• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    positive electrode composition for secondary non-aqueous electrolyte battery and method for producing positive electrode slurry using positive electrode composition. the present invention relates to a positive electrode composition which has improved characteristics of output power and low costs, and is also easily handled by producing a positive electrode, and exhibits improved performance. a positive electrode composition comprising a positive electrode active material composed of a lithium transition metal complex oxide represented by the general formula li ~ 1 + x ~ ni ~ y ~ co ~ z ~ m ~ 1-yzw ~ l ~ w ~ o ~ 2 ~ (where 0 <243> x <243> 0.50, 0.30 <243> y <243> 1.0, 0 <z <243> 0.5, 0 <243> w <243> 0.1, 0.30 <y + z + w <243> 1, m represents at least one type selected from mn and al, and l represents at least one type of an element selected from the group consisting of zy, ti, mg and w), and additive particles composed of acid oxide particles are used for the positive electrode.
    公开号:BR112012032891B1
    申请号:R112012032891
    申请日:2011-06-16
    公开日:2020-01-14
    发明作者:Kinouchi Chika；Sadamasu Hisato；Ooishi Kengo；Kawai Kenta；Yoshida Yasuhiro
    申请人:Nichia Corp；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for COMPOSITION OF POSITIVE ELECTRODE FOR SECONDARY BATTERY OF NON AQUEOUS ELECTROLYTE AND METHOD TO PRODUCE FLUID POSITIVE ELECTRODE PASTE WITH THE USE OF POSITIVE ELECTRODE COMPOSITION.
    BACKGROUND OF THE INVENTION
    FIELD OF THE INVENTION
    The present invention relates to a positive electrode composition for a secondary non-aqueous electrolyte battery, such as a secondary lithium ion battery. In particular, the present invention relates to a positive electrode composition that can improve the output power characteristics of a secondary lithium ion battery, and can also improve the viscosity stability of a positive electrode slurry. The present invention also relates to a method for producing a positive electrode slurry that has improved viscosity stability.
    DESCRIPTION OF RELATED TECHNIQUE
    With progress in the diffusion and miniaturization of mobile devices, such as VTR, mobile phone and notebook computer, a secondary non-aqueous electrolyte battery, such as a secondary lithium ion battery, has then been used recently as a power source. In addition, in order to deal with a recent environmental problem, the secondary non-aqueous electrolyte battery has also attracted special interest as a battery powered by an electric vehicle or the like.
    Generally, it has been widely used as a positive electrode active material for a secondary lithium ion battery, LiCoO 2 (lithium cobalt oxide) which can constitute a class 4 V secondary battery. When LiCoO 2 is used as the positive electrode active material, it is put into practice at a discharge capacity of about 160 mA / g.
    Cobalt as a raw material for LiCoO 2 is a scarce resource and is also unevenly distributed, which leads to high costs and
    2/17 which can cause anxiety about the supply of raw materials.
    In response to these circumstances, LiNiO 2 (lithium nickel oxide) has also been examined. Practically, LiNiO 2 can make a class 4 V secondary battery having a discharge capacity of about 200 mA / g. However, there is a problem with the stability of a crystal structure of a positive electrode active material upon loading and unloading.
    Thus, a study has also been carried out to carry out a discharge capacity at the same level as that of LiCoO 2 at a low cost, as it improves the stability of a crystal structure by replacing LiNiO 2 nickel atoms with other elements. For example, LiNio, 33Co 0 , 33Mno, 330 2 is considered to be more advantageous than LiCoO 2 in terms of costs.
    In addition, LiNio, 5Coo, 2Mno, 3 0 2) has also been proposed, in which costs are reduced by decreasing the proportion of Co and the discharge capacity is improved by increasing the proportion of Ni. However, deterioration in output power characteristics is not generally prevented when the proportion of Co decreases. Thus, a technology has been proposed in which an arrangement of Ni atoms in disorder in a crystal structure is reduced by making Li more excessive than a stoichiometric ratio, thereby compensating for the output power characteristics.
    [Patent Document 1] JP-A-2007-188878 [Patent Document 2] JP-A-2002-075367 [Patent Document 3] JP-A-2000-106174 [Patent Document 4] JP-A-2003 -142101
    By the way, a positive electrode from a secondary non-aqueous electrolyte battery is formed by mixing a positive electrode active material with a binder, such as polyvinylidene fluoride (PVDF) or N-methyl-2-pyrrolidone (NMP), to obtain a positive electrode slurry and when applying a positive electrode slurry to a current collector, such as an aluminum foil. At that moment, when lithium
    3/17 is released from the positive electrode active material, the lithium reacts with the moisture contained in the binder to form lithium hydroxide. The lithium hydroxide then formed reacts with the binder and, thus, the positive electrode slurry is subjected to gelation, which results in unsatisfactory operability and a decrease in yield. This trend becomes noticeable when the proportion of lithium in the positive electrode active material is more excessive than a stoichiometric ratio and, also, the proportion of nickel is high.
    SUMMARY OF THE INVENTION
    Under these circumstances, the present invention was carried out. An object of the present invention is to provide a positive electrode composition that has improved the characteristics of output power and low costs, and is also easily handled by producing a positive electrode and exhibits improved performance.
    In order to achieve the above objective, the present inventors studied intensively and, thus, the present invention was concluded. The present inventors have found that the gelation of a positive electrode slurry can be suppressed by mixing a positive electrode active material composed of a lithium transition metal complex oxide that has a specific composition with particles composed of an acid oxide ( in the course of the present invention, they can also be referred to as additive particles) to obtain the positive electrode composition. It has also been found that the output power characteristics are improved.
    It was also found that gelation is suppressed by producing the positive electrode slurry by obtaining the positive electrode composition in advance and then by dispersing and dissolving it in a dispersion medium, together with a binder, and thus, output power characteristics are improved in a secondary non-aqueous electrolyte battery after coating.
