of the positive electrode active material for a lithium ion battery according to the present invention, the Li-containing transition metal composite oxide has a composition formula of: li1+xNi1-yMeyO2+zTo indicate.
(in the formula, Me is any one or more of Mn, Co, Al and Mg, x is-0.1 to 0.1, y represents a total composition of metals represented by Me and is 0.1 to 0.5, and z is-0.1 to 0.2.)
Another aspect of the present invention is a positive electrode for a lithium ion battery, which uses the positive electrode active material for a lithium ion battery of the present invention.
Still another aspect of the present invention is a lithium ion battery using the positive electrode for a lithium ion battery of the present invention.
Effects of the invention
According to the present invention, a positive electrode active material for a lithium ion battery having excellent battery characteristics can be provided.
Detailed Description
(constitution of Positive electrode active Material for lithium ion batteries)
The positive electrode active material for a lithium ion battery of the present invention comprises: a Li-containing transition metal composite oxide and an inorganic ceramic having an average particle diameter of 0.02 to 1 μm and 10 to 1000 wtppm. According to this configuration, the inorganic ceramic functions as particles having a small particle diameter, and the Li-containing transition metal composite oxide, which is particles having a large particle diameter, is promoted to be in contact with each other, so that the rate characteristics of a battery using the positive electrode active material are improved. Further, since the Li-containing transition metal composite oxide is not used as the particles having a small particle diameter as in the conventional art, deterioration of the particles having a small particle diameter can be suppressed, and therefore deterioration of the rate characteristics of the battery using the positive electrode active material can be favorably suppressed.
If the average particle size of the inorganic ceramic is less than 0.02 μm, the above-mentioned effect of improving the rate characteristics is poor, and if the average particle size of the inorganic ceramic exceeds 1 μm, the resistance increases, and thus the rate characteristics are degraded. If the content of the inorganic ceramic is less than 10wtppm, the above-described effect of improving the rate characteristics is poor, and if the content of the inorganic ceramic exceeds 1000wtppm, the initial capacity of the battery using the positive electrode active material is reduced. The average particle size of the inorganic ceramic is preferably 0.1 to 1 μm, more preferably 0.3 to 0.9. mu.m. The content of the inorganic ceramic is preferably 50 to 1000wtppm, more preferably 100 to 500 wtppm.
The positive electrode active material for a lithium ion battery of the present invention is preferably an oxide, nitride, carbide, or combination thereof of 1 or more elements selected from Al, Si, Mg, Zr, and Y, and more preferably Al2O3、SiO2、MgO、ZrO2SiC and YSZ(yttria-stabilized zirconia) at least 1 selected from the group.
The positive electrode active material for a lithium ion battery preferably contains a Li transition metal composite oxide and has an average particle diameter of 4 to 12 [ mu ] m. If the average particle diameter of the Li-containing transition metal composite oxide is less than 4 μm, the particle size of the added ceramic particles is relatively larger than the particle size of the Li-containing transition metal composite oxide, and therefore there is a possibility that the added ceramic particles adversely interfere with the effect that the Li-containing transition metal composite oxide comes into contact with each other. Further, if the average particle diameter of the Li-containing transition metal composite oxide exceeds 12 μm, the gaps between the Li-containing transition metal composite oxide particles become large, and a large amount of ceramic particles need to be added to promote the Li-containing transition metal composite oxide particles to contact each other, which may cause a problem of lowering the discharge capacity of the battery. The average particle diameter of the Li-containing transition metal composite oxide is more preferably 4 to 10 μm, and still more preferably 6 to 10 μm.
The positive electrode active material for a lithium ion battery preferably contains a Li transition metal composite oxide and has a composition formula: li1+ xNi1-yMeyO2+zTo indicate.
(in the formula, Me is any one or more of Mn, Co, Al and Mg, x is-0.1 to 0.1, y represents the total composition of metals represented by Me and is 0.1 to 0.5, and z is-0.1 to 0.2.)
The ratio of lithium to all metals in the positive electrode active material for a lithium ion battery is 0.9 to 1.1, which is because: if the ratio is less than 0.9, it is difficult to maintain a stable crystal structure, and if the ratio exceeds 1.1, it may be impossible to secure a high capacity of the battery. Further, the composition of nickel in the positive electrode active material for a lithium ion battery is 0.5 to 0.9, and therefore, the capacity, output, and safety of a lithium ion battery using the positive electrode active material for a lithium ion battery are improved in a well-balanced manner.
(method for producing Positive electrode active Material for lithium ion batteries)
The following is a detailed description of a method for producing a positive electrode active material for a lithium ion battery according to an embodiment of the present invention.
