TW201125195A - Active material for lithium secondary battery, electrode for lithium secondary battery, lithium secondary battery and fabricating method thereof - Google Patents

Abstract

An active material for lithium secondary battery contains a solid solution of lithium transition metal composite oxide having α -NaFeO2 type crystalline structure. The active material for lithium secondary battery is characterized by composite ratio of the metal element in the solid solution satisfying Li1+(x/3)Co1-x-y-zNiy/2Mgz/2Mn(2x/3)+(y/2)+(z/2) (x > 0; y > 0; z > 0; x+y+z < 1), having a X-ray diffraction pattern belonging to space group P3112, and having discharge capacitance exceeding 200mAh/g. In addition to the foregoing features, the active material for lithium secondary battery is characterized by intensity ratio of the diffraction peak of (003) surface to (114) surface measured by X-ray diffraction being I(003)/I(114) ≥ 1.15, and/or half width of the (003) surface diffraction peak being 0.15 DEG or less, and half width of the (114) surface diffraction peak being 0.25 DEG or less.

Description

[Technical Field] The present invention relates to an active material for a lithium secondary battery, a clock secondary battery using the active material for a secondary battery, and a method for producing the same. [Prior Art] In the prior 'lithium secondary battery, LiCoO 2 was mainly used as a positive electrode active material. However, the discharge capacitance is about 120 mAh/g to 130 mAh/g. A material which forms a solid solution of LiCo 2 and other compounds is known. I^CouxNixMnJC^CiXxSlO, which has a crystal structure of a-NaFe02 type and is a solid solution of three components of LiCo02, LiNi02 and LiMn02, was published in 2001. A clock secondary battery using UNii/2Mni/2〇2 or LiCo^NimMiimO2 as an example of the above solid solution as an active material has a discharge capacity of 150 mAh/g to 180 mAh/g, which is superior to LiCo02. In Non-Patent Document 1 to Non-Patent Document 4, solid solution of Li[Li1/3Mn2/3]〇2, LiNii/2Mni/; 2〇:2 and LiCo〇2 having an a-NaFe02 type crystal structure is proposed. body. This material can be expressed as Li[Li, Mn, Ni, Co] 〇2 in LiCo〇2 with a-NaFe02 type crystal structure. At the site where Co exists, Li exists in addition to the transition metal. . Therefore, a discharge capacity of about 180 mAh/g to 200 mAh/g is reported in Non-Patent Document 1 to Non-Patent Document 4, in which a higher discharge capacity can be expected. However, an active material for a secondary battery having a larger discharge capacity is sought. An example of another active material such as LiMn 2 〇 4 of the formula 201125195 5 'orthogonal spinel structure of the transition metal compound used for the positive electrode active material for a lithium secondary battery by a different element is replaced by a transition metal site. Too many to mention, a lot of research has been done. However, the effect of replacement of different elements is different for various active substances, and it is self-evident in the technical field that it is completely difficult to predict whether the effects exhibited by different materials are similarly exhibited in the case of other materials. . Non-Patent Document 5 describes that a part of Co of LiCo〇2 is replaced by Mg, and as a result, the electron conductivity at room temperature is increased (see FIG. 2, but the discharge capacity is lowered by the addition of Mg (see Fig. 6, Fig. 8). Non-Patent Document 6 describes that a part of transition metal sites of Lic〇i/3Nii/3Mn^〇 which are a solid solution of three components of Lic〇〇2, LiNi〇2, and LiMn〇2 are replaced by Mg, and the result is still In the case of Non-Patent Document 7, LitUusNio·275, which is a solid solution corresponding to two components of LiCLi^Mn^O2 and LiNi^Mn^O2, is replaced by Mg. !!. 575]. Part of the transition metal site of 2, the result is that although the capacity retention rate with repeated charge and discharge is improved, the capacitance is still reduced (see Fig. 2). In addition, the reported discharge power 200 mAh/g (refer to the figure). Patent Document 1 discloses that "a positive electrode active pair is Li_cNidC〇eLiaM,, b] 〇2 (M, which is selected from B, 峋, ab ^ V, At least one element of the group consisting of Cr, Fe, Cu, and Zn

+ e + a + b'C + d+e + a + b=l'〇^a^〇.〇5,〇^b^〇:C 0.2W0.5, read 〇.4) Oxide=main: minute, the positive electrode active material is characterized by a specific surface area of 〇3 m /g or more and 1.5 m /g or less, which is obtained by the method of the main Narita-Cheuette 201125195-Emmett marriage, BET). The χ ray diffraction pattern ' 2 Θ = 44.1 ± 1 attributed to the space group R3/m. The relative intensity ratio of the diffraction peak at the time of the diffraction peak at 2θ = 18.6 ± 1° is 〇 6 or more, 丨 i or less, and 2 Θ = 18.6 ± 1. The half-height width of the diffraction peak (when width) is 0 2 1 ΓΓ, please. The following 'and 2e = 44.1: tl. The half-width of the diffraction peak is 1〇. In the above, 〇.17〇 or less, the positive electrode active material having a particle diameter of 3 μm or more and 20 μηι = the above-mentioned strength ratio setting of 6 or more and 丨] or less can provide both a good high rate of discharge and a good charge. The discharge is cleaned into a d2: It is described as "a positive active material containing a group ^ Μ 〇, . χΝΐ〇 ^ ( ^ + 〇 &&lt; 1 3 ^ complex two (= 范: = outer == 2 = Item L 1 positive _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Forming a non-aqueous electrolyte that can produce a high rate of 6 201125195 discharge performance and green Wei-like energy, private density: positive electrode active material of under-battery" (page 6 from bottom to top line 7 - page 4) The positive electrode active material of the fifth aspect of the patent application is characterized in that the total pore volume of the composite oxide is below, and the 2θ ==44 ι ± of the powder χ ray diffraction pattern using CuKoc ray The relative intensity ratio of the diffraction peak at the time of ι is relative to 2θ-18.6±ι. The relative intensity ratio of the diffraction peak is (10) or more and 1.05 or less. According to this configuration, a special energy system can be formed. High = electrical performance, charge and discharge (four), high energy density (positive active material of non-aqueous electrolyte secondary battery with high discharge electric valley) (Page 8 from below, on line 4 to page 9 and line 3) ), "The positive electrode ^ of the patent scope of the sixth paragraph is: the specific surface area of the above composite oxide is ... 2 1 + ι Λ using CUK (X-ray powder Χ ray diffraction pattern of 2 Θ = = phase object avoids 2θ=1δ.6±1. The diurnal peak of the yang can be opened 0.65 or more and (10) or less. According to this configuration, the non-aqueous electrolyte secondary electricity of the specific degree (high discharge capacity) is extremely high; : 彳 〜 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第The half-height width of the diffraction peak at 18·6 士1 is 0.05. The height and width are ^^: the radius of the diffraction peak at 44 1 1 〇 is 1 Λ Γ 2: Γ. a positive electrode active material of a non-aqueous electrolyte secondary battery which is excellent in shape and has the same degree of enthalpy (still discharge capacity) and charge and discharge cycle performance 201125195" 9th, 11th to 16th lines, but it is not revealed that 'the half-height width of the above-mentioned diffraction peak of the active material using Mg as the specific composition of M is significantly increased in the specific range 2'. Document 3 discloses "an active material for a lithium secondary battery containing a solid solution of a lithium transition metal composite oxide having a crystal structure of a-NaFeO type" and the active material for a lithium secondary battery is characterized by the above The composition ratio of Li, Co, Ni, and Μη contained in the solid solution satisfies Lii+i/3xCo1.x.yNiy/2Mn2X/3+y/2 (x + y^l ' i _x_y = z ), at (x ) -LiNii/2Mni/2〇2 (y)丄1(^〇〇2 (z) is a triangular phase diagram, (X, y, z) is present at point A (0 45, 〇 55 points Β (0·63, 0.37, 0), point C (0.7, 0.25, 0.05), point d (0.67, 〇18

0.15), point E (0.75, 0, 0_25), point F (〇.55, 〇, 〇.45) and point G (0.45, 0.2, 0.35) as the value of the range of the inner corner of the octagonal ABCDEFG In addition, the intensity ratio of the diffraction peaks of the (003) plane and the (104) plane obtained by the ray diffraction measurement is I (003) /1 (104) 21.56 before charge and discharge, and is ϊ at the end of discharge. (〇〇3) 发明 (1〇4f &gt; 1) (Application No. 1 of the patent application) and "Manufacturing method of a lithium secondary battery", wherein the maximum reaching potential of the positive electrode during charging is 43 V ( Vs. Li/Li+) A method of manufacturing a clock secondary battery according to the above-mentioned charging method, which is characterized in that it comprises the following steps: performing over 4.3 V (vs. Li/Li+) In addition, the electric potential change in the positive electrode potential range of 4.8 v or less (vs Li/Li+) is charged in at least the flat region (see Patent Application No. 1), and the other active material is described in 201125195. In the case of generating such a disorder phase, smooth movement of ions from the Li layer does not occur. In contrast, in the active material of the present invention, since I ( 〇〇3 ) /1 ( 1 〇 4 ) $ 1 56 , the generation of the disorder phase is extremely small, and it is considered that excellent discharge capacitance can be obtained. (Paragraph [0068]), as an example, also reveals that the intensity ratio of the diffraction peaks of the (003) plane and the (1〇4) plane obtained by the ray diffraction measurement is I (003) /1 before charge and discharge. (1〇4) = ι·77, active material for lithium secondary batteries with I (〇〇3) /1 (1〇4) - 1.67 at the end of discharge and a discharge capacitance of 225 mAh/g, but the activity The material does not contain Mg, and the discharge capacity is not significantly increased when the relative intensity ratio of the active material having a specific composition of Mg is within a specific range. Further, the solid solution described in Patent Document 3 is used as an active material of lithium. The secondary battery has a problem that the capacitance at the time of high rate discharge cannot be obtained as in the comparative example described later. Patent Document 4 describes that "the species has LiaNixMny (: Gz 〇 (4) & + y + z = 1.00 1.00 &lt; a &lt; L3, 〇9&lt;〇·3) The chemical composition of the layered structure of the lining • nickel • ray • drilling composite bismuth 'this composite The diffraction peak angle of the (003) plane and the (104) plane of the powder X-ray diffraction of the oxide using the CuKa ray (Miller 丨) is respectively i865. Above and 44.50. The half-height widths of the diffraction peaks of the faces are 0_18. The following diffraction angles 2θ of the (108) plane and the (110) plane are 64.40, respectively. And 65.15. The above and the diffraction peak widths of the respective faces are both 0.18. The invention of the following (Application No. 1 of the patent application): 201125195 (10) The Miller Index C 03) surface of the powder x-ray shot and the diffraction peak angle 2 of the (104) plane are smaller than the right ^^ belt 44·50 . Then, the interval is reduced, the diffusion of lithium ions is suppressed, and the characteristics of the L η are deteriorated. In addition, if the half-height widths of the diffraction peaks of these faces are respectively ^ _18 ', the growth of the crystal may be insufficient and the variation of the composition may be large Π 04? The characteristic deterioration" (paragraph Tao 7), but the (_) surface is not revealed and ^ Patent Document 5 of the diffraction peak half-height width (full width at half maximum) and high-rate discharge characteristics describes a positive electrode active material, which is contained in a space group R_3m and corresponds to a (1〇4) plane ^= The half-height of the diffraction peak is in the team, 15. The lithium-containing metal composite oxide particles having an average value of the shape factor SF1 calculated by the following formula (1) are larger than 丨 and are in the range of η :::. The invention of the patent application (the first paragraph of the patent application), and the disclosure that the crystal structure of the metal-containing composite oxide particles is attributed to the space group _3111 and corresponds to the X-ray diffraction peak of the (104) plane. The half width is at 0.06. ~〇 15. In the range of the above, a higher discharge load characteristic (high rate discharge characteristic) can be obtained; and if the full width at half maximum exceeds 0.15. 'The crystallinity of the lithium-containing metal composite oxide is lowered and it is difficult to obtain a high high-rate discharge characteristic (paragraph [secret]); however, the inclusion of Mg in the metal-containing composite oxide is completely undocumented and has not been revealed. The high-rate discharge characteristics are remarkably improved by setting the full width at half maximum of the diffraction peak of the cerium-containing metal composite oxide containing Mg. Patent Document 6 describes that "the LiNiwMnwCowO2 of the present invention can be doped with a different element to exhibit an additional function, and the electron conductivity can be greatly improved by adding magnesium in 201125195" (paragraph [0077]); It is also disclosed that 'the oxide represented by LitLi/NiwMnwCch/UOz (in the formula 'O^xSO.3) which increases the lithium atomic ratio can be used to dry-mix the composite oxide compounded with the lithium hydroxide in a dry manner. The nickel-manganese-cobalt composite oxide calcined under looot: is a hexagonal system belonging to the layer structure R3m (paragraphs [0028] to [0030]); however, it is not suggested that magnesium is contained in the nickel-manganese-cobalt composite oxide. When it is a solid solution component, the discharge capacity is remarkably improved, and the high rate discharge characteristics are remarkably improved. Patent Document 7 describes "a composite of a choline-type composite oxide powder for a lithium secondary battery positive electrode material, which is composed of a crystal structure belonging to a layered structure, and its composition is as follows (I ), expressed as %

Li[Liz/(2+z) {(LixNi(1_3x)/2Mn(1+x)/2)(1.y)C〇y} 2/(2+z)]〇2... (I) (in which '0.01SxS0.15, 0Sy$0.35, 0.02(ly) (1_3χ) SzS0.15 (1-y) (l-3x))" (the scope of claim 6); and reveals that 'important is The amount of Li is slightly richer than the stoichiometric composition, whereby the battery performance (especially the rate characteristic ^ output characteristic) is improved (paragraph [0014] and paragraph [〇〇15]), but it is not revealed When the lithium nickel manganese cobalt composite oxide is a specific composition containing magnesium, the 'electrical capacitance is significantly improved' and the high rate discharge characteristics are remarkably improved. In addition, the positive electrode active material for a lithium secondary battery described in Patent Document 1 to Patent Document 7 is not assumed to be Li[Li1/3Mn2/3]〇2 'LiNi^Mn^O2, LiC〇〇2, and LiMg^Mr^O2. In the case of the above-described positive electrode active material, if the content of the positive electrode active material is Mg and the relative strength ratio is satisfied, the discharge capacity cannot be expected to be improved from the descriptions of Non-Patent Documents 5 to 5. [Prior Art Document] [Non-Patent Document] [Non-Patent Document 1] Electrochim. Acta, vol. 51, page 5581-5586, 2006.

[Non-Patent Document 2] J.p〇wer Sources, vol. 146, page 598-601, 2005.

[Non-Patent Document 3] J. Electrochem. Soc., vol_l52, no.l, page A171-A178, 2005.

[Non-Patent Document 4] Mater丄ett., vol.58, page 3197-3200, 2004.

[Non-Patent Document 5] J. Electrochem. Soc., vol. 144, page 3164-3168, 1997.

[Non-Patent Document 6] Solid State Ionics, vol. 178, page 849-857, 2007.

[Non-Patent Document 7] J. Mater. Chem., vol 13, page 319-322, 2003.