    The positive electrode composition of the present invention comprises an active positive electrode material composed of an oxide of
    4/17 lithium transition metal complex represented by the general formula Lii + x NiyCo z Mi.y. 2 .wLwO 2 (where 0 <x <0.50, 0.30 <y <1.0, 0 <z <0.5, 0 <w <0.1, 0.30 <y + z + w1 , M represents at least one type selected from Mn and Al, and L represents at least one type of an element selected from the group consisting of Zr, Ti, Mg and W), and additive particles composed of acid oxide particles.
    It is preferred that the acid oxide particles are composed of at least one type selected from the group consisting of tungsten oxide, molybdenum oxide, vanadium pentoxide, tin dioxide and boron oxide.
    It is preferred that the content of the acid oxide particles is 5.0 mol% or less expressed in terms of a ratio between a metallic element and / or a semi-metallic element in the relative acid oxide particles and the positive electrode active material .
    The method for producing the positive electrode slurry of the present invention comprises a step of mixing a positive electrode active material composed of a lithium transition metal complex oxide represented by the general formula: Li 1 + x NiyCOzMi.yzwL w O2 ( 0 £ x 0.50, 0.30 <y <1.0, 0 <z <0.5, 0 <w <0.1, 0.30 <y + z + w <1, M represents at least one type selected from Mn and Al, and L represents at least one type of an element selected from the group consisting of Zr, Ti, Mg and W) with additive particles composed of acid oxide particles to obtain the positive electrode composition; and a step of mixing the positive electrode composition, a binder and a dispersion medium to obtain the positive electrode slurry.
    Since the positive electrode composition of the present invention has the aforementioned resources, the positive electrode slurry is not subjected to gelation by producing a positive electrode and, thus, operability is improved and an throughput increases. The use of the positive electrode active material of the present invention in the positive electrode makes it possible to produce a secondary battery of aqueous electrolyte that has improved output power characteristics at low cost.
    5/17
    Since the method for producing the positive electrode slurry of the present invention has the aforementioned resources, gelation upon production is suppressed and the yield increases. In addition, the output power characteristics of the secondary non-aqueous electrolyte battery produced by coating the positive electrode slurry are improved.
    Without adhering to any specific theory, a relationship between the constitution and the aforementioned effects is generally estimated as follows. That is, lithium is eluted from a positive electrode active material into a positive electrode slurry under the production of a positive electrode, and the lithium reacts with a moisture contained in a binder to form lithium hydroxide. The lithium hydroxide then formed reacts preferentially with an acidic oxide and thereby suppresses a reaction between the then formed lithium hydroxide and a binder. Thus, a gelation of the positive electrode slurry is suppressed. Furthermore, acid oxide serves as a conductive agent on a positive electrode, whether the acid oxide reacts with lithium hydroxide or not, and decreases the resistance of the entire positive electrode and thus contributes to an improvement in the power characteristics battery output.
    BRIEF DESCRIPTION OF THE DRAWINGS
    Figure 1 shows a time-dependent change in viscosity of positive electrode slurries prepared using a positive electrode composition from Examples 3, 8, 11 and Comparative Example 1.
    Figure 2 shows a correlation between the content of an acidic oxide (in terms of the content of a metallic element and / or a semi-metallic element) in a positive electrode composition and the residual amount of LiOH.
    Figure 3 shows a correlation between the content of an acidic oxide (in terms of the content of a metallic element and / or a semi-metallic element) in a positive electrode composition and the internal resistance of direct current (CC-IR).
    Figure 4 is a result of an analysis of the mapping of
    6/17 im two-dimensional concentration that shows an example of the distribution of acid oxide particles in a positive electrode composition.
    DETAILED DESCRIPTION OF THE INVENTION
    The positive electrode composition of the present invention will be described in detail by means of modalities and examples. However, the present invention is not limited to these modalities and examples.
    The positive electrode composition of the present invention includes a positive electrode active material composed of a lithium transition metal complex oxide that contains essentially lithium and nickel, and additive particles composed of acid oxide particles.
    The composition of the positive electrode active material is represented by the general formula: Lii + x Ni y Co z Mi.y. z . w L w O2 (0 <x £ 0.50, 0.30 <y <1.0, 0 <z £ 0.5, 0 <w <0.1, 0.30 <y + z + w £ l , M represents at least one type selected from Mn and Al, and L represents at least one type of an element selected from the group consisting of Zr, Ti, Mg and W). x is preferably as large as possible from the point of view of output power characteristics. However, when x is greater than 0.5, due to the increased amount of the unreacted Li component, particles are synthesized in a calcination step, which results in a difficulty in production. Therefore, a substantial upper limit of x is 0.5. When y is less than 0.3, it is disadvantageous from the point of view of the output power characteristics and thus, y is preferably 0.3 or more. When z is greater than 0.5, a cost advantage cannot be found and thus, z is preferably 0.5 or less for the purpose of cost reduction. When an additional amount of a metallic element L increases, the capacity decreases and thus w is preferably 0.001 or more, and 0.1 or less. Based on these facts, the most preferred ranges are, broadly, as follows: 0 <x 0.2, 0.3 <y £ 0.8, 0 <z <0.35, and 0.001 <w <0 ,1.
    In addition, the Li, Ni, Co and M sites can be replaced by the other element L for another purpose. L is preferably Zr from the point of view of storage characteristics. At least one type of a Ti or Mg element is preferred from the point of view of the characteristics of
    7/17 cycle. At least one type of a Zr or W element is particularly preferred since the output power characteristics are notably enhanced by a combination with an acidic oxide that constitutes the present invention.
    Acid oxide refers to an oxide that reacts with a base (alkaline base) to form a salt. In this specification, an amphoteric oxide is also included in the acid oxide from the point of view of reaction with a base. Examples of the metallic element and / or semimetallic element that forms the acid oxide include tungsten, molybdenum, vanadium, tin, boron, manganese, tellurium, aluminum, zinc, magnesium and the like. From the point of view of reactivity with lithium hydroxide, the property of electrical conduction before and after the reaction of a substance and the like, tungsten, molybdenum, vanadium, tin and boron are preferred. Among these elements, tungsten and molybdenum are particularly preferred.
