TW201242156A - Positive electrode active material for lithium-ion battery, positive electrode for lithium-ion battery, and lithium-ion battery - Google Patents

Abstract

Provided is a positive electrode active material for a lithium-ion battery that exhibits excellent battery characteristics. The positive electrode active material for the lithium-ion battery is represented by the composition formula LixNi1-yMyO2+a (in the formula, M is one or more elements selected from Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Bi, Sn, Mg, Ca, B, and Zr, with 0.9=x=1.2, 0< y=0.7, and a> 0.1). The primary particle size is 1.6-2.3 μ m, the carbon content as measured by the LECO method is 0.40 mass% or lower, and the lithium carbonate content that is the residual alkali of particle surfaces as measured by neutralization titration is 0.70 mass% or lower.

Description

201242156 VI. [Technical Field] The present invention relates to a positive electrode active material for a lithium ion battery, a positive electrode for a lithium ion battery, and a lithium ion battery. [Prior Art] A positive electrode active material of a lithium ion battery generally uses a lithium-containing transition metal oxide. Specifically, it is an acid chain (LiCo02), lithium acid recording (LiNi〇2), lithium manganate (LiMn2〇4), etc., in order to improve the characteristics' (high power makes money characteristics, storage characteristics, lower internal resistance, Ratio () characteristics) or improve security, and constantly compositing them. For lithium or ion batteries in large-scale applications for vehicle or load leveling, 4 seek the characteristics of the trip to date. In order to improve the battery characteristics, the Dingle electric beta tongue or the personal computer is used to improve the battery characteristics. For example, in the patent 1, the patented τ method does not have the following lithium two method, Li Texin#. (10) Positive electrode for human battery The manufacturer of the material "specially lies. Will LixNi yMy〇2_5 (〇·8 each X彡1.3, 〇&lt; 〇5

Fe, V, Ti, C... M is not free, Co, Mn,

At least cats in the group consisting of Ta, Be, B, Ca, s^7 Sn, Zn, Mg, Ge, Nb, and Zr "seek to be oxygen deficient or oxygen excess, indicating -〇ι: to:- The element, the composition of the recorded composite oxide is separated by the composition of the flat.]) and the larger particle size and the smaller particle separation particle size: 10 °: ° the larger the blended particle size and smaller. : 重量 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : The nickel composite oxide is one in which the amount of oxygen in the group is excessive, but there is still room for improvement in the positive electrode active material for 卽#t τ. Therefore, the object of the present invention is to provide a positive electrode for a clock-cell battery. The active material. The battery was specially studied by the inventors, and the result was between the battery and the battery characteristics. The amount of oxygen in the oxygen substance was a certain value and the positive activity of the field was 2, which was particularly good. Battery special 矣. See the carbon content of the positive active material and the tear of the positive active material The residue of the subsurface is the amount of carbonic acid, and the particle correlation with :: that is, the carbon content of the dice between the four rows of the hairpin is in the case of the grass I, and when the mass of the positive electrode is When a certain value is less than or equal to a value, a special amount of lithium carbonate can be obtained at a certain number of battery characteristics. The above-mentioned findings are based on the Hn lithium ion battery. Electrode also uses a positive active material, which