[Patent Document 1] Japanese Patent No. 4320548 [Patent Document 2] WO 2002/086993 A1 [Patent Document 3] WO 2009/063838 A1 [Patent Document 4] Japanese Patent No. 4216669 No. 12 201125195 [Patent Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The problem is to provide an active material for a lithium secondary battery having excellent discharge electric power and high south rate discharge characteristics, and a lithium secondary battery using an active material for a smectic lithium secondary battery. The technical concept of the configuration and effects of the present invention will be described. Among them, the mechanism of action includes presumption, and its correctness does not limit the invention. Further, the present invention can be embodied in other various forms without departing from the spirit or essential characteristics thereof. Therefore, the embodiments or experimental examples described below are merely illustrative and not limiting. Further, all of the changes to the equivalent of the patent application are all within the scope of the present invention. A material having a crystal structure of a-NaFe〇2 type and which can be expressed as Li[Li,Mn,Ni,Co]〇2 should pay attention to the valence of each element of the transition metal site. That is, 'in the case of synthesizing a material which can be expressed as Li[Li Mn, Ni, the domain ratio of U and _ which is not arbitrarily set as a metal element contained in the complement 岐" is present in each metal quinone present at the transition metal site. The valence becomes the condition of Li1+, Ni2+, c〇3+ Γΐ ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί When the secondary battery is used as an active material, it can exhibit a high discharge capacity. The valence of each metal element becomes a strip of Li丨+, Mn〇, Nia, c〇3+. 201125195 can be imagined by considering Li[Li1/3Mn2/3]02, LiNi1/2Mn1/202 and LiCo〇2 Provided by a solid solution. That is, by envisioning xLitLimMr^/JCVyLiNimMn^C^-(1-xy)LiCo02 (where x&gt;0, y&gt;0, x + y&lt;l), and arbitrarily selecting x and y, theoretically a- The valence of each metal element present in the transition metal site of the NaFe〇2 type crystal structure is Li1+, Mn4+, Ni2+, Co3+. The active material for a lithium secondary battery of the present invention is characterized by containing Mg, but at this time, it is also necessary to pay attention to the valence of the metal element present at the transition metal site. In other words, the effect of the present invention is remarkably exhibited by setting the ratio of each metal element under the condition that the valence of each metal element present at the transition metal site becomes Li1, Co3+, Ni2+, Mn4+, and Mg2+. Here, when the Mg ratio is set under the condition of maintaining Li1+, Mn4+, Ni2+, Co3+, and Mg2+, several ideas can be employed. The first idea is to set the Mg ratio according to the idea of replacing the Νθ+^Μη4'/2 portion of the envisioned LiNi^Mn^O2, as in the case of Example 2-1 to Example 2-6. Detailed details. The first idea is to replace the constituent LiELimMn2/3] by the substitution. The method of setting the Mg ratio by the idea of [Li^Mn2/3]3&quot;1 part of 2 is specifically described in detail in the present specification as Example 2_7 to Example 21(). The third idea is to think of a method of setting the Mg ratio based on the idea of replacing Co3+ by [Mgi/2Mni/2]3+. Also think of ways to repeat the application of two or three of these ideas. When using any of the above ideas, it can be known that the valence of each metal element becomes Li1+, Mn4+, Ni2+, C〇p, Mg2+, and the assumption can be made by envisioning 14 201125195

A solid solution of four components of Li[Li1/3Mn2/3]02, LiNi1/2Mn1/2〇2, LiCo02, and LiMg1/2Mn1/2〇2 is provided. That is, by considering a solid solution xLi[Lii/3Mn2/3]〇2-yLiNii/2Mn1/2〇2-zLiMg1/2Mni/2〇2-(1 -xyz) LiCo〇2 (x>0, y&gt; 〇, z &gt; 〇, x + y + z &lt; l) and arbitrarily select x, y and z 'The theoretical valence of each metal element present in the transition metal site of the a_NaFe02 type crystal structure is Li1+, Co3+, Ni2+ Mn4+, Mg2+ 〇 right' The above formula xLi[Li1/3Mn2/3]02-yLiNi1/2Mn1/2〇2_zLiMg1/2Mn1/2〇2-(1-xyz) LiCoC^a is deformed, which can be obtained Formula Ul+(x/3) C〇ixy-zNiy/2Mgz/2Mn (2X/3) + (y/2) + (z/2) 〇2. Here, the present invention is an active material for a lithium secondary battery, which comprises a solid solution of a lithium transition metal composite oxide having a crystal structure of a_NaFe〇2 type, and the active material for a lithium secondary battery is characterized by the above The composition ratio of the metal element contained in the solid solution satisfies Li1+(x/3) Cok.yJSiiMMg^Mn(2x/3) + (y/2) + (z/2) (x&gt;0, y&gt;〇, z&gt ; 〇, x + y + z &lt; l), having an X-ray diffraction pattern ' attributable to the space group P3! 12 and having a discharge capacitance exceeding 2 mAh/g. As shown in the comparative example described later, even if the active material satisfies the composition ratio of the metal element and has an X-ray diffraction pattern that can be attributed to the space group P3ll2, the discharge capacity may be 2 mAh/g or less. In the present invention, the active material is limited to an active material having a discharge capacity of more than 200 mAh/g obtained by a charge and discharge cycle test described later. In order to make the above-mentioned active material have a discharge electric current of more than 200 mAh/g, the influence of the calcination temperature is large, and the solid solution of the inner transition metal composite oxide satisfying the composition ratio of the above metal elements is more than 9 〇〇. Its temperature, for example, calcination at a temperature of 920 C or higher, can obtain an active material having a discharge capacity of more than 2 mAh/g. When the calcination temperature exceeds (1) (8) Å, an active material having a x-ray diffraction pattern attributable to the space group 1 &gt; 3112 may not be obtained, and therefore it is preferably 1000 ° C or less. The present inventors have found for the first time that when the solid solution of the above-mentioned Mg-containing lithium transition metal complex oxide is made into an active material having a large discharge capacity of more than 2 mAh/g, the high rate discharge characteristics are remarkably improved. From the viewpoint of satisfying the composition ratio of the above-described metal element and having an X-ray diffraction pattern attributed to the space group P3! 12, for example, the (〇〇3) surface obtained by X-ray diffraction measurement When the intensity ratio of the diffraction peak to the (114) plane is 15, the half-height of the diffraction peak of the (〇〇3) plane is 〇.15. The half-height width of the diffraction peak of the following (114) plane is 0.25. The following has a discharge capacitance of more than 200 mAh/g. ^Generally, if a compound having an a-NaFe02 type crystal structure = transition metal composite oxide is synthesized by a calcination step, and the compound actually obtained by the ore is subjected to knife analysis to determine the elemental composition ratio, it is actually known that There is a slight (about 5%) change in the composition calculated from the composition ratio. The capital invention may be carried out without departing from its technical idea or main features, and it should not be construed that the material obtained by synthesis is not within the scope of the invention only because the composition is not strictly consistent with the above composition. In particular, regarding the amount of Li, it is known that it is easily volatilized in the calcination step. Further, the 201125195 coefficient of the oxygen atom may vary depending on the synthesis conditions and the like, and the case where it is not strictly limited to 2 should not be construed as being in the range of the present invention due to the oxygen deficiency. Further, j is t, and the coefficient of oxygen is not defined in the above formula in which the metal element composition ratio is specified. In addition, the active material of the present invention may contain an element other than Li, Co, Ni, Μη, Mg, or yttrium containing "Li, c〇, milk, Μη, 〇, 〇::" It is also required that the valences of '^, Co, Ni, Μ, and Mg in the first solid solution constituting the solid solution satisfy the valence conditions of +, Μ, 44+, and Μ§2+, respectively. Furthermore, the amount of Li in the active material changes with the discharge of the battery, and the valence of the transition metal is also improved, but even if the self-charge and discharge depth is not (four) the active substance taken by the battery can also be coupled by inductive coupling. The plasma contains the metal element of u when the active material is synthesized, so that it can be judged as the active substance of the 疋 亥 活性 活性 活性 1 1 1 1 1 1 1 ICP ICP ICP ICP 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成 合成Whether it is within the technical scope of the present invention. This j, a powder which is simply a mixture of LiCo〇2 powder, LiNii/2Mni 2〇2 powder, postal-feng 2 powder, etc. cannot be regarded as a η "solid solution". . The individual materials of these materials have different peak positions corresponding to the respective lattice constants observed during the ray-ray diffraction measurement. Therefore, it is possible to perform the χ-ray diffraction measurement on the simple mixtures. The diffraction pattern corresponding to each item. Here, by selecting the value of the range of 1/3 &lt; χ &lt; 2/3 as X, it is preferable to use the material synthesized as the active material for the clock secondary battery as compared with the 201125195 H capacitance. . The value of x or y can be determined by considering the battery characteristics of the battery to be used for the chain = electroactive substance, and the appropriate selection is two: 1, and the amount of Mg is related, but as shown in the example below, even if Mg ίί In the case of Mg, the number of discharges is also remarkably improved. Since the second two 2'Mg does not occur, even if it is charged and discharged, it is not useful, and it is preferably not excessively contained. The expression of the yarn of the present invention at the time of ζ·? value is different depending on the value of Χί y. Therefore, it is necessary to determine the value of X, 'and then the value of Χ and Υ according to the design of the battery. According to the above technical idea, the value of z which is appropriate for the value of z can be increased by 4, and the vehicle father is 0 &lt; y &lt; 2 / 3, 〇 &lt; z < 〇 3. As described above, the "active material for a secondary battery contains a solid solution of a clock transition metal composite oxide having an aNaFe〇2 type crystal structure, and the metal element contained in the above m solution is tested. The ratio satisfies LH+(χ/3) Co^^Ni^Mg^Mn (2x/3) + (y/2) + (z/2) ( x&gt; 〇, y &gt; 〇. Z&gt;0, X + y +z&lt;1)", which can exhibit a high discharge capacity; in the present invention, in order to significantly increase the discharge capacitance and the high rate discharge impurity, the JU solution of the above-mentioned clock transition metal composite oxide has a function attributable to The X-ray diffraction pattern of the space group Phu is such that the intensity ratio of the diffraction peaks of the (003) plane and the (114) plane obtained by the x-ray diffraction measurement is j (〇〇3) / (114) $1.15, and / or the half-height of the diffraction peak of the (〇〇3) plane is 0.15. Hereinafter, the full width at half maximum of the diffraction peak of the money (114) plane is 〇25. the following. Furthermore, the x-ray diffraction pattern of the above solid solution of the present invention can be attributed to the 201125195 space group P3J2' but it is not impossible to belong to the space group R3 卬 to the (four) group! &gt;3ll2, the diffraction peak of the (114) plane is the other part of the space group R3-4. The space of the (104) plane is the genus of the diffraction wave, and the expression of the space group, "R3_m" In the case of "3", the horizontal line (ba〇 "_" is used, but the specification sheet is "R3-m". The active material for the lithium secondary battery of the present invention is expressed by the use of the present invention. , 艮 采用 采用 采用 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电 充电In the manufacturing process of the secondary battery, the charging step of the active material for the clock secondary battery of the present invention is considered. That is, the same as the active material of the clock secondary electric power described in Patent Document 3, the present invention is Containing a Mg_secondary battery substance, if it is used for a positive electrode and continuous constant current charging, as shown in the later example, in a range of positive electrode potentials 4 3 v to 4 8 v for a relatively long period of time A region in which the potential change is relatively flat is observed. Here, the present invention A method for producing a lithium secondary battery, which is a method for producing the above-described lithium secondary battery by using a maximum electric potential of a positive electrode at the time of charging, which is 4.3 V (vs. Li/Li+) The special feature consists in the steps of performing a charge change occurring in a positive electrode potential range of more than 4 3 V (vs Li/Li+) and below 48^ (vs. Li/Li+) to at least a relatively flat region. Here, the charging of the initial charging and discharging step before the completion of the battery must be performed until at least the potential flat region is reached. The potential flat region phase 2 19 201125195 (for example, 1 () 〇 mAh / g J ^) continues, so it is better It can be continuously charged by the method of _ Cheng. In addition, when the end point of the electrolysis zone is detected due to the potential, the charging can be set accordingly, and the constant current can be used according to the condition. According to the present invention, it is possible to provide an active material for a lithium secondary battery having a large discharge capacity and a high rate of release, by the constant voltage charging and the electric enthalpy value being attenuated to a constant value of 2. Ming as follows The above and other objects, features and advantages of the present invention will become more apparent from the aspects of the preferred embodiments of the invention. The method is to say that the active material f of the secondary battery can basically be composed of the following two elements, ie, a metal element ai, Mn, c constituting the active material. Right horse (6) mesh "active material (oxidation) The composition of the material is adjusted in the same way and burned. Among them, regarding the amount of Li raw material, : ^ is the part of the material disappeared - so the excess is added 1 % ~ 5% left ^

In the case of oxides composed of Mn and If 2, it is known that Li, Co, and Ni are referred to as "solid phase method - co-precipitation precursor of T. Biw human 〇 Ni Mn, Mg, and j; It is difficult to uniformly obtain a sample with a uniform distribution of each element in the particle with respect to Co and Ni [20 201125195 to date or Co f ' ( ^ 止 ' has been extensively carried out in the literature and the like by solid phase method Attempts to dissolve in a part of Nl (LiNilxMnx02, etc.), but it is easier to obtain a homogeneous phase at the atomic level by selecting the "Qiu Shen Dian Method". Therefore, the "common test" is used in the example. Again, this precursor For example, referring to the description of Patent Document 2, it is extremely important to make an inert environment in a solution for obtaining a coprecipitation precursor in the production of a pre-precipitate precursor. The reason is that c, Ni, shirt, In the Mg, Μη is easily oxidized, and it is difficult to produce a co-precipitated hydroxide which is uniformly distributed in a state in which c〇, Mn, and the core are uniformly distributed in a valence state. Therefore, uniform mixing of atomic levels of Co, Ni, Mn, and Mg is likely to become impossible. Sufficient, especially in the composition range of the present invention, due to the high ratio of Μη In the ratio of c〇 and Ni, it is more important to make the solution inert in the solution. In the following examples, the inert gas is bubbling in an aqueous solution to remove dissolved oxygen, and the reducing agent is simultaneously added dropwise. The method for adjusting the precursor is not limited. The Li compound, the Μ 化合物 compound, the Ni compound, the c 〇 compound, and the Mg compound may be separately mixed, or the transition metal element-containing hydroxide may be co-precipitated in the solution, and the The Li compound is mixed. In order to produce a uniform composite oxide, a method in which a common compound of Mn, Ni, Co, and Mg is mixed with a Li compound and calcined is preferably used. A compound obtained by uniformly mixing Mn, Ni, Co, and Mg is preferable. The precursor is not limited to a hydroxide, and other elements such as a carbonate and a citric acid 21 201125195 salt are uniformly present at an atomic level. The poorly soluble salt can be used in the same manner as the hydroxide. Further, it is also possible to produce a bulk density by using a crystallization reaction using a complexing agent or the like. At this time, since the living substance 1 having a higher density and a smaller specific surface area can be obtained by mixing and calcining with the Li source, the energy density per unit electrode area can be increased. Examples of the raw material of the material include manganese oxide, manganese carbonate, manganese sulfate, manganese nitrate, and manganese acetate. Examples of the Ni compound include nickel hydroxide, nickel carbonate, nickel sulfate, nickel nitrate, nickel acetate, and the like, and Co. Examples of the compound include cobalt sulfate, cobalt nitrate, and cobalt acetate. Examples of the Mg compound include magnesium sulfate, magnesium nitrate, and acetic acid. The raw material for preparing the coprecipitated hydroxide precursor is preferably a base. The aqueous solution can be used in any form, and it is preferred to use a metal salt having a high solubility. The active material for a lithium secondary battery of the present invention can be suitably produced by mixing the above-mentioned coprecipitated hydroxide precursor with a Li compound and then heat-treating it. It can be suitably produced by using a hydroxide, a carbonic acid clock, a sulphuric acid clock, an acetic acid clock or the like as a Li compound. When obtaining an active material with a significantly increased discharge capacitance, the choice of the firing temperature is extremely important. By setting the calcination temperature to 92 ° ° C to ioooc as described later, "the composition ratio of the metal element contained in the solid solution satisfies Lii + (χ / 3) C〇1.xy2Niy/2Mgz/2Mll ( 2x/3) + (y/2) + (z/2) (χ&gt;〇- y&gt;〇χ z &gt;〇, x + y + z&lt;1)" solid solution of lithium transition metal composite oxide With 22 201125195 =: 彳 而 而 rt quality accompanied by oxygen release

Li[Li1/3Mn2/3]〇2 type, the tendency to observe monoclinic crystals other than hexagonal crystals, L becomes a solid solution phase and decreases in phase, so the reversible capacitance of poor active materials is large. 45. Observe the X-ray diffraction pattern on the nearby 35. The oxygen release near and below the active material is reversed, and the temperature of the burn is important to set the oxygen release temperature to the group of the present invention; = = == The oxygen = degree has a slight deviation, so the Γη I contained in the 槐 is better, temperature. In particular, because the male recognizes the test shift, it is necessary to use the method of 'the main oxygen release temperature of the precursor to the oxygen release temperature of the low temperature side. The mixture of L_2〇 is used for the thermogravimetric analysis: a total of two:): := Sample volatilization...