    The method for producing the positive electrode composition of the present invention will be described below. The positive electrode composition can be obtained by properly mixing the positive electrode active material with additive particles. The chemical-mechanical coating layer can also be formed by stirring at a high speed. However, it is sufficient when mixed, as long as a drastic uneven distribution does not occur.
    There is no particular limitation on the mixed amount of acid oxide particles. However, when the mixed amount is very small, the gelling suppression effect of the positive electrode slurry and the output power characteristics are insufficient. In contrast, when the mixed quantity is very large, the proportion of the positive electrode active material in the positive electrode only decreases and thus the mixed quantity is appropriately adjusted depending on the purposes.
    Considering the amount of a binder and the amount of positive electrode active material by producing a positive electrode, the content of acid oxide particles in the electrode composition
    8/17 active is preferably 5.0 mol% or less, expressed in terms of a ratio between the metallic element and / or semimetallic element in the acid oxide particles and the positive electrode active material, since several characteristics are well balanced. The content is more preferably 0.01 mol% or more and 1.0 mol% or less (see figure 3).
    The median diameter of acid oxide particles in the positive electrode composition is preferably the smallest possible. However, when the median diameter is very small, the acid oxide particles tend to aggregate and, therefore, the median diameter is appropriately adjusted. The median diameter is preferably from 0.1 pm to 2 pm and, more preferably, from 0.5 pm to 1.5 pm. It is preferred that the median diameter of the positive electrode active material in a positive electrode composition is relatively larger than that of the acid oxide particles. Taking into account the balance with other characteristics, in addition, the median diameter is preferably from 4 pm to 8 pm.
    The positive electrode active material can be appropriately produced by a known technique. For example, the positive electrode active material can be obtained by mixing powdered raw materials, each containing constituent elements capable of being decomposed at a high temperature in an oxide using a mixer, and by calcining the mixture obtained at 700 ° C to 1,100 ° C.
    The positive electrode slurry of the present invention is produced by mixing the positive electrode composition produced by the aforementioned method with a binder and a dispersion medium. Alternatively, the positive electrode slurry can be produced by dispersing and dissolving the positive electrode active material, the additive particles and a binder in a dispersion medium so that the positive electrode active material meets the binder in the presence of the particles additives. It is possible to use, as the binder, for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and the like. The binder is preferably mixed in a proportion of 2% by weight or more and 10% by weight or less. It is possible to use, as a dispersion medium, for example, N
    9/17 methyl-2-pyrrolidone (NMP). In addition to the binder and dispersion medium, a conductive agent, such as black acetylene, can be mixed. The conductive agent is preferably mixed in the proportion of 2% by weight or more and 10% by weight or less.
    Example 1
    In a reaction vessel, pure water is prepared with stirring, and an aqueous solution of nickel sulphate, an aqueous solution of cobalt sulphate and an aqueous solution of manganese sulphate are added dropwise at a Ni flow rate ratio : Co: 5: 2: 3 mn in terms of a molar ratio. After the dropwise addition is complete, a liquid temperature is adjusted to 65 ° C and a given amount of an aqueous sodium hydroxide solution is added dropwise to obtain a coprecipitate nickel-cobalt-manganese hydroxide. The coprecipitated hydroxide obtained is washed with water, filtered, separated and then mixed with lithium carbonate and zirconium (IV) oxide so that Li: (Ni + Co + Mn): Zr becomes 1.10: 1: 0.005 to obtain a mixed raw material. The mixed raw material obtained is calcined under atmospheric conditions at 850 ° C for 2.5 hours and then calcined at 900 ° C for 4.5 hours to obtain a sintered body. The sintered body obtained is crushed and subjected to dry sieving to obtain a positive electrode active material represented by the composition formula: Li-ijoNio.sCoo ^ Mno, sZro.oosCk. The positive electrode active material obtained has a median diameter of 6.0 pm.
    The positive electrode active material obtained is mixed with tungsten oxide (VI) which has a median diameter of 1.0 pm as additive particles with the use of a high speed shear mixer so that (Ni + Co + Mn + Zr): W become 1: 0.001 to obtain a positive electrode composition.
    Example 2
    In the same way as in example 1, except by mixing with tungsten oxide (VI) as additive particles so that (Ni + Co + Mn + Zr): W becomes 1: 0.002, a positive electrode composition is obtained.
    10/17
    Example 3
    In the same way as in example 1, except by mixing with tungsten oxide (VI) as additive particles so that (Ni + Co + Mn + Zr): W becomes 1: 0.003, a positive electrode composition is obtained.
    Example 4
    In the same way as in example 1, except by mixing with tungsten oxide (VI) as additive particles so that (Ni + Co + Mn + Zr): W becomes 1: 0.005, a positive electrode composition is obtained.
    Example 5
    In the same way as in example 1, except by mixing with tungsten oxide (VI) as additive particles so that (Ni + Co + Mn + Zr): W becomes 1: 0.010, the positive electrode composition is obtained.
    Example 6
    In the same way as in example 1, except for the mixture with molybdenum oxide (VI) which has a median diameter of 1.0 pm as additive particles so that (Ni + Co + Mn + Zr): Mo is taken 1: 0.001 , a positive electrode composition is obtained.
    Example 7
    In the same way as in example 6, except by mixing with molybdenum oxide (VI) as additive particles so that (Ni + Co + Mn + Zr): Mo is taken 1: 0.002, the positive electrode composition is obtained.
    Example 8
    In the same way as in example 6, except for mixing with molybdenum oxide (VI) as additive particles so that (Ni + Co + Mn + Zr): Mo becomes 1: 0.003, a positive electrode composition is obtained.
    Example 9
    In the same way as in example 6, except for mixing with molybdenum oxide (VI) as additive particles so that (Ni + Co + Mn + Zr): Mo becomes 1: 0.006, a positive electrode composition is obtained11 / 17 gives.
