JP2011216201A - Electrode active material and lithium ion battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode active material and a lithium ion battery, capable of enhancing a rate characteristic, a cycle life and durability.SOLUTION: One part of phosphate ion (PO) of the electrode active material having olivine structure expressed by LiAPO, wherein A represents one kind, two kinds or more selected from the group consisting of Cr, Mn, Fe, Co, Ni and Cu, 0<x≤2, and 0<y≤1.5, is substituted with an oxo-acid ion such as silicate ion (SiO) and borate ion (BO) excluding phosphate ion (PO), in this electrode active material.

Description

  The present invention relates to an electrode active material and a lithium ion battery, and more particularly, is an electrode of a lithium ion battery that is one of phosphate-based electrode active materials having an olivine structure and has excellent rate characteristics, cycle life, and durability. The present invention relates to an electrode active material suitable for use as a material, and a lithium ion battery including an electrode using the electrode active material.

In recent years, non-aqueous electrolyte secondary batteries such as lithium ion batteries have been proposed and put into practical use as batteries that are expected to be reduced in size, weight, and capacity.
This lithium ion battery includes a positive electrode and a negative electrode having a property capable of reversibly removing and inserting lithium ions, and a non-aqueous electrolyte.
Lithium-ion batteries are lighter, smaller, and have higher energy than secondary batteries such as conventional lead batteries, nickel cadmium batteries, and nickel metal hydride batteries, and are portable for portable telephones, notebook personal computers, etc. Although it is used as a power source for electronic devices, it has recently been studied as a high-output power source for electric vehicles, hybrid vehicles, electric tools, and the like. High-speed charge / discharge characteristics are required for the electrode active materials of batteries used as these high-output power supplies. In addition, smoothing of the power generation load and application to large batteries such as stationary power supplies and backup power supplies are also being studied, and the resources are abundant and inexpensive with long-term safety and reliability. (There is no problem).

The positive electrode of a lithium ion battery is composed of an electrode material including a lithium-containing metal oxide called a positive electrode active material, which has a property of reversibly removing and inserting lithium ions, a conductive additive, and a binder. The material is applied to the surface of a metal foil called a current collector to form a positive electrode.
As the positive electrode active material of this lithium ion battery, lithium cobaltate (LiCoO ₂ ) is usually used, but in addition, lithium nickelate (LiNiO ₂ ), lithium manganate (LiMn ₂ O ₄ ), iron phosphate Lithium (Li) compounds such as lithium (LiFePO ₄ ) are used.
Among these lithium compounds, lithium cobaltate and lithium nickelate have various problems such as toxicity to the human body and the environment, the amount of resources, and instability of the charged state. Further, it has been pointed out that lithium manganate is dissolved in an electrolytic solution at a high temperature.
Therefore, in recent years, a phosphate-based electrode active material having an olivine structure typified by lithium iron phosphate, which has excellent long-term safety and reliability, has attracted attention.

Phosphate-based electrode active materials having an olivine structure represented by this lithium iron phosphate do not necessarily have sufficient electron conductivity and ion diffusivity, and therefore there is difficulty in charging and discharging a large current. This is a factor preventing high output.
Therefore, in order to solve these problems, a phosphate-based electrode active material whose surface is coated with a conductive material typified by carbon, and a phosphate-based electrode in which ion diffusion distance is reduced by making fine particles. Active materials have been proposed. Such a phosphate-based electrode active material has achieved a certain result, and is an important means for putting the phosphate-based electrode active material into practical use (Patent Document 1).
In addition, as an electrode active material in which the properties of the phosphate-based electrode active material itself are changed, a part of lithium (Li), which is a mobile ion, or a transition metal element, which is an electrochemically active element, is replaced with another element. A phosphate-based electrode active material has been proposed (Patent Document 2).

JP 2001-15111 A JP 2008-130525 A

However, the conventional phosphate electrode active material whose surface is coated with a conductive material has a problem that the conductivity and ion diffusibility inside the particles of the phosphate electrode active material cannot be improved. .
In addition, although the ionized phosphate electrode active material can shorten the ion diffusion distance, it cannot improve the ion diffusivity itself. There is a problem that the amount of the conductive material and binder used for making the electrode plate for practical use of the salt-based electrode active material is increased, and rather the battery performance is lowered.
Furthermore, in the case of phosphate-based electrode active materials in which lithium (Li) or part of transition metal elements that are electrochemically active elements are substituted with other elements, the effect is not limited, and the electrode active material There was a fundamental problem of lowering the theoretical capacity.