尤女·心 “Green is better to use 50 (TC crystallization of a certain degree of composition for the heat r: surface: the temperature is too low, the crystallization is not fully carried out, Ιϋ 'by X-ray The intensity ratio of the diffraction peak of the (〇〇3) plane* (1 4) plane obtained by the diffraction measurement is 1 (_~) &lt; 115, and the capacitance of the 201125195 is lowered, so the less than the less than 9003⁄4 is better. In the invention, the calcination temperature must be set so as to smoothly crystallize, and it is important to reduce the impedance of the grain boundary, and the promotion method is more important. The crystallization loss is determined by visual observation of the electron microscope. θ Λ s snn. When scanning electron microscope observation, if the sample is synthesized = in = ', the sample is formed by nano-order particles, and the synthesis temperature is crystallized until: In addition, in the aspect of γ λ, another standard indicating the degree of crystallization is the above-mentioned six-, half-height width of the Ί scale. In the present invention, in order to improve Not only the discharge valley but also the A-rate discharge characteristics, preferably the 'shots belonging to the space group Ρ3! In the diffraction pattern, the full width at half maximum of the diffraction peak of the (GG3) plane is 〇15. The following is the case where the half-height width of the diffraction peak of the (114) plane is 〇25 or less. (〇〇3) The full width at half maximum of the diffraction peak is preferably 〇14. 〇15., (114) The full width at half maximum of the diffraction peak is preferably 0.23. ~0.25. To make the diffraction peak of the (003) plane The full width at half maximum is 〇15. The full width at half maximum of the diffraction peak of the (114) plane is 〇25. Below, the temperature of the sinter is also increased. As described above, the preferred calcination temperature is based on the oxygen release temperature of the active material. However, it is difficult to set the preferred range of the calcination temperature, but it is preferably 900 ° C to l 〇 5 〇 t:, more preferably 920 ° C to 1 〇 00. (:, can exhibit high characteristics The full width at half maximum of the diffraction peak is governed by the amount of deformation indicating the degree of mismatch of the crystal lattice, and the crystallite size as the minimum domain. The factors are determined according to the factor of the semi-high width. The degree of crystallinity must be separately grasped. The inventors confirmed by the detailed analysis of the full width at half maximum of the active material of the present invention. In the sample synthesized at a temperature lower than C, deformation is left in the crystal lattice, and the deformation can be almost removed by synthesis at a temperature higher than the temperature. Correction, the size of the crystallite becomes larger in proportion to the increase in the synthesis temperature. Therefore, the composition of the active material of the present invention is also only y in the system, and y is formed into particles having a sufficiently large crystallite size, whereby a good discharge capacity can be obtained. Specifically, it is preferred that A synthesis temperature (calcination temperature) in which the amount of deformation affecting the lattice constant is 1% or less and the crystallite size is increased to 15 Å or more. The active material is formed into an electrode and charged and discharged, and expansion is also observed. The change caused by shrinkage is also preferable in that the crystallite size is maintained at 130 nm or more in the charge and discharge process. Namely, by selecting the calcination temperature as close as possible to the oxygen release temperature of the above-mentioned active material, an active material having a reversible capacitance significantly large can be obtained. The nonaqueous electrolyte used in the lithium secondary battery of the present invention is not limited, and a nonaqueous electrolyte which is generally proposed for use in a lithium battery or the like can be used. Examples of the nonaqueous solvent used for the nonaqueous electrolyte include cyclic carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, chloroethylene carbonate, and ethylene carbonate. ; γ-butyrolactone, γ-valerolactone and other cyclic esters; chain carbonates such as dinonyl carbonate, diethyl carbonate, carbonate ethyl fluorenyl; Chain esters such as decyl ester, decyl acetate, decyl butyrate; tetrahydrofuran or its derivatives; 1,3-dioxane, 25 201125195 1, 4-dimethoxy ethane, 1,2-dimethoxy ethane, 1,4-dibutoxyethane, methyl diglyme, etc. Mysteries; nitriles such as acetonitrile and benzoquinone; dioxolane and its derivatives; ethylene sulfide, sulfolane, and sultone And a derivative thereof, or the like, or a mixture of two or more of them, but is not limited to the solvents.

Examples of the electrolyte salt used for the nonaqueous electrolyte include lithium (Li) and sodium (LiC104, LiBF4, LiAsF6, LiPF6, LiSCN, LiBr, Lil, Li2S04, Li2B10Cl10, NaC104, Nal, NaSCN, NaBr, KC104, KSCN, etc.). An inorganic ion salt of one of Na) and potassium (K); LiCF3S03, LiN(CF3S02)2, LiN(C2F5S02)2, LiN(CF3S02)(C4F9S02), LiC(CF3S02)3, LiC(C2F5S02)3, ( CH3) 4NBF4, (CH3)4NBr, (C2H5)4NC104, (C2H5)4NI, (C3H7)4NBr, (n-C4H9)4NC104, (n-C4H9)4NI, maleic acid-(C2H5)4N ( C2H5)4N-maleate ) 'benzoic acid-(C2H5)4N ((C2H5)4N-benzoate), phthalic acid-(C2H5)4N ((C^HAN-phtalate), stearyl mineral acid chain, octyl acid clock An organic ionic salt such as lithium dodecylbenzenesulfonate or the like, which may be used singly or in combination of two or more. Further, by having a perfluoroalkane such as LiBF4 and LiN(C2F5S02)2 The mixed use of the base bell salt can further reduce the viscosity of the electrolyte, so that the low temperature characteristics can be further improved, and the self-discharge can be suppressed, which is more desirable. The ionic liquid is used as the non-aqueous electrolyte. 26 201125195 Regarding the concentration of the electrolyte salt in the non-aqueous electrolyte, in order to reliably obtain a non-aqueous electrolyte battery having high battery characteristics, it is preferably 〇丨m 〇 1 / 1 to more preferably 0. 5m〇1/1~25m〇iA. ▲The negative electrode material is not limited to 'as long as it can precipitate or absorb ions.' For example, it can be exemplified: u is a large spar type represented by melon muscle. Titanium-based material such as lithium titanate having a crystal structure, Si or Sb, Sn-based alloy-based material, clock metal, and alloy (Li-Shixi, Li-Aluminum, Chain_, Lithium-tin, Lithium-Aluminum- Tin, lithium-gallium and alloys containing clock metal such as Wood's metal, chain composite oxides (Li-titanium), oxidized stone eve, in addition to: absorbing and releasing An alloy of lithium, a carbon material (for example, graphite, hard carbon, hard alloy, low-temperature calcined carbon, amorphous, etc.), etc. The powder of the positive electrode active material and the powder of the negative electrode material are preferably average particle size. It is below 100 μηη, especially to improve the nonaqueous electrolyte battery. In the output characteristics, the powder of the positive electrode active material is preferably not more than μηη, and the powder is obtained in a specific shape, and a pulverizer or a knife-level machine can be used. For example, a mortar, a ball mill (bau miu), a sand mill, a vibratory ball mill, a planetary ball mill, a jet mill, a counter jet mill, a vortex jet mill or Sieves, etc. In the case of crushing, it is also possible to use wet pulverization of organic or solvent which coexists with water or hexane. The classification method is not limited, and the dry or wet type of the _ or the wind classification is used as needed. The above is a detailed description of the positive electrode active material and the negative electrode material which are main constituent components of the positive electrode and the negative electrode, and the positive electrode and the negative electrode include a conductive agent, a binder, a tackifier, and a sand cell performance slit in addition to the above 27 201125195. No (four) ringing electron conduction 'is not limited' can usually include natural graphite (scaly graphite, two, graphite, earthy graphite, etc.), artificial graphite, carbon black (C (10) ac, acetylene black, One or more of conductive materials such as Ketjenblack, carbon whisker, carbon fiber, metal (copper, nickel, aluminum 'silver, gold, etc.) powder, metal fiber, conductive material, etc. In the above, from the viewpoint of electron conductivity and coatability, the conductive agent is ruthenium acetylene black. The amount of the conductive agent added is preferably 0.1% by weight relative to the total weight of the positive electrode and the negative electrode. % (% by weight) ~ 5 〇 wt%, particularly preferably 0.5 wt% 〜 30 wt%. Especially if acetylene black is pulverized into ultrafine particles of 〇] μιη~〇5 μιη, the amount of carbon required can be reduced. Therefore, it is ideal. The mixing method of the components is physical mixing, and it is desirable to uniformly mix. Therefore, it is possible to mix a powder mixer such as a V-type mixer, an S-type mixer, a crusher, a ball mill, or a planetary ball mill in a dry or wet manner. The above-mentioned bonding agent can usually be a thermoplastic resin such as polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF), polyethylene or polypropylene, and an ethylene-propylene-diene terpolymer. One or two of rubber-elastic polymers (ethylene-propylene-diene tei^polymer, EPDM), feldsparized butadiene rubber (SBR), fluororubber, etc. The mixture on 201125195. The amount of the binder added is preferably from 1 wt% to 50 wt〇/0, particularly preferably from 2 wt% to 3 〇 wt%, based on the total weight of the positive electrode and the negative electrode. The material that adversely affects the performance may be any material. Generally, a olefinic polymer such as polypropylene or polyethyl amide, amorphous cerium oxide, aluminum oxide, zeolite, glass, carbon, etc. may be used. The amount of the material to be added is 30% by weight or less based on the total weight of the positive electrode and the negative electrode. The positive electrode and the negative electrode are suitably produced by the following main components: the positive electrode is a positive electrode active material, and the negative electrode is a negative electrode. The material and other materials are kneaded into a mixture, and mixed into an organic solvent such as N-methyl-Pyrrolidinone or benzene (e) (e), and the resulting mixture is applied to a current collection which will be described in detail later. In the body, the line is crimped and placed at 50. (: ~25 (heat treatment for about 2 hours at a temperature of about TC. The above coating method is preferably, for example, roll coating using a applicator roll or screen coating (like a coffee maker) A method such as a doctor blade method, a spin coating method, or a bar coater (bar coate O) is applied to any thickness and any shape, but is not limited thereto. A separator is preferred. In order to use a porous film or a non-woven fabric which exhibits excellent high rate discharge performance, the material for forming a separator for a nonaqueous electrolyte battery is, for example, a polyolefin resin represented by polyethylene or polypropylene. Polyethylene terephthalate, polybutylene terephthalate, etc., represented by polyg-type resin, polyvinylidene fluoride, diethylene glycol, hexamethacrylic copolymer, defluoridation B; B County (4) Copolymer, partial 2 29 201125195 Vinyl fluoride-tetrafluoroethylene copolymer, partial ethylene ethylene _ trifluoroethylene copolymer, vinylidene fluoride _ fluoroethylene copolymer, vinylidene fluoride - hexafluoroacetone copolymer, partial fluoroethylene ethylene-ethylene copolymer, partial Ethylene-propylene copolymer, vinylidene fluoride-difluoropropene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-ethylene-tetrafluoroethylene copolymer, etc. The porosity of the separator is preferably 98 v〇l% (volume percent) or less from the viewpoint of the strength, and the porosity is preferably 20 vol% or more from the viewpoint of charge and discharge characteristics. As the separator, for example, acrylonitrile, ethylene oxide, propylene oxide, methyl methacrylate, vinyl acetate, vinyl pyrrolidone, polyvinylidene fluoride or the like can be used. When a non-aqueous electrolyte is used in a gel state as described above, it is preferable to use a non-aqueous electrolyte in the gel state as described above. Further, if the separator is as described above, When a porous film, a nonwoven fabric, or the like is used in combination with a polymer gel, the liquid retention property of the electrolyte is improved, that is, it is preferably formed on the surface of the polyethylene microporous film and the surface of the microporous layer to have a thickness of several μm or less. a film of a solvophilic polymer that will be charged The solvophilic polymer forms a gel in the micropores of the film. The solvophilic polymer includes, in addition to polyvinylidene fluoride, a propylene group having an epoxy group or an S group. a polymer obtained by crosslinking a dilute acid, a monomer, an epoxy monomer, or a monomer having an isocyanate group, etc. The monomer may be combined with a radical initiator to use heat or ultraviolet rays (UV), or to use electrons. A cross-linking reaction is carried out by using an active light such as a beam (EB). In the case of a battery having a positive electrode, a negative electrode, a flat battery, or the like, a cylindrical battery having a roll-shaped separator is not particularly limited. A square battery is cited as an example. / [Example 1] (Example 1-1) and =, pentahydrate, sulfur _ hexahydrate, sulfur sulphate sulphate == heptahydrate with CG, N1, Mn, Mg each element becomes 12.5: and IHH75 · The ratio of the ratio of 1312 was dissolved in the ion-exchanged water at this time 'the total concentration was G.667 mol/1, ft 0 ml. Then, in a 1 L (liter) beaker, the ion-exchanged water of the medium was kept in a thief using a hot water bath, and 8 ' aOH' was added to adjust the value of ρ 为 to 12 〇. In this state, the chlorine (Ar) drum was bubbled for 30 minutes, and the dissolved oxygen in the solution was sufficiently removed. The inside of the beaker was stirred at a rotation speed, and a mixed aqueous solution of the above sulfate was added dropwise at a rate of 3 ml/min. In the meantime, the temperature of the water bath was kept constant, and 8 N of NaOH was intermittently added thereto to keep the pH constant. At the same time, 50 ml of a hydrazine aqueous solution having a concentration of 2 〇 mol/Ι as a reducing agent was added dropwise at a rate of 0.83 ml/min. After the completion of the dropwise addition, the mixture was allowed to stand still for 12 hours or more while the stirring was stopped, and the coprecipitated hydroxide was sufficiently grown to grow the particles. Further, if the dropping rate of each solution is too fast in the above procedure, a uniform precursor cannot be obtained at the elemental level. For example, when the drop acceleration is set to 10 times the above speed, the element distribution in the precursor becomes significantly uneven. Further, when the active material is synthesized using such a non-uniform precursor, the distribution of the elements after calcination in 31 201125195 is also uneven, and sufficient electrode characteristics cannot be exhibited. Incidentally, when Li〇H.H20, C〇C〇H)2, Ni(OH)2, MnOOH, and Mg(OH)2 are used as the raw material powder by the solid phase method, they are more uneven, so Poor. Then, the coprecipitated product was taken out by suction filtration, and dried in an air atmosphere at normal pressure at 100 ° C in an oven. After drying, a dry powder was obtained by pulverizing the pellets in a uniform manner with a diameter of about 120 mm (p) for several minutes. It was confirmed by X-ray diffraction measurement that the dry powder was P_Ni(〇H)2 type. In addition, it was confirmed by ΕΡΜΑ measurement that c〇, Ni, and Mn were uniformly distributed. The amount of Li with respect to the metal element (Ni + Mn + Co + Mg) satisfies the composition formula of Example 1-1 of Table 1. The lithium hydroxide monohydrate powder (LiOH, H2 〇) was weighed and mixed to obtain a mixed powder. Then, the mixed powder was pelletized at a pressure of 6 MPa. The precursor powder for pellet molding The amount is determined by converting the weight of the synthesized product to 3 g. As a result, the molded pellet has a diameter of 25 mmcp and a thickness of about 1 mm to 12 mm. 1 〇〇mm alumina boat (b〇at), placed in a box-type electric furnace, calcined in an air atmosphere at normal pressure at 1 〇〇 (rc for 12 h. The above-mentioned box-type electric furnace The internal dimensions are 10 cm in length, 20 cm in width, 30 cm in ice, and 2 cm in width. Put the electric heating line between them. Calcination ^, cut off the heater switch, keep the aluminum boat in the furnace and let it cool naturally. As a result, the temperature of the furnace drops to about 32 after 2011. After about C, the temperature of the subsequent cooling was slightly slow. After a day and night, it was confirmed that the temperature of the furnace was 100 ° C or less, and then the particles were taken out and pulverized to a uniform particle size using a mortar. Composition