Preparation of Li-containing transition Metal composite oxide powder
First, a metal salt solution is prepared by dissolving nickel nitrate, cobalt nitrate, manganese nitrate, aluminum nitrate, and magnesium nitrate as needed in pure water so that the metal atoms are in a predetermined amount. Then, while stirring, lithium carbonate is added so that the total molar number of lithium and the metal element is 0.9 to 1.1: 1 into pure water, and dropping the above metal salt solution while dispersing the solution to prepare a slurry containing Li, Ni, and optionally Co, Mn, Al, and Mg.
Next, the slurry is spray-dried using, for example, a fine powder dryer having a three-fluid nozzle, to obtain a powder containing Li, Ni, and optionally Co, Mn, Al, and Mg.
Next, when the powder contains 70% to 90% of Ni with respect to the total metal amount, the powder is fired at 880 ℃ for 2 hours using, for example, a roller kiln, then cooled to 700 ℃ over 1 hour, held for 2 hours, and then cooled to room temperature over 3 hours. When the powder contains 50% or more and less than 70% of Ni relative to the total metal content, the powder is fired at 900 ℃ for 2 hours using, for example, a roller kiln, then cooled to 700 ℃ over 1 hour, held for 2 hours, and then cooled to room temperature over 3 hours.
Next, the fired product obtained is pulverized using, for example, a roll mill and a pulverizer, to obtain a Li-containing transition metal composite oxide powder.
Preparation of inorganic ceramic powder
The inorganic ceramic powder is appropriately pulverized by, for example, a jet mill to prepare a material having a predetermined particle size.
Preparation of positive electrode active Material
The positive electrode active material for a lithium ion battery of the present invention can be obtained by adding the inorganic ceramic powder to the powder containing the Li transition metal composite oxide and mixing the mixture using, for example, a ball mill.
(Positive electrode for lithium ion Battery and Structure of lithium ion Battery Using the same)
The positive electrode for a lithium ion battery according to the embodiment of the present invention has a structure in which a positive electrode mixture prepared by mixing the positive electrode active material for a lithium ion battery, a conductive additive, and a binder is provided on one surface or both surfaces of a current collector made of, for example, an aluminum foil or the like. The lithium ion battery according to the embodiment of the present invention includes the positive electrode for a lithium ion battery having such a configuration.
Examples
Hereinafter, examples for better understanding of the present invention and advantages thereof will be provided, but the present invention is not limited to these examples.
Preparation of Li-containing transition Metal composite oxide powder
(examples 1 to 7, 9 to 23, comparative examples 1 to 14, reference examples 1 to 3, and 9)
First, the molar ratios of Ni, Mn, and Co atoms were adjusted to 8: 1: 1 a metal salt solution obtained by dissolving nickel nitrate, manganese nitrate, and cobalt nitrate in pure water. Next, lithium carbonate was stirred so that the molar ratio of the sum of lithium and the above-mentioned metal element became 1.04: 1, the above metal salt solution was added dropwise to a solution obtained by dispersing the above solution in pure water, thereby preparing a slurry containing Li, Ni, Co and Mn. Next, the slurry was spray-dried using a fine powder dryer having a three-fluid nozzle, to obtain a powder containing Li, Ni, Co, and Mn. Subsequently, the powder was heated from room temperature to 880 ℃ for 1 hour using a roller kiln, held for 2 hours, fired, then cooled to 700 ℃ for 1 hour, held for 2 hours, and then cooled to room temperature for 3 hours. Next, the obtained fired material was pulverized using a roll mill and a pulverizer, and the pulverization strength of the pulverizer was adjusted to obtain Li-containing transition metal composite oxide powder a having 3 kinds of particle sizes.
(examples 24 to 25, comparative example 15 and reference example 4)
The preparation is carried out so that the molar ratio of Ni atoms to Mn atoms is 8: 2, a metal salt solution obtained by dissolving nickel nitrate and manganese nitrate in pure water. Next, lithium carbonate was stirred so that the molar ratio of the sum of lithium and the above-mentioned metal elements became 1.02: the method 1 was added to a solution obtained by dispersing the above-mentioned metal salt solution in pure water, and the above-mentioned metal salt solution was added dropwise to prepare a slurry containing Li, Ni and Mn. Next, the slurry was spray-dried using a fine powder dryer having a three-fluid nozzle, to obtain a powder containing Li, Ni, and Mn. Subsequently, the powder was heated from room temperature to 880 ℃ for 1 hour using a roller kiln, held for 2 hours, fired, then cooled to 700 ℃ for 1 hour, held for 2 hours, and then cooled to room temperature for 3 hours. Next, the obtained fired product was pulverized by a roll mill and a pulverizer to obtain Li-containing transition metal composite oxide powder B.