  The present invention has been made to solve the above problems, and an object thereof is to provide an electrode active material and a lithium ion battery capable of improving rate characteristics, cycle life and durability.

As a result of intensive studies to solve the above problems, the present inventors have found that Li _x A _y PO ₄ (where A is one selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu) Alternatively, a part of the phosphate ion (PO ₄ ³⁻ ) of the electrode active material having an olivine structure represented by 2 or more types, 0 <x ≦ 2, 0 <y ≦ 1.5) It has been found that an electrode active material excellent in rate characteristics, cycle life and durability can be obtained by substitution with an oxo acid ion other than (PO ₄ ³⁻ ), and the present invention has been completed.

That is, the electrode active material of the present invention is Li _x A _y PO ₄ (where A is one or more selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, 0 <x ≦ 2 , 0 <y ≦ 1.5), a part of the phosphate ion (PO ₄ ³⁻ ) of the electrode active material having an olivine structure is represented by an oxo acid other than the phosphate ion (PO ₄ ³⁻ ) It is characterized by being substituted with ions.

The oxoacid ion is preferably one or two of silicate ion (SiO ₄ ⁴⁻ ) and borate ion (BO ₃ ³⁻ ).

  The lithium ion battery of the present invention includes an electrode using the electrode active material of the present invention.

According to the electrode active material of the present invention, Li _x A _y PO ₄ (where A is one or more selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, 0 <x ≦ 2 , 0 <y ≦ 1.5), a part of the phosphate ion (PO ₄ ³⁻ ) of the electrode active material having an olivine structure is represented by an oxo acid other than the phosphate ion (PO ₄ ³⁻ ) Since it is substituted with ions, the rate characteristics, cycle life and durability can be improved without impairing the theoretical capacity, and the safety and resource stability are excellent.

  According to the lithium ion battery of the present invention, since the electrode using the electrode active material of the present invention is provided, a lithium ion battery excellent in rate characteristics, cycle life and durability can be provided.

A Examples 1 to 3 and X-ray diffraction pattern of LiFePO ₄ based electrode active material of Comparative Example Each of the present invention. Is a graph showing changes in the lattice constants of Examples 1 to 6 and LiFePO ₄ based electrode active material of Comparative Example Each of the present invention.

The form for implementing the electrode active material and lithium ion battery of this invention is demonstrated.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

The electrode active material of the present embodiment is Li _x A _y PO ₄ (where A is one or more selected from the group of Cr, Mn, Fe, Co, Ni, Cu, 0 <x ≦ 2, A part of the phosphate ion (PO ₄ ³⁻ ) of the electrode active material having an olivine structure represented by 0 <y ≦ 1.5) is converted into an oxo acid ion other than the phosphate ion (PO ₄ ³⁻ ). It is the electrode active material substituted by.

The oxoacid ion is preferably one or two of silicate ion (SiO ₄ ⁴⁻ ) and borate ion (BO ₃ ³⁻ ).
In this case, the electrode active material is Li _x A _y (PO ₄ ) _1-u (SiO ₄ ) _u (where A is one selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu) Or 2 or more, 0 <x ≦ 2, 0 <y ≦ 1.5, 0 <u ≦ 0.05), or Li _x A _y (PO ₄ ) _1-v (BO ₃ ) _v (where A Is represented by one or more selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, 0 <x ≦ 2, 0 <y ≦ 1.5, 0 <v ≦ 0.05) Can do. U and v represent the amount of substitution of oxo acid ions other than phosphate ions in each electrode active material.

  As for A, one or more selected from the group consisting of Cr, Mn, Fe, Co, Ni, and Cu, in particular, Fe and Mn have high rate characteristics, long cycle life, durability, and abundant resources. It is preferable from the viewpoints of quantity and safety.