Lii.2Co01Ni0139Mg0011Mn0.55〇2 ' As for the crystal structure, the powder X-ray diffraction measurement using Cu (Κα) tube was confirmed to be the main phase of the c^NaFe〇2 type hexagonal crystal structure, and partial observation To

20 visible in monoclinic crystals of Li[Lii/3Mn2/3]〇2 type. ~30. The nearby diffraction peaks. The crystal structure analysis of all the ray rays of S is determined by the Rjetveld method, and the result is very different from the crystal structure model attributed to the space group Ρ3ι12 according to 2Θ: 18.6±1. At the time of the diffraction peak, the area of the diffraction peak of the (〇〇3) plane is obtained, according to 2Θ: 44.1±1. At the time of the diffraction peak, the area of the diffraction peak of the (114) plane was obtained, and the intensity ratio (area ratio) of the two diffraction peaks (area ratio) 1 (003) / 1 (114) was calculated, and the result was 1.41. ώ曰: The monthly intensity of the drink” refers to the cumulative value of the X-ray detector's value for the X-ray, so there is no difference in the width of the X-ray diffraction pattern or the peak ' in the compared peak. When the width is not ten, as long as the height of the peak is compared, the height of the peak is compared, and the area is compared. The diffraction peaks are d,, '. The result is 〇·14. 'Based on 2Θ: 44.14. Time 0.23. . The half-height width of the diffraction peak of the () plane is 33 201125195. Further, the Rietveld analysis is performed on the data of the X-ray diffraction pattern on the computer. In the analysis process, the Gaussian function and the Laudz function are used. The crystal parameters contained therein were refined, and the crystal lattice and the crystallite size were calculated based on the crystal numbers thus obtained, and the crystallite size ribs (Example 1-2 to Example 1_5) were changed except for Example 1 of Table 1. 2 to the calcination temperature production shown in Examples 1-5 (980 ° C, 960 ° (:, 940 t, 920. 〇, the synthesis of the active material of the present invention is exemplified. 7 X-ray diffraction measurement results and examples 丨-i is the same, confirming that the hexagonal structure of the o^NaFeO2 type is the main phase, and partially observed

Li[Li wMn2/3]. 2 可见 visible in the type 2 monoclinic crystal. ~3〇. The nearby diffraction peaks. All of the diffraction rays were analyzed by the Rietveld method for the structure of the gentleman crystal, and the results were the same as those of the (4) group P3112. In the same manner as in Example 1-1, the intensity ratio (〇〇3)/1 (114) of the diffraction peak was calculated and found to be 1.15 to 1.35. (Comparative Example 1-1 to Comparative Example 1-5) The temperature was changed to the comparative example to the comparative example of Table 1 (_. (:, 80 (TC, 70 (TC, 5 pit, 1 Wc)) The active material of the comparative example was synthesized. For Comparative Example 1-1 to Comparative Example 1_4, the crystal structure analysis was carried out in the same manner as in the Example, and the π-fruit was confirmed to be attributable to the space group enthalpy diffraction pattern. 1 ^ 201125195 =Comparative example W 'Space group is (3) In the same way as in Example 1.·1, the radiance &amp; _ _, 1 / 丨 婊 is calculated. The result is the intensity of the peak of the wave with an area ratio of 1 (Example 1-6~) Example 丨 _9) and 笱 S two deaths; t hydroxide hydroxide precursor composition of metal elements ι · ϋ # two, the amount of the mixture 'according to the examples 1-6 to the example of Table 1 In the same manner as in Example 1-1, the active material of the invention was used in the same manner as in Example 1-1. In the same manner as in Example 1, the crystal structure analysis was carried out, and the county peak recognized that it was an empty 'group P3llW X-ray diffraction pattern. In the case of Shili f, the intensity ratio (area ratio) ((8)3) to 114) of the diffraction peak was calculated, and the result was 1.35 to 1.51. (Comparative Example 丨-6~Comparative Example 1_9) Comparative Example In the same manner as in Example 1-1, the active material of 1-6 to Comparative Example 1-9 was set to have the same solid solution as that of Example 16 to Example i-9, and the temperature of the firing stage was changed to 'Other than Example 1-1. The crystal structure analysis was carried out in the same manner as in Example 1-1, and it was confirmed that the X-ray diffraction pattern attributable to the space fP3 "2" was calculated. The intensity ratio (area ratio) of the diffraction peak was calculated (〇〇3). /1 (114), the result was 1.12 to 113. (Comparative Example 1-10 to Comparative Example M5) The Mg' was removed from the metal element contained in the coprecipitated hydroxide precursor, and the composition was changed to UuC〇Q1NiQ_15Mn〇_ 55〇2, and changed to the calcination temperature shown in Comparative Example M〇~Comparative Example M5 of Table 1 (1〇〇〇°c, 35 201125195 90 (TC, 80 (TC, 700°C, 55 (TC, 11) The active material of the comparative example was synthesized in the same manner as in Example 1-1 except for 〇(rc).

With respect to Comparative Examples M0 to M-14, the crystal structure analysis was carried out in the same manner as in the example. As a result, it was confirmed that X which is attributable to the space group PH] is different from P3ll2 in the case where the space group of Comparative Example 1-15' is C2/IH. In the same manner as in Example 1-1, the intensity ratio (area ratio) of the diffraction peaks was calculated in summer (〇〇3)/1 (114), and as a result, it was 0.94 to 1.422. (Comparative Example 1-16) In order to compare the properties of the active material with the substance of the present invention, solid solution containing A1 instead of Mg was prepared.

Lii.aCoojNio.wAlo.ouMnoMA. :. Manganese sulfate pentahydrate, nickel sulfate hexahydrate, and cobalt sulfate heptahydrate were dissolved in ion-exchanged water in a ratio of 12.69: 18.28 : 69.03 to prepare a mixed aqueous solution. At this time, the total concentration of j吏 is 0.667 mol/bu and the volume is 180 m, followed by i L . 600 ml of ion-exchanged water was prepared in a beaker, kept at 5 〇p using a hot water bath, and 8 N of NaOH was added thereto, thereby adjusting the pH to 12.0. Argon gas was bubbled in this state for 30 minutes to sufficiently remove dissolved oxygen in the solution. The inside of the beaker was stirred at a number of revolutions of 700 rpm, and the mixed aqueous solution of the above sulfate was added dropwise at a rate of 3 ml/min. In the meantime, the temperature was kept constant using a hot water bath, and 8 n of NaOH was intermittently dropped to maintain the pH at 疋. At the same time, the concentration of 2.0 〇l/i of hydrazine aqueous solution as a reducing agent was added dropwise at a rate of 0.83 ml/min. After the addition of the sputum, the granules were suspended at a temperature of 36 201125195. growing up. For more than 12 h, the coprecipitated hydroxide is charged, and the coprecipitated product is taken out by suction filtration, and then air-cooled under a vacuum. After the money, to make the grain =

/ Consistent manner using a diameter of about 12 G mm (p of the ground material for several minutes = dry powder. X) Lithium hydroxide monohydrate powder (Li) was weighed to satisfy the composition formula of Comparative Example 1-16 of Table 1. 〇H.H20) and aluminum hydroxide are mixed to obtain a mixed powder. 15 Next, the mixed powder is subjected to pellet molding under a pressure of 6 MPa. The amount of the precursor powder supplied to the pellet is a product of the synthesized product. The weight was determined by the conversion of 3 g. As a result, the formed pellets were mnup in diameter and about 1 cucurve-丨] mm in thickness. The pellets were placed in a boat of oxidized shrimp having a total length of about 100 mm. It is placed in a box-type electric furnace and calcined in an air atmosphere at normal pressure at 10 °C for 12 h. The internal dimensions of the above-mentioned box-type electric furnace are 1 cm in length, 20 cm in width and 30 cm in depth. A heating wire is placed between the intervals of 20 cm in the width direction. After the calcination, the switch for cutting off the heater 'maintains the state in which the alumina boat is placed in the furnace and is naturally placed and cooled. Result 'The temperature of the furnace drops to about 200 after 5 hours. 〇C or so, the subsequent cooling rate is slightly slower. After a painting night It is confirmed that the temperature of the furnace becomes 1 〇〇〇c or less' and then the granules are taken out and pulverized to a uniform particle size using a research spider. The composition of the obtained active material is Lil.2C〇〇.iNi〇_i44Al〇 .Q12Mn〇.544〇2 ' As for the crystal structure, a powder X-ray diffraction measurement using a Cu (Κα) bulb was observed as a main phase of the 37 201125195 a-NaFe〇2 type hexagonal crystal structure. All of these ray diffractions were analyzed by the Rietveld method, and the results were in good agreement with the crystal structure model attributed to the space group P3il2. (Comparative Examples 1-17) In order to compare the properties of the active material with the substance of the present invention, The solid solution Lii.2C〇〇.iNi〇.1395Al〇021Μη0·5395〇2 containing A1 instead of Mg is synthesized. The composition of the transition metal element contained in the coprecipitated hydroxide precursor and the lithium hydroxide monohydrate and The active material of the comparative example was synthesized in the same manner as in Example 1-16 except that the amount of the aluminum hydroxide was changed according to the composition formula shown in Comparative Example 1-17 of Table i. (Comparative Example M8) For the substance of the invention The solid solution 52〇2 containing Ti instead of Mg is synthesized as a property of the active material: the composition of the transition metal element contained in the coprecipitated hydroxide precursor and the mixing amount of lithium hydroxide monohydrate and titanium dioxide, The active material of the comparative example was synthesized in the same manner as in Comparative Example 1-16 except that the composition formula shown in Comparative Example 1-18 of Table 1 was changed. (Comparative Example 1-19) For the substance of the present invention Comparing the characteristics as an active material, a solid solution Lii 2C〇〇 containing Ti instead of Mg was synthesized as i5Ti〇〇5Mn〇5〇2. The composition of the transition metal element contained in the coprecipitated hydroxide precursor and the mixing amount of the lithium hydroxide monohydrate and the titanium oxide were changed according to the composition formula shown in the table of Comparative Example M9, and the comparison was made. 38 201125195 The active material of the comparative example was synthesized in the same manner as in Example 1-16. (Preparation and Evaluation of Clock Secondary Battery) Using each of the examples 1-1 to 1-9 and the comparative example w to the comparative example 丨19, the biobes are used as the positive electrode active material for the secondary battery, in the following order Gas clock - under battery, evaluate battery characteristics. , the active material, B-black (AB) and polyvinylidene fluoride (pvdF) are mixed at a weight ratio of 85:8:7, and N_ as a dispersion medium is added.