(examples 26 to 27, comparative example 16 and reference example 5)
The preparation is carried out so that the molar ratio of Ni atoms to Co atoms to Al atoms is 8: 1: 1 a metal salt solution obtained by dissolving nickel nitrate, cobalt nitrate, and aluminum nitrate in pure water. Next, lithium carbonate was stirred so that the molar ratio of the sum of lithium and the above-mentioned metal elements became 1.00: the method 1 was added to a solution obtained by dispersing the above-mentioned metal salt solution in pure water, and the above-mentioned metal salt solution was added dropwise to prepare a slurry containing Li, Ni, Co and Al. Next, the slurry was spray-dried using a fine powder dryer having a three-fluid nozzle, to obtain a powder containing Li, Ni, Co, and Al. Subsequently, the powder was heated from room temperature to 880 ℃ for 1 hour using a roller kiln, held for 2 hours, fired, then cooled to 700 ℃ for 1 hour, held for 2 hours, and then cooled to room temperature for 3 hours. Next, the obtained fired product was pulverized by a roll mill and a pulverizer to obtain Li-containing transition metal composite oxide powder C.
(examples 28 to 29, comparative example 17 and reference example 6)
The preparation is carried out so that the molar ratio of Ni atoms to Co atoms to Mg atoms is respectively 8: 1: 1 a metal salt solution obtained by dissolving nickel nitrate, cobalt nitrate, and magnesium nitrate in pure water. Next, lithium carbonate was stirred so that the molar ratio of the sum of lithium and the above-mentioned metal element became 1.04: the method 1 was added to a solution obtained by dispersing purified water, and the above-mentioned metal salt solution was added dropwise to prepare a slurry containing Li, Ni, Co, and Mg. Next, the slurry was spray-dried using a fine powder dryer having a three-fluid nozzle, to obtain a powder containing Li, Ni, Co, and Mg. Subsequently, the powder was heated from room temperature to 880 ℃ for 1 hour using a roller kiln, held for 2 hours, fired, then cooled to 700 ℃ for 1 hour, held for 2 hours, and then cooled to room temperature for 3 hours. Next, the obtained fired product was pulverized by a roll mill and a pulverizer to obtain a Li-containing transition metal composite oxide powder D.
(examples 30 to 31, comparative example 18 and reference example 7)
The molar ratios of Ni, Mn and Co atoms were 5: 3: 2, a metal salt solution obtained by dissolving nickel nitrate, manganese nitrate, and cobalt nitrate in pure water. Next, lithium carbonate was stirred so that the molar ratio of the sum of lithium and the above-mentioned metal element became 1.04: 1, the above metal salt solution was added dropwise to a solution obtained by dispersing the above solution in pure water, thereby preparing a slurry containing Li, Ni, Mn, and Co. Next, the slurry was spray-dried using a fine powder dryer having a three-fluid nozzle, to obtain a powder containing Li, Ni, Mn, and Co. Subsequently, the powder was heated from room temperature to 900 ℃ for 1 hour using a roller kiln, held for 2 hours, fired, then cooled to 700 ℃ for 1 hour, held for 2 hours, and then cooled to room temperature for 3 hours. Next, the obtained fired product was pulverized by a roll mill and a pulverizer to obtain Li-containing transition metal composite oxide powder E.
(examples 32 to 33, comparative example 19 and reference example 8)
The preparation method is that the molar ratio of Ni atoms to Co atoms to Al atoms to Mg atoms is 5: 3: 1: 1 a metal salt solution obtained by dissolving nickel nitrate, cobalt nitrate, aluminum nitrate, and magnesium nitrate in pure water. Next, lithium carbonate was stirred so that the molar ratio of the sum of lithium and the above-mentioned metal element became 1.04: 1, the above metal salt solution was added dropwise to a solution obtained by dispersing the above solution in pure water, thereby preparing a slurry containing Li, Ni, Co, Al, and Mg. Next, the slurry was spray-dried using a fine powder dryer having a three-fluid nozzle, to obtain a powder containing Li, Ni, Co, Al, and Mg. Subsequently, the powder was heated from room temperature to 900 ℃ for 1 hour using a roller kiln, held for 2 hours, fired, then cooled to 700 ℃ for 1 hour, held for 2 hours, and then cooled to room temperature for 3 hours. Next, the obtained fired product was pulverized by a roll mill and a pulverizer to obtain a Li-containing transition metal composite oxide powder F.