The average particle size of the electrode active material is preferably 5 nm or more and 500 nm or less, more preferably 20 nm or more and 200 nm or less.
The reason is that if the average particle size is less than 5 nm, the crystal structure is destroyed by the volume change due to charge and discharge, resulting in a decrease in cycle life and durability, and if the average particle size is greater than 500 nm. This is because the supply amount of electrons to the inside of the electrode active material is insufficient and the utilization efficiency is lowered.

  Since this electrode active material has a sharp average particle size range and excellent monodispersibility, when this electrode active material is used for the positive electrode of a lithium ion battery, the electrical characteristics of this positive electrode are extremely uniform. The variation in characteristics is extremely small. Therefore, the obtained lithium ion battery is excellent in high rate characteristics, long cycle life, durability and safety.

  In order to produce the electrode active material of the present embodiment, a Li source, an A source, a phosphoric acid source (P), and an oxo acid source (Ox) have a predetermined molar ratio Li: A: (P + Ox). The mixture is mixed so as to obtain a ratio, and the obtained mixture is hydrothermally synthesized.

Examples of the Li source include lithium inorganic acid salts such as lithium hydroxide (LiOH), lithium carbonate (Li ₂ CO ₃ ), lithium chloride (LiCl), and lithium phosphate (Li ₃ PO ₄ ), lithium acetate (LiCH _3). One or more selected from the group of lithium organic acid salts such as (COO) and lithium oxalate ((COOLi) ₂ ), and hydrates thereof are preferably used.
As the A source, one or more sulfates, nitrates, chlorides and the like selected from the group consisting of Cr, Mn, Fe, Co, Ni, and Cu are preferably used.

Examples of phosphoric acid sources include phosphoric acid such as orthophosphoric acid (H ₃ PO ₄ ) and metaphosphoric acid (HPO ₃ ), ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ), and diammonium hydrogen phosphate ((NH ₄ )). ₂ HPO ₄ ), ammonium phosphate ((NH ₄ ) ₃ PO ₄ ), and hydrates thereof are preferably used.
Examples of oxo acid sources include Si sources such as silicon oxide (SiO ₂ ) and silicon tetramethoxide (Si (OCH ₃ ) ₄ ), B such as boron oxide (B ₂ O ₃ ) and boric acid (H ₃ BO ₃ ). One or more selected from the group of sources are preferably used.

Li _x A _y PO ₄ (where A is one or more selected from the group of Cr, Mn, Fe, Co, Ni, Cu, 0 <x ≦ 2) , 0 <y ≦ 1.5), a part of the phosphate ion (PO ₄ ³⁻ ) of the electrode active material having an olivine structure is an oxo acid other than the phosphate ion (PO ₄ ³⁻ ) Li _x A _y (PO ₄ ) _1-u (SiO ₄ ) _u (0 <x ≦ 2, 0 <y ≦ 1.5, 0 <u ≦ 0.05) or Li _x A _y (PO ₄ ) _1-v (BO ₃ ) _v (0 <x ≦ 2, 0 <y ≦ 1.5, 0 <v ≦ 0.05, preferably 0 <v ≦ 0.03) is obtained. .

The temperature during hydrothermal synthesis is preferably 120 ° C. or higher and 250 ° C. or lower, and more preferably 150 ° C. or higher and 220 ° C. or lower. Further, the pressure during the hydrothermal synthesis is preferably 0.2 MPa or more, more preferably 0.4 MPa or more. The hydrothermal synthesis time depends on the temperature at the time of hydrothermal synthesis, but is preferably 1 hour or longer and 24 hours or shorter, more preferably 3 hours or longer and 12 hours or shorter.
In this case, by adjusting the temperature, pressure and time during hydrothermal treatment, Li _x A _y (PO ₄ ) _1-u (SiO ₄ ) _u particles (0 <x ≦ 2, 0 <y ≦ 1.5, 0 <u ≦ 0.05), or Li _x A _y (PO ₄ ) _1-v (BO ₃ ) _v particles (0 <x ≦ 2, 0 <y ≦ 1.5, 0 <v ≦ 0.05, Preferably, the particle size of 0 <v ≦ 0.03) can be controlled to a desired size.