The mercaptopyrrolidinium is kneaded and dispersed to prepare a coating liquid. Further, pvdF was subjected to a solid weight exchange using a solution in which a solid component was dispersed. The coating liquid was applied to a potential plate of a collector body having a thickness of 2 inches. Furthermore, all battery deductions are the same test condition, and the electrode weight and thickness are unified. Dependent 2 is relatively heterogeneous. In order to (4) the sole behavior of the positive electrode, Lijin will be dressed. The clock metal is adhered to the (four) current collector. Among them, the grain amount of the second time is prepared in such a manner as to be sufficiently positively controlled. EC/Ε^^λ疋湘使咖6 is dissolved in a solution of liquid n C in a mixed solvent of 6:7:7 in a concentration of 1 mGl/1 to make the polyacrylic acid (4) =: : r poly, microporous membrane. Further, 丄 = benzophene &gt; white matter was used as a reference electrode. The outer casing is made of a metal-resin composite film composed of poly-p-i (1) μη〇/1(9) (5G μη〇/metal-adhesive polypyre 5 (50,)), and the terminal and the reference electrode terminal are accommodated at the positive electrode end. The square electrode 'exposed to the outside is exposed to the surface of the above-mentioned metal-resin composite_201119195. The portion where the melted portion becomes the liquid-filling hole is hermetically sealed, and the lithium-manufactured as described above is used. The secondary battery is supplied to the 5-cycle initial charge and discharge step. The voltage control is all set to the positive electrode = 2, the electric power is A, the power plant is strong. 4. The charging termination condition is set to the current value. When the attenuation is 1/6, the discharge is set to the current αι ItA, the end of the electric dust 2〇, and the U1 of the example 1_1 after the charging and U minutes after the discharge. From the vicinity of 〇〇mAh/g, a relatively flat region with a potential change was observed during the long period. The potential at the nearby potential was tested in the charge-discharge cycle. The control of the electric power was all in addition to the positive V Λ Nrayrand condition. Set the test to the same. The condition of the silk-discharge step is set to 30 minutes after the discharge and after the discharge, the electric capacitance (mAh/g) is set." Electric power!. Who has been recorded as a person who has been placed:: ^: Say the South rate discharge test. The Μ control is all about the positive potential. In addition to the charge and discharge cycle test, the positive electrode voltage V (private Li/Li+), on the disk, the condition f / sets the charging voltage to 4.3, and the discharge is set to 2. The conditions of the ItA charge and discharge steps are the same. Electricity. After charging and silting; ^, s stop voltage 2·〇V constant current discharge - ° ^ (rate) The (003) plane and (114) plane diffraction peak The calculation results of the intensity ratio (area 201125195 ratio) 1 (003) / 1 (114), the charge and discharge cycle test results (0.1 c capacitance), and the rate ratio are shown in Table 1. [Table 1] 41 201125195 --98- Rate ratio % 00 (0 i〇to Φ CO CO 5S o If) (0 m CO sa in 5 ss (O CO in in CM in to in in O in SS (0 Ln CM ΪΛ Λ in 1Λ discharge capacitor mAh) /g 242 233 225 210 201 203 218 245 211 185 165 152 115 o (0 135 142 170 168 | 223 186 166 154 116 g 194 181 183 172 Wave bee intensity ratio I 003 / I H4 1. 41 1.35 CNJ 1.23 1.15 1.48 1.51 1.47 1*35 CO 1» 1.05 0.95 1.42 1.13 1.12 1.12 1.13 1.414 ! 1.109 ! 1.108 〇0.94 1.422 1.43 1.42 1.47 1.45 Normally burnt temperature °c 1000 980 960 940 920 1000 1000 1000 1000 900 800 700 550 1100 800 800 800 800 1000 900 800 700 550 1100 1000 1000 1000 1000 Space group CM ▼ — CO Q. CM a CM CO a CM CO a CM CO 0. CM CO a. CSl CO a CNJ CO Q. CM CO CL CNJ CO a Μ CO a CsJ CO 0. CNJ CO 0. C2/m CM T— CO 0. r— CO a. CM Strict CO a CM CO CL CO 0. CM CO CL CM CO a Csi CO 0. CM CO CL C2/m CM T- co 0. ι- ΓΟ a OJ T-&quot; CO 0. CM CO a 1 Li| 2C〇〇jNi〇ΐ39Μβ〇.οπΜη〇55〇2 ; I Li1 2Co〇j Ni0j39Mg〇01, Mn〇55〇2 | Li! 2Co0 tNi013gMg0〇11Mn〇55〇2 LiJi2Co0_tNi0_139MgOOnMn〇.55〇2 Lii.2C〇〇.iNi0.139Mg0.ot #门0.55〇2 Li1t7Co0 .09Ni01BMg002Mn054〇2 Lit 2iCo0&gt;2tNi〇oeMg002Mn〇5〇〇2 *-i t. 1〇〇. i N i〇j 5 M g〇〇3 Μ n〇_54 O 2 Li! 2Co〇〇8Ni〇l5Mg001Mn 〇56〇2 Lii, 2〇〇ο. Niai 39Mg〇.01, Mn0.55O2 Li, 2C〇〇jNiq 139Μ^οηΜη〇55〇2 Lii.2G〇o.iNi0.139Mg〇.0&quot;Mn0.55〇2 Lit.2Co〇tNi〇139Mg0〇i tMn 〇55〇2 Li|_2Co0_1Ni〇&gt;l39Mg0&gt;〇nMn0_55〇2 Lit.i7G〇o.〇9Ni〇.i8Mg0.〇2Mna54〇2 Lii .21C o〇&gt;21N i0_06M g〇_02Mn〇_5002 ί- Ϊ́ι.ΐ8^〇〇.ιΝί〇i5Mg〇&gt;〇3Mn〇54〇2 Lii.2Co008Ni015Mg〇01Mn〇s6〇2 L*i.2^°oi Ni〇.i5Mn0_5502 Li1i2C〇〇.iNi0_15Mn0_55〇2 L Bu 2G 〇oi Ni〇.i5Mn0.5502 υ1_2〇ο0_1Νΐ〇ί|5Μη0&gt;55〇2 Li1_2Co〇.tNi0_)5Mn0_S5〇2 Lii.2C〇〇,iNi0.15Mn0.5502 Li! 2C〇〇.iNi〇144AI〇〇12Mn 〇544〇2 Li1_2Co0&gt;tNi0i1395Al0_〇2iMn〇_5395〇2 Li) 2C〇〇j N i〇t δΤί0 Q3M n〇52〇2 Li, 2C〇〇iNi〇ϊ5Τΐ0〇5Μη〇5〇2 Example 1-1 Examples 1-2 Examples 1-3 i Examples 1-4 I Examples 1-5| | Examples 1-6 I Examples 1-7 Examples 1-8 I Examples 1-9 Comparative Examples 1-1 Comparative Examples 1-2 Comparative Examples 1-3 Comparative Example 1-4 Comparative Example 1-5 Comparative Example 1-6 Comparative Example 1-7 Comparative Example 1-8 | Comparative Example 1-9 I Comparative Example 1-10 Comparative Example 1-11 Comparative Example 1-12 Comparative Example 1-13 Comparative Example 1-14 Comparative Example 1-15 Comparative 彳 1-16 Comparative Example 1-17 Comparative Example 1-18 Comparative Example 1-1 9 201125195 For complex oxidation of lithium transition metal The composition ratio (metal element ratio) of the metal element contained in the solid solution of the substance is set to Lii+(x/3) Co i_x-y_zNiy/2Mgz/2Mn (2x/3) + (y/2) + (z/2 When, Example 1 to Example 1-5 are x = 0.6, y = 0.278, ζ = 〇·〇22, and Examples 1-6 are χ = 〇51, y = 0.36, Z=0.04, and Examples 1-7 are x = 0.63, y==〇12, ζ = 〇〇4, examples 1-8 are \ = 0.54, 3^〇.30, 2 = 0.〇6, and Example 19 is 乂= 〇6〇, y=0.3 〇, ζ=0.〇2, both satisfying the ratio of the above-mentioned metal elements, having an X-ray diffraction pattern attributable to the space group P3il2's diffraction of (003)® and (114) planes obtained by the ray diffraction measurement The intensity ratio of the peaks is 1 (〇〇3) / 1 Sichuan 4) 21.15, so the active material of Example 1-1 to Example 丨9 can obtain a discharge capacity of more than 200 mAh/g and a rate ratio of 65% or more. Therefore, it was confirmed that the discharge capacity was large and the high rate discharge characteristics were excellent. The above ratio of the active material of Comparative Example 比较 to Comparative Example 44 was the same as that of Example Μ to Example U, and had an X-ray diffraction pattern attributable to the space group P3il2, but the calcination temperatures were C and 700, respectively. 〇, 550〇C ′ is lower than the coffee of example w~example 15. . ～920, so the intensity ratio of the diffraction peak is as small as that, only a discharge capacitance of less than 2 〇 0 mAh/g can be obtained, and the rate ratio is also Na. In addition, the ratio of the above metal elements of the active materials of Comparative Examples 1-5 is Example 1-1 ~ Example M is the same, while the satin burning temperature is high. C, so the intensity ratio of the wave peak satisfies y 15, but the ray diffraction that does not belong to the space group P3!12 is extremely close to the discharge capacitance and rate ratio. 43 201125195 The above-mentioned metal element ratios of the active materials of Comparative Examples 1-6 to Comparative Examples 1-9 are the same as those of Examples 1-6 to 1-9, respectively, and have an X-ray diffraction pattern attributable to the space group P3J2, but calcined. The temperature is 8 〇〇. 〇, less than 1〇00 of Example 1-6~Example丨_9. Therefore, the intensity ratio of the diffraction peak is as small as 1 (〇〇3) / I(u4) &lt; 1.15 ', and only a discharge capacitance of less than 200 mAh/g can be obtained, and the rate ratio is also 56% or less. The active materials of Comparative Example M0 to Comparative Example M5 did not contain Mg, but the active material was also as in Comparative Example 丨-10. When the calcination temperature was 1000 ° C, the solid solution of the lithium transition metal composite oxide was attributable to In the X-ray diffraction pattern of the space group P3J2, the intensity ratio of the diffraction peaks satisfies (ii4) ^ 1.15, and a discharge capacitance exceeding 200 mAh/g can be obtained. However, the rate ratio was 52%', which was the same as that of the active materials of Comparative Example 1-11 to Comparative Example ι_15, and the high rate discharge characteristics were inferior. Therefore, as in the case, the active substance contains Mg and is at 1 Torr. When calcination was carried out under the armpit, the discharge capacity and the high-rate discharge characteristics were improved together, and as in the case of Comparative Example M0, if the active material contained no Mg, it was at 1 Torr. When the crucible is calcined, the discharge capacity is increased, and the high-rate discharge characteristics are not improved. Further, when Example 1-1 was compared with Comparative Example M, the discharge capacity of the active material of Example 1-1 was 242 mAh/g, whereas the discharge capacity of the active material of Comparative Example M0 was 223 mAh/ g, it can be seen that by replacing a part of Ni with Mg, the discharge capacitance is remarkably improved, and thus the case where the discharge capacitance is remarkably improved by containing Mg is not predictable. Further, 'Examples 1-3 and Comparative Example M0 are discharge capacitors of the same degree', but the active material of Comparative Example 1-10 is a material 44 201125195 which is calcined at 1000 ° C. In contrast, the activity of Examples 1-3 The substance is a substance calcined at 960 ° C, and thus can be realized by obtaining Mg at a low calcination temperature in order to obtain an active material of the same degree of discharge capacity. Therefore, by using the active material of the present invention, the effect of supplying energy to the furnace at the time of firing can be reduced. On the other hand, the Mg-free active material was also calcined at a temperature of 900. In the following, as in Comparative Example 1-11 to Comparative Example 1-14, the intensity ratio of the diffraction peak was 1 (.3) / 1 (114) &lt;1.15; however, if the calcination temperature was 900X: In the case of Comparative Example 1-11, the discharge capacity of the active material of Comparative Example 1-1 containing Mg was 185 mAh/g, whereas the active material of Comparative Example 1-11 containing no Mg was used. The discharge capacity was 186 mAh/g; in addition, when Comparative Example 1-2 having a calcination temperature of 800 ° C was compared with Comparative Example 1-12, the discharge capacity of the active material of Comparative Example 1-2 containing Mg was 165 mAh/g, the discharge capacity of the active material of Comparative Example 1-12 containing no Mg was 166 mAh/g, so the discharge capacity was the same (the calcination temperature was 700 ° C, 550 ° C) To the same extent, even if a part of Ni is replaced by Mg, the discharge capacity does not increase. Therefore, in order to remarkably increase the discharge capacity, it is necessary to make the composition ratio of the metal element contained in the solid solution of the lithium transition metal composite oxide Lii+(x/3) C〇ixy-zNiy/2Mg2/2Mn (2x/ 3) + (y/2) + (z/2) ( X > 〇 y &gt; 0, z &gt; 〇, x + y + z &lt; l), and the (003) plane obtained by X-ray diffraction measurement is required The intensity ratio of the diffraction peak to the (114) plane is I (〇〇3) (in) ^ 1.15. For example, as in Comparative Example 1-16 to Comparative Example 1-19, A1 or Ti is substituted instead of 45 201125195

A

The intensity ratio of the diffracted Mg under the TC (the active material of the lithium transition metal composite oxide, the X-ray diffraction pattern attributable to the space group P3J2) is satisfied with I (QQ3) / 1 (114) 2 1.15, but a discharge capacity of more than 200 mAh/g cannot be obtained, and high rate discharge characteristics are also poor. As described above, the active material of the present invention satisfies "a solid solution of a lithium transition metal composite oxide" The composition ratio of the metal element contained satisfies Lii+(x/3) Co^xy^Niy^Mg^Mn(2χ/3) + (y/2) + (ζ/2) ( χ&gt;〇' y&gt; 〇^ z&gt ;0, x + y+z &lt;1)", "having a ray diffraction pattern attributable to the space group Ρ3ι12", and "(3) plane and (114) plane obtained by X-ray diffraction measurement" The intensity ratio of the diffraction peak is 1 (〇.3)/1(114)^15", and a large discharge capacitance exceeding 200 mAh/g can be obtained, and the high-rate discharge characteristics are excellent. [Example 2] (Example 2_1) An active material having a composition of Lii.2Co01Ni〇139Mg0.011Mn〇.55〇2 was synthesized at a calcination temperature of 10003⁄4 in the same manner as in Example 1-1. Regarding the crystal structure of the obtained active material, Example 1_丨 A powder X-ray diffraction measurement using a Cu (Κα) bulb was carried out in the same manner, and as a result, it was confirmed that δ endured the hexagonal structure of the a-NaFe〇2 type as the main phase' and was partially observed.

LitL—Mri2/3]. 2 可见 visible in the type 2 monoclinic crystal. ~3〇. The nearby diffraction peaks. The crystal structure analysis of all these ray rays by the Rietveld method is very consistent with the crystal structure model attributed to the space group P3l12. In addition, 'by 2Θ: 18.6±1. At the time of the diffraction peak, the half-height of the diffracted peak of the 2011 1953 surface is obtained. The result is 〇 14. , the wave: find the full width at half maximum of the diffraction peak of the (114) plane: the result is = and further, the X-ray secret image (4) is expected to be included in the computer field RRietvdd analysis process to make the Gaussian function and the labor function The parameters were refined, and the lattice deformation and the crystallite size were calculated from the crystal parameters thus obtained, and the crystallite size was 180 nm. (Example 2-2 to Example 2-10) It is understood that the composition of the metal element contained in the hydroxide precursor of the common hall and the mixing amount of the lithium hydroxide monohydrate are as shown in Example 2_2 to Example 2_1 of Table 2 The active material of the present invention was synthesized in the same manner as in Example 2-丨 except that the composition formula was changed. The results of the X-ray diffraction measurement were the same as in Example 2U, and it was confirmed that the hexagonal structure of the a-NaFe〇2 type was the main phase, and the 2〇 visible in the monoclinic crystal of the LitLi^MndO2 type was partially observed. ~30. The nearby diffraction peaks. The crystal structure analysis of all the diffraction rays by the Rietveld method is very consistent with the crystal structure model belonging to the space group Ρ3ι12. In addition, 'by 2Θ: 18.6±1. At the time of the diffraction peak, the full width at half maximum of the diffraction peak of the (003) plane was obtained, and as a result, it was 0.14. ~0.15. , by 2Θ : 44.1±1. At the time of the diffraction peak, the full width at half maximum of the diffraction peak of the (114) plane was obtained, and as a result, it was 0.23 〇 to 0.25. . Further, the crystallite size was calculated in the same manner as in Example 2-1, and as a result, the crystallite size was 180 nm to 200 nm. (Comparative Example 2-1 to Comparative Example 2-4) 47 201125195 The Mg was removed from the metal element contained in the hydroxide precursor of the coprecipitation, as shown in Comparative Example 2-1 to Comparative Example 2-4 of Table 2 In the case of Comparative Example 2-1 to Comparative Example 2-4, the calcination temperature was changed to 1000 ° C, 900 ° C, 800 ° C, and 700 ° C, respectively, and the same as Example 2-1. The active material of the comparative example was synthesized. The full width at half maximum of the diffraction peaks of the (003) plane and the (114) plane were obtained in the same manner as in Example 2-1, and the crystallite size was calculated. (Comparative Example 2-5 to Comparative Example 2-7) For Comparative Example 2-5 to Comparative Example 2-7, calcination of a solid solution having the same composition as that of Example 2-2 (calcination temperature l〇〇〇°C) was carried out. The active material of the comparative example was synthesized in the same manner as in Example 2-1 except that the temperature was changed to 700 ° C, 800 ° C, and 900 ° C, respectively. The full width at half maximum of the diffraction peaks of the (〇〇3) plane and the (114) plane were obtained in the same manner as in Example 2-1, and the crystallite size was calculated. (Comparative Example 2-8 to Comparative Example 2-14) Comparative Example 2-8 to Comparative Example 2-10 were set to have the same solid solution composition as in Example 2-3, Example 2-B Example 2-4, and Comparative Example 2-11 to Comparative Example 2-14 were set to the same solid solution composition as in Examples 2-7 to 2-10, and the firing temperature was changed from 1000 ° C to 900 ° C. In addition, examples and examples 2-1 The active material of the comparative example was synthesized in the same manner. The full width at half maximum of the diffraction peaks of the (〇〇3) plane and the (il4) plane were obtained in the same manner as in Example 2-1, and the crystallite size was calculated. (Comparative Example 2-15, Comparative Example 2-16) The composition of the transition metal element contained in the common hydroxide precursor of the 48 201125195 and the mixing amount of the hydroxide monohydrate were as shown in Comparative Example 2 of Table 2. 15. The active material of the comparative example was synthesized in the same manner as in Example 2-1 except that the composition formula shown in Comparative Example 2-16 was changed. The full width at half maximum of the diffraction peaks of the (003) plane and the (114) plane were obtained in the same manner as in Example 2-1, and the crystallite size was calculated. (Comparative Example 2-17) An active substance containing A1 instead of Mg was synthesized in the same manner as in Comparative Example 1-16, LiuCoo.iNio.wAlo.ouMno.wC^. (Comparative Example 2-18) An active substance containing A1 instead of Mg was synthesized in the same manner as in Comparative Example 1-17, LiuCoo.iNio.msAlo.c^iMno.s^O!. (Comparative Example 2-19) An active material containing Ti instead of Mg was synthesized in the same manner as in Comparative Example 1-18, LiuCoo.iNiojsTio.t^Mno.wC^. (Comparative Example 2-20) An active material containing Ti instead of Mg was synthesized in the same manner as in Comparative Example 1-19. LiuCoo.iNio.uTio.osMnojC^. (Production and Evaluation of Lithium Secondary Battery) Each of the active materials of Examples 2-1 to 2-10 and Comparative Example 2-1 to Comparative Example 2-20 was used as a positive electrode active material for a lithium secondary battery, and Example 1 was used. A lithium secondary battery was fabricated in the same order, and battery characteristics were evaluated. The measurement results of the full width at half maximum, the calculation results of the crystal size, the charge and discharge cycle test results (0.1 C capacitance), and the rate ratio are shown in Table 2. [Table 2] 49 201125195 ^-98^ ss δ s inch ws 0Λ z10 1·° ssssss ε ssss tL uu ω/χ&lt;αι 铋铗钗柘tv03&quot; 趔趔ΝΙΓΧΙ-, liw+&lt;sl)^*+ (εοο) *οοοπ Ζ Λ χ ζ0ΖΛε2~, -Μ5!Ί~ο~, £Σ~/·-ζπ~0^,~υ2&quot;··-π】π w inch-ou εβ-SI 06-061 &quot ;6·-«61 901·- Ώβι on s- 991 S3 Ns Λ inch 3 OS ~s 53 -s ~s 3Z zs oe·-061 ow·-OtH οει 0·°··-on οει OM ou OS OS Ou ow 061 0rol 081 OS 081 06-06-OS oe·-081 08·-