    Example 10
    In the same way as in example 6, except by mixing with molybdenum oxide (VI) as additive particles so that (Ni + Co + Mn + Zr): Mo becomes 1: 0.010, a positive electrode composition is obtained.
    Example 11
    In the same way as in example 1, except for the mixture with vanadium oxide (VI) which has a median diameter of 1.0 pm as additive particles so that (Ni + Co + Mn + Zr): V becomes 1: 0.004 , a positive electrode composition is obtained.
    Comparative Example 1
    Only the positive electrode active material in example 1 is considered as a comparative example.
    The results of the analysis of the two-dimensional concentration mapping of ΕΡΜΑ are shown in figure 4 in relation to the positive electrode composition of Example 1. As is evident in figure 4, tungsten oxide (VI) particles that have a particle size of about 1 pm are distributed almost evenly in a positive electrode composition. In addition, in relation to other Examples, almost the same results are obtained.
    With respect to examples 1 to 11 and comparative example 1, the residual amount of LiOH in a positive electrode composition is measured by the following method.
    First, 10.0 g of a positive electrode composition (or a positive electrode active material for comparison) is placed in a styrol bottle with a cap and 50 ml of pure water is added and then the bottle is capped, followed by shaking with shaking for 1 hour. After the end of stirring, the supernatant is filtered with a 5C filter paper. An initial filtrate (a few ml) is discarded and 20 ml of the subsequent filtrate is collected in a test tube. The collected filtrate is transferred to a 200 ml conical beaker and diluted with 50 ml of water
    12/17 pure. For dilution, a 1% phenolphthalein solution is added and a 0.025 N sulfuric acid is added by dripping until the solution becomes clear. Based on the amount of 0.025 N sulfuric acid used in the titration, the residual amount of LiOH in the positive electrode composition is calculated.
    With respect to examples 1 to 11 and comparative example 1, the viscosity of the positive electrode slurry is measured as follows.
    A positive electrode composition (30 g), 1.57 g PVDF and 12.48 g NMP are placed in a 150 ml polyethylene container and mixed at normal temperature (about 25 ° C) for 5 minutes. After mixing, the viscosity of the slurry obtained is measured immediately by a type E viscosity meter. With the use of a straight corn plate blade as a blade, the measurement is performed by a rotor at a rotational speed of 5 rpm. Thus, a measured value of an initial viscosity is obtained.
    Then, the slurry in the polyethylene container is left in a constant temperature bath at 60 ° C. After 24 hours, 48 hours and 72 hours, the viscosity is measured again by the type E viscometer. Before the measurement, the slurry is mixed at a normal temperature for 2 minutes.
    In relation to examples 1 to 11 and comparative example 1, the CC-IR is measured as follows.
    The positive electrode slurry is prepared by dispersing 85 parts by weight of a positive electrode composition, 10 parts by weight of black acetylene and 5.0 parts by weight of PVDF in NMP. The obtained positive electrode slurry is coated on a dry aluminum foil, formed by compression through a roller press and then cut to a given size to obtain a positive electrode.
    A negative electrode slurry is prepared by dispersing 90 parts by weight of lithium titanate, 3 parts by weight of black acetylene, 2.0 parts by weight of a carbon fiber produced in the vapor phase
    13/17 (VGCF, registered trademark) and 5.0 parts by weight of PVDF in PWN. The obtained negative electrode slurry is coated on a dry aluminum foil formed by compression through a roller press and then cut to a given size to obtain a negative electrode.
    An ethylene carbonate (EC) is mixed with methyl ethyl carbonate (MEC) at a volume ratio of 3: 7 to obtain a solvent. A lithium hexafluorophosphate (LiPF 6 ) is dissolved in the mixed solvent obtained so that the concentration becomes 1 mol / l to obtain a non-aqueous electrolyte.
    A lead electrode was respectively attached to current collectors of the above positive and negative electrodes, followed by vacuum drying at 120 ° C. Then, a separator produced from porous polyethylene is supplied between the positive electrode and the negative electrode, and they are placed in a laminated pouch-shaped package. After that, the absorbed moisture for each member is removed by vacuum drying at 60 ° C. After vacuum drying, the aforementioned non-aqueous electrolyte is injected into the laminated package, followed by a seal to obtain a secondary battery of laminated non-aqueous electrolyte for evaluation.
    The obtained battery is aged with a microcurrent, thus allowing the electrolyte to permeate sufficiently the interior of the positive and negative electrodes. Then, a high current is applied and a microcurrent is applied again. Loading-unloading is carried out ten times in total. A battery capacity in the load 10 is regarded as (1), then the battery is charged to 40% (1).
    In a constant temperature bath set at 25 ° C, the aforementioned battery charged to 40% is discarded, and a current of 0.04 A, 0.08 A, 0.12 A, 0.16 A and 0.20 A it is alternately applied in a loading direction and in a discharge direction. A voltage is used if the current is applied in the direction of discharge. The abscissa denotes an applied current value, while the ordinate denotes an achieved voltage, and a gradient of a straight line that connects intersection points is considered 14/17 as a CC-IR value at 25 ° C.
    After measuring the CC-IR at 25 ° C, the battery was discharged and then charged to 40% (1). After being charged, the battery is placed in a constant temperature bath set at -25 ° C and left for 6 hours and then a current of 0.02 A, 0.04 A and 0.06 A is applied in a direction of discharge. The abscissa denotes an applied current value, while the ordinate denotes an achieved voltage, and a straight line gradient that connects intersection points is considered to be a CC-IR value at -25 ° C.
    With respect to examples 1 to 11 and comparative example 1, a lithium component eluted from a positive electrode active material and a change in viscosity of a positive electrode slurry are shown in Table 1, and the discharge capacity of a battery, a CC-IR value at 25 ° C and a CC-IR value at -25 ° C are shown in Table 15 2. A state of a time-dependent change in the viscosity of a positive electrode slurry is shown in figure 1.