Preparation of inorganic ceramic powder
For use in examples, commercially available inorganic ceramic powder was appropriately pulverized by a jet mill to prepare a material having a predetermined particle size. The particle size was measured by a laser diffraction/scattering particle size distribution measuring apparatus (MICROTRAC, manufactured by NIGHOGEN TOYO CO., LTD.), and the particle size at a volume cumulative frequency of 50% in the obtained particle size distribution curve was defined as an average particle size. In addition, Al used in comparative example 32O3The particle size of (B) was smaller than the measurement range of the present apparatus, and thus the particle size was observed by a scanning electron microscope to be about 0.01. mu.m.
Preparation of Li-containing transition Metal composite oxides of Small particle size-
For use in comparative examples, the Li-containing transition metal composite oxide powder pulverized in the above-described pulverizer was further pulverized by a jet pulverizer to prepare a Li-containing transition metal composite oxide having a small particle size for addition in comparative examples.
(evaluation)
Evaluation of Li-containing transition Metal composite oxide composition
The metal content in each Li-containing transition metal composite oxide was measured by an inductively coupled plasma emission spectrometer (ICP-OES), and the composition of each metal was measured. The lithium content was measured by ion chromatography, and the oxygen content was measured by LECO method.
The Li-containing transition metal composite oxide A used in examples 1 to 7 and 9 to 23, comparative examples 1 to 14, and reference examples 1 to 3 and 9 has a composition of Li1.04Ni0.80Mn0.10Co0.10O2.15。
The Li-containing transition metal composite oxide B used in examples 24 to 25, comparative example 15, and reference example 4 had a composition of Li1.02Ni0.80Mn0.20O2.12。
The compositions of the Li-containing transition metal complex oxides C used in examples 26 to 27, comparative example 16, and reference example 5 wereLi1.00Ni0.80Co0.10Al0.10O2.04。
The Li-containing transition metal composite oxide D used in examples 28 to 29, comparative example 17, and reference example 6 had a composition of Li1.04Ni0.80Co0.10Mg0.10O2.07。
The Li-containing transition metal complex oxide E used in examples 30 to 31, comparative example 18, and reference example 7 had a composition of Li1.04Ni0.50Mn0.30Co0.20O2.12。
The Li-containing transition metal complex oxide F used in examples 32 to 33, comparative example 19, and reference example 8 had a composition of Li1.04Ni0.50Co0.30Al0.10Mg0.10O2.16。
Evaluation of the average particle diameter-
The particle size distribution of the large-particle-diameter Li-containing transition metal composite oxide and the particle size distribution of the small-particle-diameter Li-containing transition metal composite oxide (comparative example only) were measured by a laser diffraction/scattering particle size distribution measuring apparatus (MICROTRAC, manufactured by japan electronics corporation), and the particle size at a volume cumulative frequency of the obtained particle size distribution curve was defined as the average particle size.
Preparation of positive electrode active Material
The inorganic ceramic powder (examples and comparative examples) or the Li-containing transition metal composite oxide having a small particle size (comparative example) was added to the powder of the Li-containing transition metal composite oxide, and the mixture was mixed using a ball mill, thereby producing a positive electrode active material for a lithium ion battery.
Evaluation of cell characteristics
96 wt% of a positive electrode active material, 1.6 wt% of PVDF, and 2.4 wt% of carbon black were weighed, PVDF was dissolved in N-methylpyrrolidone, a mixture obtained by mixing the positive electrode active material and carbon black was added to the obtained solution, and the obtained slurry was coated on an Al foil, dried, and pressed to obtain a positive electrode. Li metal is used as the electrode, and 1M-LiPF is used as the electrolyte6A solution obtained by dissolving EC-DMC (1: 1),a 2032 type coin cell for evaluation was produced. In a 25 ℃ thermostat, the charge-discharge voltage range was set to 3.0V to 4.3V, and in all cycles, the charge was performed at 0.1C, the 1 st cycle and the 21 st cycle of the discharge were performed at 0.1C, and the other cycles were performed at 1C. The discharge capacity at 1C in the 2 nd cycle was divided by the discharge capacity at 0.1C in the 1 st cycle to calculate an initial rate characteristic, and the discharge capacity at 1C in the 22 nd cycle was divided by the discharge capacity at 0.1C in the 21 st cycle to calculate a rate characteristic after the 21 st cycle.
The results are shown in tables 1 and 2.