SO ε'0 8ΖΌ 6ΖΌ so 6-0 8-0 SO 3Ό 8S -3 5.0 3Ό ε.ο so εζ.ο SO so so so so so so inch s ε'0 so SO no no 9L.0 95 95 no 91Ό 95 Ao ΖΛΌ Ls -ss ·0 uo wo ΜΌ wo no PIO WIO 寸 inch Ό tnd inch-0 inch 5 ο ο ο 5 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ·ο SS 005 090.0 sod S00 zloo οηο.0 so.o ΖΞΌ §00 SOO Id 0 0 0 0 0900 35.0 soo W5.0 sl.o 0900 os.o Nto.o id 30Ό &quot;εεΌ ss.o ε.ο Ss ε_0 05Ό 85Ό s-0 S3 S3 SZO 3 ssss ε·ο s εο 08-0 os.o OSO ss szo 85Ό 9 9 9 9 9 9 9 9 9.0 os.o SSO SSO SSO ·0 90 90 9Ό 9Ό 90

000.0 000.0 oso SSO Φ 卜 SO SSO woooocson.o^zonooo^ «os.oc5S.OM5»2f S.0OOJ ^OSOC2SOM2«3~2-0〇〇*-.-□ 3οε5.0Ε250ώ5®-·-ζ_°οοβ2 ··-η Z09SOU5~10.0MS2.--ZSO°S r·--1 2083.0=2^8.03^-.0^-000^1-1-1 ~0SOC5S5.0MSSC5I2500~II-, WOS.0C2-- Ootoss-.oz-.0〇〇«-□ ~°s,oc5e8OMs5-OI2ro0ur--J «OSOC508.0W25-.O^Z-.OOON.-D z°ss.ou2§oss5rol2so°rlj-, 208.0= 208.032551-.0002.13 2OSOc5s-02tOOQZ-J-} ~os°'u 2 S 5J-.0O 02 J-| NOS0C5W-.05-.0〇〇«-□ ZOSS.0 JslOJ-.oo°'-ll ZOSOUSSOgssroj -ooos.·--, ~o5s&quot;0c2-s.0s5*5-z-°o°s-·-- «Oesocs«-O.OM2W- 0-z- ooos- WOI.OC5SOOW2«-.0- Z-0〇0»*-·-□ wos.oc5eodM2JZ-OOON.-D ~0®·ου23.032ζιΌΙ2ιΌΟϋ~·-ρι NOWW.OC2®5.0M2W«-.0-Z-.OOON.-^ ZOSOU2eg. 0323 5l250°sn 308.0=210325-012-0002--1 ζο8.0υ5ιιοΌ353·'-ζ·οοϋ~·-η 9T3?&quot;qq St 丨S$sq1 MIZ5&quot;^ ετζ5^^ U-Z5窠e 01 丨25馨^6-z5粲玉Tz5&quot;-9lz?^&quot; s—-^^qq inch-3r-4m- ?妾 anchor e apricot anchor&quot; L--_牟耷qi OTZf#Jjt! 612 5^ 1 ?-条^i Bu--Every A 9-two 杳?3: pull work f^v Z丨Z Tg one °~oon °lvn°~z/-c~, --zn°c*, *c5®, -n]n (O CM ιο L〇194 181 180 180 0.24 0.24 0.14 0.14 o' Ο 0.012 0.021 0.288 0.279 to (〇oo Lit^CootNig i44Al0012Mn〇S44〇2 LitJCo0 tNi〇1395Ala〇2iMn053g5〇2 Comparative Example 2-17 Comparative Example 2-18 "ooon ζ °ζ/·-~,·-2π°*, -css!2n°[sc2sn]n ιη 〇ιη ιη 183 172 180 190 0.24 0.25 0.14 0.15 6 ο 0.06 0.1 0.24 0.2 (D (〇ό ό Li, jCo〇 1Ni015Ti003MnOH〇2 Lit.2Co0.tNi0.1sTi0.0SMn0.sO2 Comparative Example 2-19 Comparative Example 2-20

OS 201125195 Example 2-1 to Example 2-6, Comparative Example 2-5 to Comparative Example 2-10 are contemplated as solid solution xLi[Li1/3Mn2/3]02-yLiNi1/2Mn1/2〇2-zLiMgi/2Mn1 /2〇r (1-xyz) LiCo02 (x&gt;0, y&gt;〇, z&gt;0, x + y+z&lt;l) is based on 'replacement by Mg2+1/2Mn4+1/2 The idea of Νθ+^Μη4'/2 part of LiNi1/2Mn1/202 to satisfy the formula Li1+ ( x/3 ) C〇ix.y.zNiy/2Mgz/2Mn (2x/3) + (y/2) + ( z/2) (x &gt; 0 ' y &gt; 0 ' z &gt; 0 ' x + y + z &lt; l) The composition ratio (metal element ratio) of each metal element is set. With respect to the examples 2-1 to 2-2, the above metal ratio is within the prescribed range of the present invention, and the half-height width of the diffraction peak of the '003' plane is 0.14. ~0.15. And the full width at half maximum of the diffraction peak of the (114) plane is 〇.23. ~0.25. . The above metal element ratios of Comparative Example 2-5 to Comparative Example 2-7 were the same as those of Example 2-2', but the calcination temperatures were 700 ° C, 800 ° C, and 900 ° C, respectively, which was lower than 1000 ° C of Example 2-2. Therefore, the half-height width of the diffraction peak of the (003) plane is 0.31. 0.21. , 0.17. , greater than 0.14 of Example 2-2. The half-height of the diffraction peak of the (114) plane is also 0.45. '0.31. 0.28. , greater than 0.24 of Example 2-2. . Further, regarding the crystallite size, Example 2-2 was 180 nm, whereas Comparative Example 2-5 to Comparative Example 2-7 were 80 nm, 110 nm, and 140 nm, respectively, and it was found that the lower the calcination temperature, the more the crystallite size was. small. The above metal element ratios of Comparative Example 2-8 to Comparative Example 2-10 were the same as those of Example 2-3, Example 2-; 1, Example 2-4, but the calcination temperature was 900 ° C, which was lower than Examples 2-3, Examples. 2-;!, 1000 °C of Example 2-4, so the half-height of the diffraction peak of 51 201125195 of the (003) plane is 0.16. ~0.17. , greater than Example 2-3, Example 2-1, and Example 2-4 of 0.14. The half-height of the diffraction peak of the (114) plane is also 0.28°~〇.29. , greater than 0.23 of Example 2-3, Example 2-1, and Example 2-4. ~0.24. . In addition, regarding the crystallite size, Examples 2-3, 2-1, and Examples 2-4 are 180 nm to 200 nm, whereas Comparative Examples 2-8 to 2-10 are 130 nm to 140 nm. The crystallite size is small. Examples 2-7 to 2-10, and Comparative Examples 2-11 to 2-14 are similarly assumed to be solid solution 胄xLi[Li1/3Mn2/3]02-yLiNi1/2Mn1/2〇2-zLiMg1/2Mn1/ 2〇2-(1-xyz) LiCo02 (x&gt;0, y&gt;0, z&gt;0, x + y+z&lt;l) is based on 'replacement by [Mgl/2Mni/2]3+ The idea of the [Lii/3Mn2/3]3+ part to satisfy the formula Li1+ (x/3)C〇lx, y-zNiy/2Mgz/2Mll(2x/3) + (y/2) + (z/2 (X&gt; 〇, y &gt; 〇, z &gt; 〇, x + y + z &lt; l) The ratio of each metal element is set. With respect to Examples 2-7 to 2-10, the above-described metal ratio is within the range of the present invention, and the full width at half maximum of the diffraction peak of the '(3) plane is 〇 14. ~ 0.15. And the full width at half maximum of the diffraction peak of the (114) plane is 〇.23. ~〇 25. . The above metal element ratios of Comparative Examples 2-11 to Comparative Examples 2-14 were the same as those of Examples 2-7 to 2-10, but the calcination temperature was 9 Torr (TC, which was lower than 1000 of Examples 2-7 to 2-10). °C, so the half-height of the diffraction peak of the (003) plane is as large as 0.16°~0.17°. The half-height width of the diffraction peak of the (114) plane is also as large as 0.28.~0.29. In addition, regarding the crystallite size 'Example 2-7~Example 2-1〇 is 18〇nm 52 201125195~200 nm, whereas Comparative Example 2-11 to Comparative Example 2-14 are 130 nm to 140 nm, and the crystallite size is small. The half-height width of the diffraction peak of the (〇〇3) plane is 0.15. The half-height width of the diffraction peak of the (114) plane is 0.25. Examples 2-1 to below The active material of 2-10 can obtain a discharge capacity of more than 200 mAh/g, and the active material phase of Comparative Example 2-1 to Comparative Example 2-4 having the same composition as Example 2-2 except that the solid solution does not contain Mg. The discharge capacity of '0.1 C was increased. In addition, the rate ratio of the active materials of 'Example 2-1 to Example 2-1〇 was 58% or more' compared with the active materials of Comparative Examples 2-1 to 2-4, The rate ratio was remarkably improved, and the high rate discharge characteristics were excellent. On the other hand, as in the case of the active materials of Comparative Example 2-5 to Comparative Example 2-14, even if the solids contained the above-mentioned metal element ratio, the () surface was satisfied. The half-height of the final shot peak exceeds 〇.15. When the diffraction peak of the (114) plane exceeds 0.25°, only the discharge capacitance of less than 200 mAh/g can be obtained, and the ratio is also 54% or less. The discharge capacity and the rate ratio (high rate discharge characteristics) of the active materials of Comparative Example 2·1 to Comparative Example 2_4, which are the same as those of the solid solution, which are not substantially the same as Mg, are not mentioned. _ (the full width at half maximum of ^ = is 0.15. Hereinafter, the second &amp; 旳 diffraction peak is 0.25. Hereinafter, in the comparative example 2_2~ ratio outside the range of the half-height width invention of the present invention, "When the solid solution contains no Mg, the above-mentioned solid solution does not only have the hoisting of the 丨 丨 , but only the ( 〇〇 3 ) surface and the half of the 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 The high rate discharge characteristics are not improved. Comparative Example 2-15 is to become Lii+, Mn4+, see 2+, c〇3+, μ§2+ Substituting Mg for the equivalent of X = G, y=2/3, z = G activity = 3⁄4 a LiCo1/3Ni1/3Mn1/3〇2 (5) part of the transition metal site, specifically the equivalent of x = 〇, y = 〇56, z=〇1〇 results. Forging the temperature, the same example and A _.., (10)) and (114) diffracted waves; the semi-south width is also (four). At this time, the valence condition is maintained, but the amount of money in Non-Patent Document 6 is compared with Comparative Example 2-16 which is the above-mentioned active material containing no Mg, although the same burning temperature (10) and diffraction peaks are used. Half width and width, it can also be seen that the discharge is reduced. On the peak, the diffraction wave of the (〇〇3) plane of the active material of Example 2 is 0.25 T, and the crystallite size is also as large as 18 〇. In the same manner, the active material of Comparative Example 2_2 to Comparative Example 2-14 was as small as the crystallite size to 14 Gnm or less, and the high rate discharge characteristics were not evaluated. Further, the half-height of the active material of (1) is as small as that of the examples 21 to 2-1G, so that the crystallite size is (10) (10), but since the solid solution does not contain Mg, the high-rate discharge characteristics are not mentioned. The active material of Comparative Example 2·15 contained Mg and had a size of 180 nm or more. However, the discharge capacity and rate ratio (high rate discharge characteristics) containing Li+ and G] c at the transition metal site were not improved. The active material of Comparative Example 2-i6 had a crystallite size of i8 〇M or more, and 54 201125195 was excellent in high rate discharge characteristics, but the transition metal site contained Li+, and the discharge capacity of ο"c was not improved. Therefore, in order to maintain the discharge electric valley and increase the high rate discharge characteristics, it is preferable that the solid solution satisfies the above metal element ratio and the crystallite size is 180 nm or more. With respect to Comparative Example 2-17 to Comparative Example 2-20, A1 or Ti was substituted for Mg, and the solid solution of the lithium transition metal composite oxide was classified as a space group P3J2. The X-ray diffraction pattern 'the full width at half maximum of the diffraction peak of the (003) plane in the X-ray diffraction pattern is 〇"5. Hereinafter, the full width at half maximum of the diffraction peak of the (114) plane is 0.25. However, it is not possible to obtain a discharge capacitor of more than 200 mAh/g. The high rate discharge characteristics are also poor. As described above, the active material of the present invention satisfies the composition of the metal element contained in the solid solution of the lithium transition metal composite oxide. The ratio satisfies ^1+ Cx/3) COj.x_y.zNiy/2Mgz/2Mn (2χ/3) + (y/2) + (z/2)( X&gt;〇' y&gt;〇&gt;z&gt;〇, x + y + z &lt;l)"'" has an x-ray diffraction pattern attributable to the space group P3il2", and "the full width at half maximum of the diffraction peak of the (003) plane in the X-ray diffraction pattern is 0.15 or less. The (114) half-height of the diffraction peak of the surface is 0.25° or less. Three large discharge capacitors exceeding 200 mAh/g can be obtained, and the high-rate discharge characteristics are remarkably improved. [Example 3] (Example 3-1) An active material having a composition of Lii.2Co〇.丨Nio.^Mgo.ouMno.55. 2 was synthesized in the same manner as in Example 1-1 (Comparative Example 2-1 in Example 2) The same active substance). 55 201125195 (Comparative Example 3·1) The active material of Comparative Example 3_1 was synthesized in the same manner as in Example 3-1 except that Mg was removed from the metal element contained in the hydroxide precursor of the common hall. Comparative Example 2-1 the same active substance). (Comparative Example 3-2) The composition of the transition metal element contained in the hydroxide precursor of the common hall and the mixing amount of the cerium oxide clock monohydrate were changed according to the composition formula shown in Comparative Example 32 of Table 3. Except for the above, the active material of LiCoo.nNimMgo.ouMnowC^ was synthesized in the same manner as in Example 3_丨. (Comparative Example 3-3) The active material of Comparative Example 3-3 was synthesized in the same manner as in Comparative Example 3-2 except that Mg was removed from the metal element contained in the coprecipitated hydroxide precursor (in Example 2) Comparative Example 2-16 the same active substance). In the same manner as in Example 2, the full width at half maximum of the diffraction peak of the (〇〇3) plane and the full width at half maximum of the diffraction peak of the (114) plane were obtained, and the crystallite size was calculated. The active material of Comparative Example 3-2 is Li[Li1/3Mn2/3]02(x): 〇 〇〇〇,