    15/17
    After 72hours 0c5 cd 9,360 9,490 10,700 9,660 7,930 0 IDT "CO 0 co CMCO 0 CD IDCO 9,220 6,480 19,300 V) ώ CLç 5 48s 0 0 0 00 0 0 0 O O 0 0 00 Lm 0 s 10 0 CD ID ID co σ> X— O co ** Q. 0 ▼ “ COO ID I s * · CD CM ID CD CO3 < CD σ> CD X ““ σ> I s ** I s * · CO CO σ> CO X - 3 5 = -Sω COCl 5 24s O O ο O O 0 0 0 O O 0 O0 2 00ο cxiID CO co O CM co O0. n 00 0 σ> CDCD CM co X ”· co CXI 00 Φ <x: CO oo co CD σ> CD I s * - l · - CO co co CD CO 3ω Q 0 0 0 0 O O 0 O 0 0 0 0 O Q 0 2 CO CXl co cxicoCXI 00 CDM ω Q. The00 σ>I s *.ID CD coco CM > <£ CD <0 CD I s * · CO CD CO co I s * - I s * · ID co Ή residual by weight 10 CO Ο O V "0 000 V "0 0 OThe X.O 0 0 ο ’ O' 0 ’ 0 0 0 0 0 O ! © 2 0 0 V V V 0 0 ’ V V V V 0 0)3 CO3(03O additive * / (mol%) O' 0.2 0.3 0.5 OT " 0 CM O 0.3 CDO 0V 0.4</> CO 5 ω o 5 C ~ CO0 CO0 CO0 CO0 co0 CO O O COO O CO 0 0 co O O co O O m0 W X CO 5 5£ £s s s 5 > 1 i * (O O Q. CM0 CM0 CM0 CM 0 CM0 CM0 CM0 CM0 CM0 CM0 CMO CMOu 10 ID £ m y in 3 8 8 8 8 8 8 8 8 8 8 8 82 ° 0g £L ! ©£ 0> NΝcohl hl hl hl Nco hl N hiΦ 0 00 θ 0O' 0)3 c S ç C S c:> c z> c s ç ç Ç Ç c Σ c sO CM CM. CM CM O ’ CM o ’ CM O 0 " 0 ' 0 0 ’ CM CM_> O O 0 0 0 0 0 0 O Q O O 0 0 00 0 0 0 0 ω 0 0 CO 10 o in o ID Ô in<5 in Ô ID in Õ _O _O _O in <5 m Ó1___ z z z z z z z z z z z zCD 0 0 0 0 0 0 00 n> § τ— y— MM MM * -J-J-J _! -1 _J -1 -j Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1
    *
    The additive quantity is expressed in terms of the proportion of a metallic element and / or a semi-metallic element
    16/17
    Table2 _____________________________________, ____________________ CC-IR / Ω _________ A-25 ° C O 00T " 11.7 11.4 C0v— CM T - V " qr— V “ 10.9 O) oh v- 10.8 11.1 13.6 * The additive quantity is expressed in terms of the proportion of a metallic element and / or a semi-metallic element based on a positive electrode active material. A25 ° C CD 1.39 1.37 v-COt— t— CD T - jnV " 1.47 The LOT— 1.55 1.39 JD Additive quantity * / (mol%) O' 0.2 0.3 0.5 COV O 0.2 0.3 CO o ' cqT " O' 1 Additive particles CO o £ CO o% C0 o% CO o £ CO o% CO o o CO o o CO o o CO o o S COO o I'm the 1 Positive electrode active material 04 OLO OThe £The C04 oO T oÔ ZO—I Hi oall o ctthe C Σ04 OO OIOZ-J Hi oto o o £> NCO o cOI o ’O O tO ô z o V OJ OTO O O £ NCO oÇO4_O OiozOY “ Hi oLO O o 1 ° NCO oÇHIOO O10 <5ZOT " Hi otDOThe 1stthe CHi oO Oio _ô zO Hi oIO O O i ° NCO o CHi o O OtOOh zO Hi o* o o o oNCO oC SCM oO OallZ o• Τ ’ Hi oLO O o £ NCO oÇHi oO Otooh zOV-• r- OI o IO oo N CO o ' c CM o OO to z o CMOevery o 1 ° NCO o c ΣHi o ”O OIO_6 ZO HIOto o oNCOOC ΣHi ΌOOto<D zOT "v The Q. E 0)X LU Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 σ> oO.E φ XLU Example 10 Example 11 Comparative Example 1
    17/17
    As is evident in Table 1 and Figure 2, the lithium hydroxide content, which can cause a positive electrode slurry to freeze, decreases in positive electrode compositions that contain additive particles added to them, according to examples 1 to 11, when compared to a positive electrode composition that does not contain additive particles added to them, as in comparative example 1. As is evident in table 1 and figure 1, an increase in viscosity is suppressed in the prepared positive electrode pastes using a positive electrode composition from examples 1 to 11 when compared to a prepared positive electrode slurry using a positive electrode composition from comparative example 1. Furthermore, as is evident in table 2 and figure 3, power characteristics output at -25 ° C are enhanced in secondary non-aqueous electrolyte batteries produced using an electrode composition positive of examples 1 to 11 when compared to a secondary non-aqueous electrolyte battery produced using a positive electrode composition from comparative example 1. In contrast, no significant difference in the output power characteristics at 25 ° C is observed even in any of examples 1 to 11 and comparative example 1. This reveals that the effects of additive particles are noticeable in a low temperature region.
    The positive electrode composition for a secondary non-aqueous electrolyte battery of the present invention can be used in a secondary non-aqueous electrolyte battery. The secondary non-aqueous electrolyte battery using the positive electrode composition of the present invention is inexpensively priced and has improved output power characteristics and also exhibits satisfactory performance and satisfactory operability, and thus, the non-aqueous electrolyte secondary battery it can be particularly suitable for use not only on mobile devices, such as a mobile phone, laptop and digital camera, but also on a high power output source for large applications, such as a vehicle battery electric.