As described above, according to the electrode active material of the present embodiment, Li _x A _y PO ₄ (where A is one or two selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu) As described above, a part of the phosphate ions (PO ₄ ³⁻ ) of the electrode active material having an olivine structure represented by 0 <x ≦ 2, 0 <y ≦ 1.5) is converted to the phosphate ions (PO ₄ ^3- ) Since it is substituted with an oxo acid ion other than), the electrode active material can be obtained without substituting some of the mobile metal lithium (Li) and electrochemically active transition metal elements with other elements. The properties of itself can be changed, and the rate characteristics, cycle life, and durability can be improved without sacrificing the difficulty of forming an electrode plate due to excessive micronization and the reduction in the theoretical capacity of the material. .

  According to the lithium ion battery of this embodiment, since the electrode active material of this embodiment was used for the positive electrode of the lithium ion battery, lithium excellent in rate characteristics, cycle life, durability, safety, and resource stability An ion battery can be provided.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely by Examples 1-9 and a comparative example, this invention is not limited by these Examples.

(Examples 1-6)
FeSO ₄ · 7H ₂ O, Li ₃ PO ₄ , colloidal silica Snowtex O (manufactured by Nissan Chemical Co., Ltd.), LiCH ₃ COO · 2H ₂ O together with water as a raw material, the mass ratio of Li: Fe: (P + Si) is 3 + α The slurry of Examples 1-6 was produced so that it might become 1: 1: 1, and solid content might be 0.5 mol / kg (product conversion).
Here, Si: P corresponding to each of Examples 1 to 6 is set to 0.01: 0.99, 0.03: 0.97, 0.05: 0.95, 0.07: 0.93, 0. .10: 0.90, 0.15: 0.85, and α corresponding thereto were 0.01, 0.03, 0.05, 0.07, 0.10, 0.15.

Next, for each slurry of Examples 1 to 6, 170 mL of each slurry was sealed in a pressure resistant container having an internal volume of 300 mL, and then hydrothermal synthesis was performed at 170 ° C. and 1.0 MPa for 12 hours. 6 LiFe (PSi) O ₄ -based electrode active material was prepared.

(Examples 7 to 9)
Besides colloidal silica Snowtex O (manufactured by Nissan Chemical Co., Ltd.) was changed to H ₃ BO ₃ are prepared analogously to Example 1, to prepare a slurry of Example 7-9.
Here, B: P corresponding to each of Examples 7 to 9 is set to 0.01: 0.99, 0.03: 0.97, 0.05: 0.95, and α corresponding to these is set to 0. did.
Next, hydrothermal synthesis was performed on each slurry of Examples 7 to 9 according to Example 1 to prepare LiFe (PB) O ₄ -based electrode active materials of Examples 7 to 9.

(Comparative example)
A LiFePO ₄ -based electrode active material of a comparative example was prepared in the same manner as in Example 1 except that colloidal silica Snowtex O (manufactured by Nissan Chemical Industries, Ltd.) and H ₃ BO ₃ were not added.

"Evaluation of electrode active material"
Composition analysis, phase identification, and lattice constant measurement of each of the electrode active materials of Examples 1 to 9 and Comparative Example were performed.
Here, after each electrode active material was completely dissolved using hydrochloric acid, composition analysis was performed by ICP emission spectroscopic analysis. Table 1 shows the Si content (equivalent composition) in each of the electrode active materials of Examples 1 to 6 and Comparative Examples by ICP emission spectrometry, and Table 2 shows Examples 7 to 9 and Comparative Examples by ICP emission spectroscopy. The content (converted composition) of B in each electrode active material is shown.
As a result of the composition analysis, it was confirmed that each electrode active material contained Si or B proportional to the amount added.

Moreover, the identification of the phase of the electrode active material of each of Examples 1 to 9 and Comparative Example and the change in the lattice constant were determined using a powder X-ray diffractometer.
FIG. 1 is a diagram showing powder diffraction patterns of Examples 1 to 3 and Comparative Example, and shows peak intensities at the diffraction surfaces (311) and (121) of LiFePO ₄ .
According to this figure, when Si: P is in the range of 0.01: 0.99 to 0.05: 0.95, the generation of the impurity phase is not recognized, and the lattice constant also changes monotonously, and Li _{1 + a} It can be seen that a solid solution represented by Fe (PO ₄ ) _1-u (SiO ₄ ) _u (where 0 <a ≦ 0.05, 0 <u ≦ 0.05) is generated.