LiNi^MiimC^ (y) : 0.641, LiMg1/2Mn1/2〇2 (z) : 〇 〇26,

LiCo〇2 (1-x-y-z): The half-width of the diffraction peak of the 0.333 and (003) plane is 0.14°, and the full width at half maximum of the diffraction peak of the (114) plane is 〇.23. The microcrystal size is 190 nm. (Production and Evaluation of Lithium Secondary Battery) Using each active material of Example 3-1 and Comparative Example 3-1 to Comparative Example 3-3 as a positive electrode active material for a lithium secondary battery, lithium was produced in the same manner as in Example 1. The secondary battery was evaluated for battery characteristics. 56 201125195 (DSC measurement method) The initial charge and discharge process was carried out in the same order as in Example 1. The secondary battery was subjected to a constant current charging with a current voltage of 4.3 V for 15 hours. Then, in the dewpoint -4 (the argon gas tank below TC is taken out of the positive electrode), the positive electrode is punched by 3 punches, and 1 羯 is sealed with the mixture layer to DSC (differential scanning heat) 2. Analysis] 'Used stainless steel steel towel for DSC measurement. Al2〇3 is used for reference in DSC measurement, and is measured in argon atmosphere to / dish, 400C. The heating rate is set to hole / Min. Filling method of the sample and reading method of the hot peak: According to JIS K 7121-1987 (measurement method of transfer temperature of plastic). Results of charge and discharge cycle test (0.1 C capacitor), rate ratio, DSC heat peak The temperature is shown in Table 3. [Table 3] Composition discharge rate rate ratio DSC mAh/g % Heat peak temperature ---- Example 3-1 ~~---___ 匕 Comparative example 3-1 ~~~~_ &amp;Comparative Example 3-2 ---------- —------- /0C _Ll^co〇.iNi〇.l38Mg0011Mn0!i5〇, 242 71 297 L li 2C〇〇.iNi015Mn 〇55〇2 223 52 277 LlC〇〇.33Ni0.3JMg00,3Mn0.33〇2 120 63 314 This example 3-3 ------- 1ίοο〇.33Νΐ〇.33Μη0.33〇2 145 88 314 as shown in Table 3' Non-lithium-rich lithium nickel manganese cobalt composite oxide (compared with 57, 201125195, Comparative Example 3-3) The discharge capacity of the active material of Comparative Example 3-2 to which Mg is applied is deteriorated, and the thermal stability is unchanged, whereas Lithium-rich lycopene complex composite oxide (Comparative Example 3-1) The discharge capacity of the active material of Example 3-1 using Mg was increased, and the thermal stability in the charged state was also improved. Since the active material for a lithium secondary battery of the present invention has a large discharge capacity and high discharge rate characteristics, it can be effectively used for a lithium secondary battery such as an electric vehicle power source, an electronic device power source, or a power storage power source. Although the present invention has been described above by way of a preferred embodiment, it is not intended to limit the invention, and it is obvious to those skilled in the art that the present invention may be modified and retouched without departing from the spirit and scope of the invention. The scope of protection of the invention is subject to the definition of the scope of the patent application. [Simplified description of the diagram] * Benefits [Key component symbol description] Benefit 58

Claims (1)