    权利要求:
    Claims (6)
    [1]
    1. Composition of positive electrode for secondary non-aqueous electrolyte battery, characterized by the fact that it consists of a positive electrode active material composed of a lithium transition metal complex oxide represented by the general formula Li1 + xNiyCozM1-yz-wLwO2 in that 0 <x <0.2, 0.3 <y <0.8, 0 <z <0.35, 0.001 <w <0.1, 0.30 <y + z + w <1, M represents at at least one type selected from Mn and Al, and L represents Zr and additive particles composed of acid oxide particles, in which the acid oxide particles are composed of at least one type selected from the group consisting of tungsten oxide, molybdenum oxide , vanadium pentoxide, tin dioxide and boron oxide, where the content of the acid oxide particles is 5.0 mol% or less expressed in terms of a ratio between a metallic element and / or a semi-metallic element in the particles acid oxide and the positive electrode active material.
    [2]
    2. Positive electrode composition according to claim 1, characterized by the fact that the content of acid oxide particles in the general formula of the positive electrode active material is 0.01 mol% or more and 1.0 mol% or less expressed in terms of a ratio between the metallic element and / or the semimetallic element in the acid oxide particles and the positive electrode active material.
    [3]
    3. Positive electrode composition according to claim 1 or 2, characterized by the fact that the median diameter of the positive electrode active material is from 4 pm to 8 pm and the median diameter of the additive particle is 0.1 pm at 2 pm.
    [4]
    4. Method for producing a positive electrode slurry for secondary non-aqueous electrolyte battery, characterized by the fact that it comprises:
    a step of mixing a positive electrode active material composed of a lithium transition metal complex oxide
    Petition 870190041339, of 5/2/2019, p. 5/36
    2/2 represented by the general formula: Lii + xNiyCozMi-yz-wLwO2 where 0 <x <0.2, 0.3 <y <0.8, 0 <z <0.35, 0.001 <w <0.1 , 0.30 <y + z + w <1, M represents at least one type selected from Mn and Al, and L represents Zr with additive particles composed of acid oxide particles for
    [5]
    5 obtain a positive electrode composition; wherein the acid oxide particles are composed of at least one type selected from the group consisting of tungsten oxide, molybdenum oxide, vanadium pentoxide, tin dioxide and boron oxide; and a step of mixing the positive electrode composition, a
    [6]
    10 binder and a dispersion medium to obtain a positive electrode slurry, where the content of the acid oxide particles is 5.0 mol% or less expressed in terms of a ratio between a metallic element and / or an element semimetallic in the acid oxide particles and the positive electrode active material.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112012032891B1|2020-01-14|positive electrode composition for secondary non-aqueous electrolyte battery and method for producing positive electrode slurry using positive electrode composition
    JP6286855B2|2018-03-07|Positive electrode composition for non-aqueous electrolyte secondary battery
    Roberts et al.2018|The re-emergence of sodium ion batteries: testing, processing, and manufacturability
    JP6575048B2|2019-09-18|The positive electrode composition for nonaqueous electrolyte secondary batteries, the nonaqueous electrolyte secondary battery, and the manufacturing method of the positive electrode composition for nonaqueous electrolyte secondary batteries.
    Ding et al.2015|A high-capacity TiO 2/C negative electrode for sodium secondary batteries with an ionic liquid electrolyte
    JP2017174597A|2017-09-28|Lithium ion secondary battery
    JP2012174546A|2012-09-10|Nonaqueous electrolyte secondary battery
    WO2013099279A1|2013-07-04|Negative electrode for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery comprising negative electrode for nonaqueous electrolyte secondary batteries
    JP5842596B2|2016-01-13|Positive electrode composition for non-aqueous electrolyte secondary battery and method for producing positive electrode slurry for non-aqueous electrolyte secondary battery
    JP5850006B2|2016-02-03|Negative electrode active material for sodium ion battery, sodium ion battery, and method for producing negative electrode active material for sodium ion battery
    Xue et al.2015|Synthesis and performance of hollow LiNi 0.5 Mn 1.5 O 4 with different particle sizes for lithium-ion batteries
    JP2012156087A|2012-08-16|Nonaqueous electrolyte secondary battery
    JP2019114560A|2019-07-11|Positive electrode composition for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and method for producing positive electrode composition for non-aqueous electrolyte secondary battery
    JP2019140093A|2019-08-22|Coated positive electrode active material for lithium ion secondary battery, and manufacturing and evaluation methods thereof
    JP2019140091A|2019-08-22|Coated positive electrode active material for lithium ion secondary battery, and manufacturing and evaluation methods thereof
    JP2019140092A|2019-08-22|Coated positive electrode active material for lithium ion secondary battery, and manufacturing and evaluation methods thereof
    CN108598458B|2020-02-18|Nitrogen-doped lithium titanate composite material, preparation method thereof and lithium ion battery
    BR102018077251A2|2019-07-30|WATER ELECTROLYTIC SOLUTION AND WATERY ION SECONDARY BATTERY
    JP2018195419A|2018-12-06|Positive electrode material for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery arranged by use thereof, and method for manufacturing positive electrode material for nonaqueous electrolyte secondary battery
    JP5924316B2|2016-05-25|Negative electrode active material for sodium ion battery and sodium ion battery