On the other hand, when the Si: P is in the range of 0.07: 0.93 to 0.15: 0.85, the behavior of the change in the lattice constant varies as the Si ratio increases. The reason is that the phosphate ion (PO ₄ ³⁻ ) is negatively trivalent while the silicate ion (SiO ₄ ⁴⁻ ) is negatively tetravalent and the anion has a large valence. It is thought that the oxidation of Fe proceeds and Fe ³⁺ (III) increases.

The same behavior was observed in each of the powder diffraction patterns of Examples 7 to 9 and Comparative Example, the formation of an impurity phase was not observed, and the lattice constant also changed monotonously, and the range of B: P and the change of the lattice constant The boundary with the range of B: P in which the behavior of B: P is different was B: P = 0.03: 0.97, but the solid solution Li _{1 + b} Fe (PO ₄ ) _1-v (BO ₃ ) produced here _v (where 0 <b ≦ 0.03, 0 <v ≦ 0.05) is Li _{1 + a} Fe (PO ₄ ) _1-u (SiO ₄ ) _u (where 0 <a ≦ 0.05, 0 < Unlike the solid solution represented by u ≦ 0.05), there is no difference in the amount of B in the electrode active material when B: P is in the range of 0.03: 0.97 to 0.05: 0.95. It was. The reason is that SiO ₂ is insoluble in water and contained in the electrode active material regardless of the presence or absence of solid solution, whereas H ₃ BO ₃ is soluble in water. Is considered to have been removed by washing.

“Production of lithium-ion batteries”
Electrode plates for Examples 1 to 9 and Comparative Example were prepared.
Here, each electrode active material obtained in each of Examples 1 to 9 and Comparative Example, acetylene black (AB) as a conductive auxiliary agent, polyvinylidene fluoride (PVdF) as a binder (binder), and a mass ratio Electrode active material: AB: PVdF = 85: 10: 5 was added to N-methyl-2-pyrrolidinone (NMP) as a solvent and mixed to obtain a positive electrode material paste.
Here, in order to compare the performance of the electrode active material itself, a paste was prepared only by mixing with a centrifugal defoaming kneader without performing treatment such as carbon coating.

Next, these pastes were applied onto an aluminum (Al) foil having a thickness of 30 μm and dried. Then, it crimped | bonded so that it might become a predetermined density, and it was set as the electrode plate.
On the other hand, metal Li was used for the counter electrode. A porous polypropylene membrane was used as the separator. Further, a 1 mol / L LiPF ₆ solution was used as the non-aqueous electrolyte solution. As a solvent for this LiPF ₆ solution, a solvent having a volume ratio of ethylene carbonate to diethyl carbonate of 1: 1 was used.
Using the electrode plate, counter electrode, and non-aqueous electrolyte solution prepared as described above, lithium ion batteries of Examples 1 to 9 and Comparative Examples were prepared using a 2016 coin cell made of stainless steel (SUS).

"Battery performance test"
A battery charge / discharge test was performed on each of the lithium ion batteries of Examples 1 to 9 and Comparative Example.
Here, charging is performed at an environmental temperature of 60 ° C. and a charging current of 0.1 CA until the potential of the test electrode reaches a predetermined charging voltage with respect to the Li equilibrium potential, and after a pause of 1 minute, discharging of 0.1 CA and 1 CA is performed. It discharged by discharging until it became 2.0V with an electric current.
In this battery charge / discharge test, the cut-off voltage was set to 2 to 4.2V.
Table 3 shows the discharge capacities (mAh / g) of Examples 1 to 6 and Comparative Examples, and Table 4 shows the discharge capacities (mAh / g) of Examples 7 to 9 and Comparative Examples.