TABLE 1
TABLE 2
(evaluation results)
In tables 1 and 2, the composition of the Li-containing transition metal composite oxide having a large particle size as a matrix was used for the arrangement. Reference examples 1 to 8 are samples having only large particles as a matrix. The characteristics of the positive electrode active material generally vary depending on the composition. For example, the following features are provided: when Ni is large, the capacity is high, but the magnification and the magnification after the cycle are deteriorated.
When the compositions of the Li-containing transition metal composite oxide having a large particle diameter as a matrix are compared, it is found that: by adding the ceramic particles, the capacity of the 1 st cycle does not substantially change, and the magnification after the cycle has elapsed is improved. In addition, it is known that: when small-particle-diameter Li-containing transition metal composite oxide particles of the same composition are added, the magnification of the first time is slightly improved, but the period after the lapse of the cycle is considerably deteriorated as compared with the case where no Li-containing transition metal composite oxide particles are added.
In addition, in examples 1 to 7 and 9 to 33, since the Li-containing transition metal composite oxide and the inorganic ceramic having an average particle diameter of 0.02 to 1 μm and an average particle diameter of 10 to 1000wtppm were contained, the battery characteristics were all good.
In each of comparative examples 1 to 19, the inorganic ceramic particles contained no small particles or the inorganic ceramic particles contained small particles, but the average particle size was 0.02 to 1 μm and was out of the range of 10 to 1000wtppm, and therefore at least one of the battery characteristics was poor.
Claims (4)
1. A positive electrode active material for a lithium ion battery, comprising a Li-containing transition metal composite oxide and an inorganic ceramic having an average particle diameter of 0.35 to 1 μm and 100 to 1000wtppm,
the Li-containing transition metal composite oxide has a composition formula: li1+xNi1-yMeyO2+zTo indicate that the user is not in a normal position,
in the formula, Me is any one or more of Mn, Co, Al and Mg, x is-0.1, y represents the total composition of metals represented by Me and is 0.1-0.5, and z is-0.1-0.2;
the inorganic ceramic is an oxide, nitride, carbide, or combination thereof of 1 or more elements selected from Al, Si, Mg, Zr, Y;
the average particle diameter of the Li-containing transition metal composite oxide is 4-12 μm.
2. The positive electrode active material for a lithium ion battery according to claim 1, wherein the inorganic ceramic is derived from Al2O3、SiO2、MgO、ZrO2And 1 or more selected from the group consisting of SiC and YSZ, wherein the YSZ is yttria-stabilized zirconia.
3. A positive electrode for a lithium ion battery, which uses the positive electrode active material for a lithium ion battery according to claim 1 or 2.
4. A lithium ion battery using the positive electrode for a lithium ion battery according to claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| JP7091608B2 (en) * | 2017-03-22 | 2022-06-28 | 株式会社村田製作所 | Positive electrodes, batteries and their manufacturing methods, battery packs, electronic devices, electric vehicles, power storage devices and power systems |
| KR102327530B1 (en) * | 2018-05-21 | 2021-11-17 | 주식회사 엘지화학 | Positive electrode for secondary battery and secondary battery comprising the same |
| CN108777296A (en) * | 2018-06-04 | 2018-11-09 | 国联汽车动力电池研究院有限责任公司 | A kind of surface is modified nickelic tertiary cathode material and its prepares and its manufactured battery |
| CN109065858B (en) * | 2018-07-25 | 2020-08-04 | 国联汽车动力电池研究院有限责任公司 | Surface modified ternary positive electrode material, preparation method thereof and battery prepared from surface modified ternary positive electrode material |
| KR20220121778A (en) * | 2019-12-26 | 2022-09-01 | 니폰 제온 가부시키가이샤 | A binder composition for a secondary battery, a slurry composition for a secondary battery, and a solid electrolyte-containing layer, and an all-solid secondary battery and a method for manufacturing an all-solid secondary battery |
| CN115425196A (en) * | 2022-08-30 | 2022-12-02 | 山东大学 | Oxide-coated sodium battery positive electrode material and preparation method and application thereof |
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| JP2005276454A (en) * | 2004-03-23 | 2005-10-06 | Sumitomo Metal Mining Co Ltd | Positive electrode active material for lithium-ion secondary battery and its manufacturing method |
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| JP4798964B2 (en) * | 2004-05-28 | 2011-10-19 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
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| JP2009099523A (en) * | 2007-09-27 | 2009-05-07 | Sanyo Electric Co Ltd | Lithium secondary battery |
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| JP5368627B2 (en) * | 2010-12-03 | 2013-12-18 | Ｊｘ日鉱日石金属株式会社 | Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery |
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