    JP2017045633A|2017-03-02|Positive electrode active material for nonaqueous electrolyte secondary battery, method of manufacturing the same, and nonaqueous electrolyte secondary battery
    JP2020043029A|2020-03-19|Active material
    JP2021018982A|2021-02-15|Positive electrode active material for lithium ion secondary battery and method for producing the same
    JP2019140090A|2019-08-22|Coated positive electrode active material for lithium ion secondary battery, and manufacturing and evaluation methods thereof
    JP2014235856A|2014-12-15|Nonaqueous electrolyte secondary battery
    同族专利:
    公开号 | 公开日
    KR20130086279A|2013-08-01|
    WO2011162157A1|2011-12-29|
    HUE043031T2|2019-07-29|
    CN102947983A|2013-02-27|
    CN102947983B|2016-03-23|
    PL2587571T3|2019-04-30|
    EP2587571A1|2013-05-01|
    KR101888204B1|2018-08-13|
    BR112012032891A2|2016-11-29|
    JP5382061B2|2014-01-08|
    EP2587571B1|2018-12-19|
    US9716272B2|2017-07-25|
    JP2012028313A|2012-02-09|
    EP2587571A4|2015-11-25|
    US20110315918A1|2011-12-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP4114247B2|1998-09-30|2008-07-09|松下電器産業株式会社|Non-aqueous electrolyte secondary battery|
    KR100326457B1|1999-03-10|2002-02-28|김순택|A positive active material for a lithium secondary battery and a method of preparing the same|
    DE19922522A1|1999-05-15|2000-11-16|Merck Patent Gmbh|Lithium based composite oxide particles for battery cathode, which are coated with one or more metal oxides|
    US6730435B1|1999-10-26|2004-05-04|Sumitomo Chemical Company, Limited|Active material for non-aqueous secondary battery, and non-aqueous secondary battery using the same|
    JP2002075367A|2000-09-04|2002-03-15|Mitsui Chemicals Inc|Positive electrode active material for lithium battery, manufacturing method for the active material, and secondary battery using it|
    KR100709205B1|2001-04-02|2007-04-18|삼성에스디아이 주식회사|Positive active material composition for lithium secondary battery|
    US8658125B2|2001-10-25|2014-02-25|Panasonic Corporation|Positive electrode active material and non-aqueous electrolyte secondary battery containing the same|
    JP2003142101A|2001-10-31|2003-05-16|Nec Corp|Positive electrode for secondary battery and secondary battery using the same|
    JP2005251716A|2004-02-05|2005-09-15|Nichia Chem Ind Ltd|Cathode active substance for nonaqueous electrolyte secondary battery, cathode mixture for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery|
    CN100433445C|2004-04-07|2008-11-12|松下电器产业株式会社|Nonaqueous electrolyte secondary battery|
    JP2006066330A|2004-08-30|2006-03-09|Shin Kobe Electric Mach Co Ltd|Cathode active material for nonaqueous electrolyte solution secondary battery, nonaqueous electrolyte solution secondary battery, and manufacturing method of cathode active material|
    US7879494B2|2005-03-23|2011-02-01|Panasonic Corporation|Lithium ion secondary battery and manufacturing method therefor|
    JP5082204B2|2005-05-27|2012-11-28|ソニー株式会社|Method for producing positive electrode active material for lithium secondary battery and lithium secondary battery|
    JP2007188878A|2005-12-16|2007-07-26|Matsushita Electric Ind Co Ltd|Lithium ion secondary battery|
    US20070141470A1|2005-12-16|2007-06-21|Kensuke Nakura|Lithium ion secondary battery|
    KR101201170B1|2006-03-21|2012-11-13|삼성에스디아이 주식회사|Positive electrode for lithium rechargeable battery and Lithium rechargeable battery comprising the same and Method of making the lithium rechargeable battery|
    KR101264332B1|2006-09-20|2013-05-14|삼성에스디아이 주식회사|Cathode active material and lithium battery using the same|
    JP2009032647A|2007-06-25|2009-02-12|Mitsubishi Chemicals Corp|Material for positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery using it, and lithium secondary battery|
    JP5428251B2|2007-09-04|2014-02-26|三菱化学株式会社|Lithium transition metal compound powder, positive electrode for lithium secondary battery and lithium secondary battery using the same|
    JP2011060605A|2009-09-10|2011-03-24|Toyota Motor Corp|Lithium ion secondary battery, vehicle, battery mounting device, and positive electrode plate|
    WO2011078263A1|2009-12-24|2011-06-30|日本ゼオン株式会社|Electrode for secondary battery, and secondary battery|
    JP2011146158A|2010-01-12|2011-07-28|Toyota Motor Corp|Lithium secondary battery|JP2012238581A|2011-04-28|2012-12-06|Nichia Chem Ind Ltd|Positive electrode active material for nonaqueous electrolyte secondary battery|
    US20140329146A1|2011-07-28|2014-11-06|Sanyo Electric Co., Ltd.|Nonaqueous electrolyte secondary battery|
    JP6072689B2|2011-07-29|2017-02-01|三洋電機株式会社|Nonaqueous electrolyte secondary battery|
    KR20130081055A|2012-01-06|2013-07-16|삼성에스디아이 주식회사|Positive electrode material for lithium battery, positive material prepared from the material, and lithium battery including the positive electrode|
    JP6286855B2|2012-04-18|2018-03-07|日亜化学工業株式会社|Positive electrode composition for non-aqueous electrolyte secondary battery|
    CN104641497B|2012-09-25|2017-06-23|三洋电机株式会社|Rechargeable nonaqueous electrolytic battery and positive electrode active material for nonaqueous electrolyte secondary battery|
    US10224538B2|2013-01-16|2019-03-05|Samsung Sdi Co., Ltd.|Positive electrode for rechargeable lithium battery and rechargeable lithium battery including the same|
    CN105122514B|2013-03-26|2017-12-19|三洋电机株式会社|Positive electrode active material for nonaqueous electrolyte secondary battery and use its rechargeable nonaqueous electrolytic battery|
    US9991514B2|2013-08-29|2018-06-05|Lg Chem, Ltd.|Method of manufacturing lithium nickel complex oxide, lithium nickel complex oxide manufactured thereby, and cathode active material including the same|
    CN104584284B|2013-08-29|2017-11-24|株式会社Lg 化学|Lithium transition-metal compound particle and preparation method thereof and the positive active material for including it|