According to Table 3, when Si: P is in the range of 0.01: 0.99 to 0.05: 0.95, the discharge capacity is increased as compared with the comparative example not containing Si, particularly at a high rate. The increase in discharge capacity was significant. The reason is that by replacing phosphate ions (PO ₄ ³⁻ ) with silicate ions (SiO ₄ ⁴⁻ ), the properties of the electrode active material itself are changed and the diffusibility of Li, which is a mobile ion, is improved. It is thought that it was possible.
Specifically, as shown in FIG. 2, the length of the b-axis, which is the diffusion direction of Li, is reduced, while the bottleneck area (area of the ac surface) between Li sites that becomes a barrier during diffusion is reduced. This is probably because Li has become easier to diffuse.

On the other hand, when Si: P is in the range of 0.07: 0.93 to 0.15: 0.85, the discharge capacity is greatly reduced as compared with the comparative example not containing Si, and this tendency is particularly remarkable at a high rate. Met. The reason for this is considered to be the effect of increasing Fe ³⁺ (III) or the generation of an insulating phase by insoluble SiO ₂ .

  Also in Table 4, the performance was improved when B: P was in the range of 0.01: 0.99 to 0.05: 0.95. However, when B is excessive, the influence of B is smaller than that of Si. It was. The reason for this is thought to be that only an influence due to a slight shift in the composition appeared because excess B was removed by washing.

According to the above results, a part of the phosphate ion (PO ₄ ³⁻ ) of the LiFePO ₄ -based electrode active material having an olivine structure is replaced with silicate ion (SiO ₄ ⁴⁻ ), borate ion (BO ₃ ³⁻ ) And other oxo acid ions other than phosphate ions (PO ₄ ³⁻ ) to replace Li as a mobile ion and part of the transition metal element as an electrochemically active element with another element. Without changing the properties of the electrode active material itself. Therefore, a lithium ion battery having excellent rate characteristics, cycle life and durability can be produced without sacrificing difficulty in forming an electrode plate due to excessive fine particles and a decrease in the theoretical capacity of the electrode active material. .

In Examples 1 to 9, although acetylene black is used as a conductive additive, carbon materials such as carbon black, graphite, ketjen black, natural graphite, and artificial graphite may be used.
Moreover, in Examples 1-9, in order to reflect the behavior of the electrode material itself in the data, metallic lithium was used for the negative electrode, but instead of metallic lithium, carbon materials such as natural graphite, artificial graphite, coke, etc. Si alloy, lithium alloy such as Li-Sn _alloy, may be used anode material such as Li ₄ Ti _{5 O 12.}

Further, as the non-aqueous electrolyte solution, a LiPF ₆ solution in which LiPF ₆ was dissolved in a solvent having a volume ratio of ethylene carbonate to diethyl carbonate of 1: 1 was used, but LiBF ₄ or LiClO ₄ solution was used instead of LiPF _6. Alternatively, propylene carbonate or diethyl carbonate may be used instead of ethylene carbonate.
Moreover, you may use a solid electrolyte instead of electrolyte solution and a separator.

The electrode active material of the present invention is Li _x A _y PO ₄ (where A is one or more selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, 0 <x ≦ 2, 0 A part of the phosphate ion (PO ₄ ³⁻ ) of the electrode active material having an olivine structure represented by <y ≦ 1.5) is converted into an oxo acid ion other than the phosphate ion (PO ₄ ³⁻ ). Replacement makes it easy to produce lithium-ion batteries with excellent discharge capacity, rate characteristics, cycle characteristics, and stability, so that not only high discharge capacity and high output characteristics, but also long-term stability, It can also be applied to fields such as power sources for mobile vehicles such as electric vehicles and hybrid vehicles that require safety and reliability, power sources such as electric tools, and load leveling applications for power generation facilities. The effect is very large.

Claims (3)

Li _x A _y PO ₄ (where A is one or more selected from the group of Cr, Mn, Fe, Co, Ni, Cu, 0 <x ≦ 2, 0 <y ≦ 1.5) An electrode active material obtained by substituting a part of phosphate ions of an electrode active material having an olivine structure represented by oxo acid ions other than the phosphate ions.   The electrode active material according to claim 1, wherein the oxo acid ion is one or two of silicate ion and borate ion.   A lithium ion battery comprising an electrode using the electrode active material according to claim 1.

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