201125195 VII. Patent application scope: 1. An active material for a lithium secondary battery, which contains a solid solution of a clock transition metal composite oxide having a crystal structure of a_NaFe〇2 type, and a secondary battery/tongue substance It is characterized in that the composition ratio of the metal element contained in the solid solution satisfies Li1+(x/3) C〇lxy is /2Mgz/2Mn (μ) + (y/2) + (z/2) (X&gt;〇 , y &gt; 〇, Z &gt; 〇, X + y + z &lt; 1), having a x-ray diffraction pattern attributable to the space group, i.e., having a discharge capacitance of more than 2 centroids. 2. An active material for a secondary battery, comprising a solid solution having a transition metal complex oxide having a crystal structure of a_NaFe〇2 type, wherein the active material for the secondary battery depends on: the solid solution The composition ratio of the metal element satisfies Lil+(x/3) C(Wy zNiy/2Mgz/2Mn _ + _ + (z/2)U&gt;〇'y&gt;o'z&gt;o, x+y+z&lt;1) ' With an X-ray diffraction pattern attributable to the space group P3112, the intensity ratio of the diffraction peaks of the _ plane and the (m) plane obtained by the ray diffraction is 1 (_ &gt; 11^0 1 3. An active material f for a secondary battery containing a solid solution of a transition metal complex oxide having an a_Na type crystal structure, and the active material of the battery for the second battery is characterized by a composition ratio of a metal element contained in the four-phase matrix Satisfying Li1+(x/3) dy_zNiy/2Mgz/2Mn + _ + (ζ/2) x〉〇, y&gt;o, z&gt;o, x+y+z&lt;1;), having a space group P3U2 In the X-ray diffraction pattern, the half-height width of the diffraction peak of the (003) plane obtained by the diffraction of the x-ray is 〇15. Below, the half-height of the diffraction peak of the ridge is 0.25 or less. 59 20112 5195 4 kinds of clock-active materials for a human battery, comprising a solid solution of a (tetra) metal composite oxide having a leaky crystal structure, wherein the active material for a secondary battery is characterized in that the HI solution is contained The composition ratio of the metal element satisfies Lil~3) Uiy/2Mgz/2Mn (2x/3) + (y/2) + (z/2) x&gt;〇, y&gt;G, z&gt;G, x+y+z&lt;lt ; 1), having an x-ray diffraction pattern attributable to the space group P3! 12, the intensity ratio of the diffraction peaks of the (003) plane and the (114) plane obtained by the x-ray diffraction measurement is 1_)/1 ( 114) The half-height of the diffraction peaks of the $1-15 ' and (GG3) faces is 〇15. Hereinafter, the full width at half maximum of the diffraction peak of the (114) plane is 〇25. the following. 5. The secondary battery active material according to any one of the items (4) to 4, which is obtained by calcination at a calcination temperature of 92 (rc~1〇〇〇C)c. 6. The active material for a lithium secondary battery according to any one of claims 1 to 4, wherein the solid solution of the lithium transition metal composite oxide is produced by a co-precipitation method. The active material for a lithium secondary battery according to any one of the above-mentioned, wherein the lithium transition metal composite oxide has a composition ratio of a metal element of the solid solution of the lithium transition metal composite oxide of 1 /3 &lt;χ&lt;2/3, 〇&lt;y &lt;2/3, 0 &lt;ζ&lt;0·3. 8. The active material for a clock secondary battery according to any one of claims 1 to 4, wherein the solid solution of the lithium transition metal composite oxide is Li[Li1/3Mn2/3] 〇2, LiNi1/2Mni/2〇2, LiCo〇2 and LiMgmMn^O2 are solid solution compositions of four components. 9. The clock of 201125195 for a secondary battery according to any one of the first to fourth aspects of the patent application, wherein the valence of each element is formed in the upper-frequency transition metal composite oxide solid body The composition of the active material for a clock secondary battery according to any one of claims 1 to 4, wherein the synthesis of the upper frequency transition metal composite oxidation is carried out by uI+, Mn4+, Νρ+, cq3+', 1〇. The crystallite size is above 150 nm. An electrode for a lithium secondary battery, comprising the active material for a secondary battery according to any one of the above-mentioned items of the present invention. 12. A secondary battery for a lithium-ion secondary battery, comprising the electrode for a lithium secondary battery as described in the patent application (4), and the method for producing a secondary secondary battery, which is a maximum reaching potential of 4.3V using a positive electrode. (VS U/Li+) The following changes in the potential of the secondary battery described in the above-mentioned patent range 12 are at least relatively flat == surrounding 61 201125195 IV. Designated representative figure: (1) The designated representative figure is: None (2) The symbol of the symbol of the representative figure is simple: Yiwu. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: No 201125195ιχ For the Chinese manual No. 9_9131830, no underline repair] £ stomachman patent specification revision date f: 100 years January 13彳|, 1. year month e Γ&quot; supplement L (this manual format, ※ application number: ※ application 曰: steps, please do not change, ※ mark part Do not fill in) ^°//lA (χ〇^ ※Working pc classification: one from Dongying I, invention name: (Chinese / English) Clock secondary battery active material, secondary battery electrode, clock two Secondary battery and its manufacturer ACTIVE MATERIAL FOR LITHIUM SECONDARY 〇BATTERY, ELECTRODE FOR LITHIUM SECONDARY BATTERY, LITHIUM SECONDARY BATTERY AND FABRICATING METHOD THEREOF II. Abstract: The secondary battery active material contains a clock transition metal composite telluride having a crystal structure of a-NaFe02 type. In the solid solution, the active material for a lithium secondary battery is characterized in that the composition ratio of the metal element contained in the solid solution satisfies LiRG/wCchiy.zNiyaMgwMnQx/y + iyO + wz) (X &gt;0, y&gt; , z &gt; 0, x + y + z &lt; 1), having an X-ray diffraction pattern ' attributable to the space group P3ll2 and having a discharge capacitance exceeding 2 mAh/g. In addition, in addition to the above features, lithium two The secondary battery active material is characterized in that the intensity ratio of the diffraction peaks of the (〇〇3) plane and the (114) plane obtained by X-ray diffraction measurement is 2U5, and/or the diffraction peak of the (003) plane The full width at half maximum is 0.15. The full width at half maximum of the diffraction peaks of the (114) plane is 0.25° or less. 201125195 “Revised date: January 13, 1999 is the 99131830 Chinese manual without line repair ; ϊεμ 正极 The positive electrode active material of the non-aqueous electrolyte secondary battery with the discharge performance and the charge and discharge cycle, and the high energy density" (page 6 from bottom to bottom, line 7 to page 7, line 4), The positive electrode active material of the fifth aspect of the invention is characterized in that the total (four)_ of the above composite oxide is .. or less, and the powder of the CuKa ray is used as a ray diffraction _ 2 Θ to ι ± ι. The diffraction peak at the time is relative to 2Θ-18.6±1. The relative intensity ratio of the diffraction peaks at the time is (10) or more and 1. 〇5 or less. According to such a configuration, it is possible to form a positive electrode active material which is excellent in high-rate charge-discharge cycle performance and high in energy density (high-discharge electric power on the V-th row of the first nine hundred owes: pool) (page 8 from next 3 lines), "Positive application of the sixth item of the patent range === to: increase the oxidation_specific surface area. The 2 Θ of the powder X-ray diffraction pattern of the α ray = the peak relative to the 2 (four) 8.6 ± 1. The formation of the peaks: the production - soap two (10) or less. According to this configuration, in particular, non-aqueous substances which are excellent in charge and discharge cycle performance and high-energy in-between electric discharges" (page 9, line 4~ The first----------------------------------------------------------------------------------------------------------------------------------------------- The full width at half maximum of the peak is 0.05. The height and width are 0.10. The semi-energy of the diffraction peak above 44, 1 ± 1 丄 丄At θ. Under this configuration, especially k can be formed (4) Volume density (high discharge phantom, charge and discharge cycle performance 20112519' i Hl830 Chinese manual without line correction Correction of the positive electrode active material of the non-aqueous electrolyte primary battery which is excellent on the day of the first day of the month of the first day of the year (page 9, line 11 to line 16), but does not disclose the use of Mg as the specific composition of M When the full width at half maximum of the diffraction peak of the active material is within a specific range, the high rate discharge characteristics are remarkably improved. Patent Document 3 discloses "an active material for a lithium secondary battery containing a-NaFe〇2 type crystal. A solid solution of a lithium transition metal composite oxide having a structure, wherein the composition ratio of Li, Co, Ni, and Mn contained in the solid solution satisfies Lii+i/3xC〇 IxyNiy/2Mn2x/3+y/2 (x + y^l ^ 〇^y . i_x.y = z^ , in Li[Li1/3Mn2/3]〇2 (χ) -LiNi1/2MnI/2〇2 (y) _Uc〇〇2 (1) In the triangular phase diagram, (x, y, z) is present at point A (〇45, 〇55, 〇&gt;, point B(0.63, 0.37, 0), point C (0.7, 0.25, 0.05), point d (〇.67, 〇·ΐ8 0.15), point E (0.75, 0, 〇·25), point F (〇·55, 〇, 0.45), and point G (0.45 , 0.2, 0.35 ) as the apex of the octagonal ABCDEFg online or internal fan The value of the surrounding is shown, and the intensity ratio of the diffraction peaks of the (003) plane and the (1〇4) plane obtained by X-ray diffraction measurement is I (003) /1 (104) ^1.56 before charge and discharge. In the invention of I (〇〇3) j (1〇4) &gt;1" (Application No. 1) at the end of discharge, "a method for producing a lithium secondary battery, which uses a positive electrode during charging" A method of manufacturing a lithium secondary battery according to claim 9, wherein the method of manufacturing a lithium secondary battery according to claim 9 is characterized in that it comprises the following steps: performing at a voltage exceeding 4.3 V (vs Li/Li+), and the invention that the potential change occurring in the positive electrode potential range of 4 8 V or less (vs Li/Li+) reaches at least the charge of the relatively flat region (the patent application is the first item), and 201125195 Corrected flood season: January 13th, 1st year, the 991th cap towel weaving book is self-supporting: Ming i has to distinguish the degree of crystallinity according to the full width at half maximum. By analyzing the activity and the width of the present invention in detail, it was confirmed that the sample P remaining in the temperature at the temperature below the tank C remained deformed, and the deformation was removed by synthesizing at a temperature higher than the temperature. In addition, the size of the crystallites and the change in the synthesis temperature are such that the composition of the active material of the present invention is also slightly deformed within the system, and the size of the crystallites is sufficiently grown to increase the size of the input, and it is known that It is a synthesis temperature (峨 temperature) which affects the number of crystals and has a shape of 1% or less and a crystallite size of 15 μm or more. By forming the active materials f into electrodes and charging the lamps The discharge 'also shows that the expansion and contraction cause _, and the crystallite size is maintained at 13 G nm or more in the charge and discharge process, which is preferable in terms of the obtained effect. That is, by releasing the temperature by oxygen as close as possible to the above active material # The non-aqueous electrolyte used in the lithium secondary battery of the present invention is not limited, and the non-aqueous electrolyte f which is generally proposed for use in a clock battery or the like can be used. ^The non-aqueous/troreal agent used for the electrolyte may be a cyclic carbonate such as propylene carbonate, hexamethylene carbonate, chloroethylene carbonate or ethylene carbonate. ;丫_ a cyclic ester such as γ-butyrolactone or γ-valerolactone; a chain carbonate such as dinonyl carbonate or ethyl carbonate 'carbonate ethyl fluorenyl; decyl phthalate or hydrazine acetate Chain esters such as esters, decanoic acid esters, etc.; tetmhydro furan or its derivatives; deficiencies (nd^ane), 25 201125195, for the Chinese manual of No. 9131830, no scribe correction date : January 13, 100 1,4-two 11 dioxin, 1,2-dimethoxy ethane, 1,4-dibutoxy ethoxy, and diol Ethers such as methyl diglyme; nitriles such as acetonitrile and benzoquinone; dioxolane and its derivatives; ethylene sulfide; (sulfolane), a sultone, a sultone, a derivative thereof, or the like, or a mixture of two or more thereof, and the like, but is not limited thereto. Examples of the electrolyte salt used for the nonaqueous electrolyte include LiC104 and LiBF4. LiAsF6, LiPF6, LiSCN, LiBr, Lil, Li2S04, Li2B10Cl10, NaC104, Nal, NaSCN, NaBr, KC104, KSCN, etc. contain lithium (Li ), an inorganic ion salt of one of nano (Na) and potassium (K); LiCF3S03, LiN(CF3S02)2, LiN(C2F5S02)2, LiN(CF3S02)(C4F9S02), LiC(CF3S02)3, LiC(C2F5S02 3, (CH3)4NBF4, (CH3)4NBr, (C2H5)4NC104, (C2H5)4NI, (C3H7)4NBr, (n-C4H9)4NC104, (n-C4H9)4NI, maleic acid-(C2H5 4N ((C2H5)4N-maleate), benzoic acid-(C2H5)4N ((C2H5)4N-benzoate), phthalic acid-(C2H5)4N ((C2H5)4N- phthalate), lithium stearyl sulfonate An organic ionic salt such as lithium octyl sulfonate or dodecylbenzenesulfonic acid, or the like, and these ionic compounds may be used alone or in combination of two or more. Further, by using LiBF4 in combination with a lithium salt having a perfluoroalkyl group such as LiN(C2FsS〇2)2, the viscosity of the electrolyte can be further lowered, so that the low-temperature characteristics can be further improved, and self-discharge can be suppressed. ideal. Further, a normal temperature molten salt or an ionic liquid can also be used as the nonaqueous electrolyte. 26 201125195 "Improve the 曰 勘 勘 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 】 The coprecipitated product was taken out by suction filtration, and dried in an air atmosphere at normal pressure in an oven at a temperature of 1 Torr. After drying, the number of pulverized spiders having a diameter of about 120 mmcp was used in such a manner that the particle diameters were uniform. In a minute, the dry powder was taken. &amp; Lithium hydroxide monohydrate powder (LiOH, H2〇) and aluminum hydroxide were weighed in such a manner as to satisfy the composition formula of Comparative Example 1-16 of Table 1, and mixed to obtain I. The powder was mixed. σ & Next, the mixed powder was subjected to pellet molding under a pressure of 6 MPa. The amount of the precursor powder supplied to the pellet was determined by converting the weight of the synthesized product to 3 g. The formed pellets have a diameter of 25 ιηιηφ and a thickness of about 1 mm to 2 mm. The particles are placed in an aluminum boat of about 100 mm in total length and placed in a box-type electric furnace in an air environment. Under normal pressure Calcined at 100 °C (the above internal dimensions of the box type electrical ^ is 10 cm in the longitudinal direction, 20 cm in width, 30 cm in depth, and placed in the interval of 20 cin in the width direction. After the calcination, the heater is turned off. The switch keeps the aluminum boat in the state of the furnace and naturally cools it. The result 'the temperature of the furnace drops to about 2 CKTC after 5 hours, and the cooling rate thereafter is slightly slower. After a day and night, the furnace is confirmed. The temperature is changed to below it, and the particles are taken out and pulverized to a uniform particle size using a mortar. Regarding the obtained active material, the composition is LiuCoo iNioiAloouMnoiC^ 'About its crystal structure, using cu (Κα) tube The result of the powder X-ray diffraction measurement is observed in 37 201125195, the date of revision: January 13, 100 is the 99131830 Chinese description a NaFe〇2 type hexagonal crystal structure is the main phase. The ray was analyzed by the Rietveld method, and the results were in good agreement with the crystal structure model attributed to the space P3il2. (Comparative Example 1-17) In order to compare the properties of the active material with the substance of the present invention, The solid solution containing A1 instead of Mg is synthesized. LiiWoo 〇21Mii〇5395 02. For the composition of the transition metal element contained in the coprecipitated hydroxide precursor and the mixing amount of lithium hydroxide monohydrate and aluminum hydroxide, according to the table! In the same manner as in the case of the ratio M6, the active material of the comparative example was synthesized in the same manner as in the case of the comparative example 1-17. (Comparative Example 1-18) The characteristics of the active material were compared with the substance of the present invention. And a solid solution Lii 2c〇〇_i5Ti〇〇3Mn containing Ti instead of Mg was synthesized. The amount of the transition metal element 2 contained in the coprecipitated hydroxide precursor, X, and the amount of the mixture of the wind oxidation clock monohydrate and the titanium oxide is changed in accordance with the composition formula shown in Comparative Example M8 of ▲ 1 . Other than this, the active material of the comparative example was synthesized in the same manner as in the comparison &gt;1 1 16 . (Comparative Example 1-19) In order to compare the characteristics of the active material with the substance of the present invention, a solid solution Lim 2C〇〇iNi〇l5Ti0 05Mn〇 containing Ti instead of Mg was synthesized as a coprecipitated cerium oxide precursor. The composition of the transition metal element contained and the mixing amount of the hydrazine hydroxide monohydrate and the titanium oxide were changed according to the composition formula shown in Comparative Example 1-19 of Table 1, and the comparison was made with the comparison of 2011. No. 99131830 Chinese text specification No-line correction page Revision date: The composition of the composition on January 13, 100, and the composition of the hydroxide monohydrate, according to the composition formulas of Comparative Examples 2-15 and Comparative Examples 2-16 of Table 2. The active material of the comparative example was synthesized in the same manner as in Example 2-1 except that the change was carried out. The full width at half maximum of the diffraction peaks of the (003) plane and the (114) plane were obtained in the same manner as in Example 2-1, and the crystallite size was calculated. (Comparative Example 2-17) An active substance containing A1 instead of Mg was synthesized in the same manner as in Comparative Example 1-16, LiuCoo.iNio.wAlo.ouMno.wC^. 〇 (Comparative Example 2-18) An active substance containing A1 instead of Mg was synthesized in the same manner as in Comparative Example M7, LiuCoo.iNio.msAlo.c^iMno.s^^. (Comparative Example 2-19) An active substance Li12Coo.1Nioj5Tioo3Mno.52O2 containing Ti instead of Mg was synthesized in the same manner as in Comparative Example 1-18. (Comparative Example 2-20) In the same manner as in Comparative Example 1-19, an active material Q Lii, 2Co〇.iNi015Ti0 05Mn0 502 containing Ti instead of Mg was synthesized. (Production and Evaluation of Lithium Secondary Battery) Each of the active materials of Examples 2-1 to 2-10 and Comparative Example 2-1 to Comparative Example 2-20 was used as a positive electrode active material for a lithium secondary battery, and Example 1 was used. A clock secondary battery was fabricated in the same order to evaluate battery characteristics. The measurement results of the full width at half maximum, the calculation results of the crystal size, the charge and discharge cycle test results (0.1 C capacitance), and the rate ratio are shown in Table 2. [Table 2] 49 201125195 ΠΊα sigh 5 OOIsEnHT climbing u-ale se 济^斋^ s/q&lt;ul EC ^v暗# alkali 岵+(-0 1牦升(εοο) 2—λ-χ—- &quot; Ooon NOW, £sw'-a5j-Jz0~/ic5*, --zn~oc®, wcs5-n--J sssssss 0m OS ss OS s ww ss ses ssss nL uu 92 0 2&quot;6-02 0° &gt;1 St mEH s^. Oil s-οω&quot;· ωω- B S3 CS3 sz H s zs es ws Ge·- ΟΞ OS 0«l 0&quot;Production ora- f οΐ 0«_onouos sou°n cm tm cm oos Cm cm §1 OS 0»^ §·-SI 5.0 ε-ο8Sso Λ3s.°so8Sso S'G i ss 3.0 sso &quot;'0 SO 5.0 S3 E3 so WN.0so ε-ο SO sd HO -.0 95 9 -0 ©5 i'o -Ό 95 a° -*0 Is -ss '0 uo inch 5 2Ό &quot;-Ό 2Ό inch 10 i inch one inch ΪΌ inch '0 inch one inch inch-0 είΗΌ s-0 εεεο Io 0000 zasOusssj-EOO9-1 005 ss.o 000Ό NO«noc5»D.OMS-2ssooo^ 090Ό s OS 0 ZQS.OUSISSii-.ooos.5 gs°·0 8SS.0°3su5s0^2*555oosl5 inch zo. O0 ©so NOSSOUSNSOSSSJZSOGZi'-J gl°o rto Bso zoiousitlsssl.ol-OOQSr5 os.o oiz.o 9Ό°*su&quot;s,032sj-.ooqz---j 30Ό 85Ό 9Ό ϋο5ώυ2-”3·035§ΌΙ- .οοοζ·--ι Klq0 id sTMos.0u5 S0_a352.0~z-OOQ··--&quot; 9°°·°t-so 9Ό Ν°κ0υ2ε0α.0325·-ζ5ο0?·-η «00.0 ss 9Ό 2°seussoosss'--doo2n s°°s- 0 9.0 ζ°δου5§.0355·-ζ30ϋζ·'-η 0 no 9Ό°lc520!-doo2-n 0 s 9Ό 2°ss.ouss--5--ooqz5 0 3 9Ό 2qsu2sJ-.OOON-n 〇0 9Ό eoss.0cssJzl0. &quot;5 §°-0·0 OS.G wosdu2s.o32er---0n°81----1 zs.o 3 8S.G zolu2i52®[®!N5co®5·--so.os 9£0 20|&1152508281025〇°chen1.1. 二Ν5Ό ε.ο SS.G ?o*soll5eooOa2*J'zsoo?·--'-&quot; S5 OS 5 90 3°SSU5S'S5S055.0--3-, §0.0 ss 9Ό os.o OR.O 9Ό ^Olc5«-O.OM55- 3δΌ 88ΖΌ 9Ό NOSS0u5i,0s2i.'-N5OON-n 900Ό ss 9Ό 20550=21.0325----=00---1 Ns.o Ais 9Ό 508-ου^5Ό85βει.·--.αο&quot;Ί3 911-4-3^- ST??&quot;- wl-#^^ 2丨3冢 meal^ Meal u-g5^--0TS#^ -e-z ?&quot;&quot; 8— z5&quot;&quot; 卜i^l ε 丨z?粲qi ε—-#怒- Ts 吞05? Private β-z冢拉 s?^' 9- z f_i£ · T« ?z苳铋s?fc. z ΙΊ Νοοοπ *2νπ &lt;0 CM ΙΟ «Ο 1Θ4 181 180 180 0.24 0.24 0.14 0.14 5 5 0.012 0.021 0.288 0.279 &lt;0 φ dd Li f Ni0,144 Al0&gt;012Mn0 -M*O2 Lii^CoajNio |399A}0_02tMn0.a3«s〇2 Comparative Example 2-17 Comparative Example 2-18 °00π ΜΟ?·-^,·-ζπ°N,luuzn NOLSCWSn-l u&gt; cn in in 183 172 180 190 0.24 0.25 0.14 0.15 V· ΤΟ o 0.06 0.1 0.24 0.2 0.6 0.6 Lii_2C Q_iNiD jSTi0O3Mn0e2O2 U1.2Coo.1Nioj5Tio.05Mno.5O2 Comparative Example 2-19 Comparative Example 2-20 201125195ιχ For the Chinese manual No. 9_9131830, no underline repair] £ stomachman patent specification revision date f: 100 years January 13彳| 1. Year of the month e Γ&quot; Supplement L (This manual format, ※Application number: ※Application曰: Steps, please do not change any more, please do not fill in the ※ part) ^°//lA (χ〇^ ※工pc分类: 一从冬々〆一, Invention name: (Chinese / English) Clock secondary battery active material, secondary battery electrode, clock secondary battery and its manufacturing method ACTIVE MATERIAL FOR LITHIUM SECONDARY 〇BATTERY, ELECTRODE FOR LITHIUM SECONDARY BATTERY, LITHIUM SECONDARY BATTERY AND FABRICATING METHOD THEREOF II. Abstract: The secondary battery active material contains a solid solution of a clock transition metal complex telluride having an a-NaFe02 type crystal structure, and the lithium secondary battery is active. The substance is characterized in that the composition ratio of the metal element contained in the solid solution satisfies LiRG/wCchiy.zNiyaMgwMnQx/y + iyO + wz) (X &gt; 0, y &gt; 0, z &gt; 0, x + y + z &lt; 1), having an X-ray diffraction pattern ' attributable to the space group P3ll2 and having a discharge capacitance exceeding 2 mAh/g. Further, in addition to the above-described features, the active material for a lithium secondary battery is characterized in that the intensity ratio of the diffraction peaks of the (〇〇3) plane and the (114) plane obtained by X-ray diffraction measurement is 2U5, and/or The half-height width of the diffraction peak of the (003) plane is 0.15. The half-height width of the diffraction peak of the (114) plane is 0.25 or less. 201125195ι is the Chinese version of the <9131830 no-line correction page revision period: January, January, 2013, English abstract: An active material for lithium secondary battery contains a solid solution of lithium transition metal composite oxide having a- The active material for the lithium secondary battery is characterized by composite ratio of the metal element in the solid solution satisfying Lil+(x/3)C〇ixy-zNiy/2Mgz/2Mn(2x/3)+(y/ 2)+(z/2) y&gt;〇;Z&gt;0; x + y + z&lt;l), having a X-ray diffraction pattern belonging to space group P3112, and having discharge capacitance exceeding 200 mAh/g. In addition to The original features, the active material for the lithium battery is characterized by intensity ratio of the diffraction peak of (003) surface to (114) surface measured by X-ray diffraction being I(003)/I(114) 21.15, and/ Or half width of the (003) surface diffraction peak being 0.15° or less, and half width of the (114) surface diffractio n peak being 0.25° or less.