    KR20150037085A|2013-09-30|2015-04-08|주식회사 엘지화학|Cathode Active Material for Lithium Secondary Battery and Lithium Secondary Battery Comprising the Same|
    KR101666384B1|2013-09-30|2016-10-14|주식회사 엘지화학|Cathode Active Material for High Voltage Lithium Secondary Battery and Lithium Secondary Battery Comprising the Same|
    JP6575048B2|2013-10-17|2019-09-18|日亜化学工業株式会社|The positive electrode composition for nonaqueous electrolyte secondary batteries, the nonaqueous electrolyte secondary battery, and the manufacturing method of the positive electrode composition for nonaqueous electrolyte secondary batteries.|
    JP6852747B2|2013-10-17|2021-03-31|日亜化学工業株式会社|A method for producing a positive electrode composition for a non-aqueous electrolyte secondary battery, a non-aqueous electrolyte secondary battery, and a positive electrode composition for a non-aqueous electrolyte secondary battery.|
    WO2015064478A1|2013-10-28|2015-05-07|旭硝子株式会社|Lithium-containing composite oxide production method, positive electrode for lithium ion secondary battery, and lithium ion secondary battery|
    JP6743920B2|2013-12-13|2020-08-19|日亜化学工業株式会社|Positive electrode active material for non-aqueous electrolyte secondary battery and method for producing the same|
    JP6524651B2|2013-12-13|2019-06-05|日亜化学工業株式会社|Positive electrode active material for non-aqueous electrolyte secondary battery and method for producing the same|
    CN106104860B|2014-03-20|2018-11-30|三洋电机株式会社|Positive electrode for nonaqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery|
    JP6312489B2|2014-03-27|2018-04-18|オートモーティブエナジーサプライ株式会社|Non-aqueous electrolyte battery and manufacturing method thereof|
    WO2015199168A1|2014-06-26|2015-12-30|戸田工業株式会社|Positive electrode active substance particle powder for non-aqueous electrolyte secondary battery, production method therefor, and non-aqueous electrolyte secondary battery|
    CN106716701A|2014-09-26|2017-05-24|三洋电机株式会社|Nonaqueous electrolyte secondary battery|
    CN105789609A|2014-12-15|2016-07-20|上海兆维科技发展有限公司|Cathode material, preparation method and application thereof|
    WO2016136212A1|2015-02-27|2016-09-01|三洋電機株式会社|Nonaqueous electrolyte secondary cell|
    CN108352526A|2015-10-28|2018-07-31|住友金属矿山株式会社|Non-aqueous electrolyte secondary battery positive active material and its manufacturing method, non-aqueous electrolyte secondary battery anode composite material paste and non-aqueous electrolyte secondary battery|
    WO2017090378A1|2015-11-27|2017-06-01|住友金属鉱山株式会社|Positive electrode material for non-aqueous electrolyte secondary battery and method for manufacturing same, positive electrode composite paste, and non-aqueous electrolyte secondary battery|
    JP6685002B2|2015-12-11|2020-04-22|パナソニックＩｐマネジメント株式会社|Positive electrode active material for secondary battery and secondary battery|
    US20190044179A1|2016-02-29|2019-02-07|Panasonic Intellectual Property Management Co., Ltd.|Nonaqueous electrolyte secondary battery|
    KR101892612B1|2016-03-25|2018-08-28|주식회사 에코프로비엠|Manufacturing method of cathod active material for lithium rechargeable batteries and cathod active material for lithium rechargeable batteries made by the same|
    CN109155412A|2016-05-16|2019-01-04|住友金属矿山株式会社|Non-aqueous electrolyte secondary battery positive active material and its manufacturing method, non-aqueous electrolyte secondary battery anode composite material paste and non-aqueous electrolyte secondary battery|
    CN109891643A|2016-08-29|2019-06-14|住友金属矿山株式会社|Non-aqueous electrolyte secondary battery positive active material and its manufacturing method, non-aqueous electrolyte secondary battery anode composite material paste and non-aqueous electrolyte secondary battery|
    JP6637873B2|2016-11-02|2020-01-29|Ｊｘ金属株式会社|Positive active material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery|
    JP6819245B2|2016-11-30|2021-01-27|三洋電機株式会社|A method for manufacturing a positive electrode plate for a non-aqueous electrolyte secondary battery, a method for manufacturing a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery.|
    JP6343753B2|2016-12-07|2018-06-20|住友化学株式会社|Positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery, and lithium secondary battery|
    WO2018221664A1|2017-05-31|2018-12-06|住友金属鉱山株式会社|Positive electrode active substance for non-aqueous electrolyte secondary battery and method for producing same, positive electrode mixture paste for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery|
    JPWO2019039567A1|2017-08-25|2020-10-01|住友金属鉱山株式会社|Positive electrode active material for non-aqueous electrolyte secondary batteries and its manufacturing method, positive electrode mixture paste for non-aqueous electrolyte secondary batteries and non-aqueous electrolyte secondary batteries|
    JP2019139854A|2018-02-06|2019-08-22|住友金属鉱山株式会社|Positive electrode active material for nonaqueous electrolyte secondary battery and manufacturing and evaluation methods thereof, and nonaqueous electrolyte secondary battery|
    US20210013509A1|2018-03-20|2021-01-14|Sumitomo Metal Mining Co., Ltd.|Positive electrode active material for non-aqueous electrolyte secondary batteries and method for producing the same|
    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-03-12| B06T| Formal requirements before examination|
    2019-11-19| B09A| Decision: intention to grant|
    2020-01-14| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/06/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2010141828|2010-06-22|
    JP2011109958A|JP5382061B2|2010-06-22|2011-05-17|Positive electrode composition for non-aqueous electrolyte secondary battery and positive electrode slurry using the positive electrode composition|
    PCT/JP2011/063806|WO2011162157A1|2010-06-22|2011-06-16|Positive-electrode composition for a nonaqueous-electrolyte secondary battery and method for manufacturing a positive-electrode slurry using said positive-electrode composition|
    [返回顶部]