LixNi, -yMy〇2+ α ' The composition formula is: (The above formula ', Μ is selected from the group consisting of Sc, CU, Zn, Ga, Ge, Ai, Bi, Sn'M G wide, ~, more than one species, 〇 .9sx&lt;1, 1 -1.2 of Λ a, B and Zr, 〇 &lt; 〇7, the carbon amount measured by the method is ο. 40% by mass or less · υ 'Using coffee 0 Spear J measured by t and titration 201242156 The amount of the residual alkali on the surface of the particle, that is, the amount of lithium carbonate is 〇7% by mass or less. The positive electrode active material for a clock ion battery of the present invention, in one embodiment, the amount of carbon measured by the LEC method is uo mass% or less. And the residual amount of the surface of the particle measured by the titration is 0.60 mass% or less from the alkali, that is, the amount of lithium analytic acid. In another embodiment, the positive electrode active for the lithium ion battery of the present invention is further embodied. In the material state, Μ is selected from the group consisting of Μη and c〇. In the form of the positive electrode active material for a lithium ion battery of the present invention, in the composition formula, α &gt; 〇, 15. The positive electrode for a lithium ion battery of the present invention. In the form of the active material, α &gt; 0.20 in the composition formula. The present invention is a clock ion battery in another aspect. In the positive electrode, the positive electrode active material for a lithium ion battery of the present invention is used. In still another aspect, the present invention provides a positive electrode for a lithium ion battery according to the present invention. Provided is a positive electrode active material for a battery ion battery having a good battery characteristic. [Embodiment] (Configuration of a positive electrode active material for a lithium ion battery) The material of the positive electrode active material for a lithium ion battery of the present invention can be widely used as a general The compound of the positive electrode active material for the positive electrode of the ion battery is preferably a transition of a lithium cobaltate (Lic〇〇2), a lithium nickelate (Li 2), a Lithium acid (LiMn2〇4), or the like. Metal oxide. The positive electrode active material for a clock ion battery of the present invention produced by using the above materials is represented by the following formula 201242156:

LlxNii- yMy〇2+ a (In the above formula, M is selected from the group consisting of Sc, Ti, v, Cr, Mn, Fe, c.

CuHGa'Ge'AbBi'Sn'Mg'CamrSii species above, 0.9 passengers. The ratio of the clock phase in the positive electrode active material for a lithium ion battery is "this is because it is not reached. .9, it is difficult to = crystal structure, if it exceeds 12, it will not be able to ensure the high capacitance of the battery. The oxygen of the positive electrode active material for a clock ion battery of the present invention is expressed as 〇2"(α &gt;〇1) in the composition formula, and is excessively contained. When used in a plasma battery, the capacitance, The battery characteristics such as the ratio characteristics and the capacity retention ratio are good. Here, 'about', preferably 1 5 is α &gt; 0.20. In the positive electrode active material for a clock ion battery of the present invention, the amount of carbon measured by the lean method is 〇. The amount is less than or equal to eLE (3). The insoluble gas is dissolved. The external absorption method is defined, for example, in the claw R 16〇3. When the carbon content of the positive electrode private substance exceeds 0 to 40% by mass, the battery characteristics of the positive electrode active battery can be used, and in particular, the cycle characteristics are deteriorated. The amount of carbon measured by the LECO method is preferably 〇3〇% by mass or less, more preferably 0.20% by mass or less. The carbon contained in the positive electrode material exists exclusively in the interior or surface of the particles of the positive electrode material, but exists in the form of a carbonic acid clock l2C03). The weakness of the carbonated material will cause the battery to drop, so it is better to have less residual test. As described above, in the present invention, the carbon content of the extremely active material is expressed by the amount of carbon contained in the positive electrode material in the form of carbonic acid clock 6 201242156 (Ll2C〇3 ), and if the amount is small ( If it is 〇4〇 mass 〇/〇 or less), the battery characteristics become good. In the positive electrode active material for a lithium ion battery of the present invention, the amount of lithium carbonate, which is a residual alkali on the surface of the particles, which is measured by neutralizing the dropping, is 〇·7% by mass or less. The neutralization titration is carried out by using a normal neutralization drip method using hydrochloric acid or the like as a titration solution. When the amount of lithium carbonate, which is a residual alkali on the surface of the particles, exceeds 〇 7 mass%, the reaction with the electrolytic solution is repeated when charging and discharging are repeated, and the production characteristics are deteriorated. Moreover, if the test is large, gas generation occurs, and the second characteristic is deteriorated. The residual alkali on the surface of the particles measured by neutralization titration, i.e., carbon I, is preferably 〇 6 〇 mass. /. In the following, it is more preferable that the positive electrode active material for the ion battery is a secondary particle formed by aggregating primary particles or primary particles, or a mixture of primary particles and secondary particles. The positive electrode active material for a lithium ion battery preferably has an average particle diameter of primary particles or secondary particles of 2 to 15 // m. If the average particle diameter is less than 2 μm, it is difficult to apply to the current collector. When the average particle diameter exceeds 15 μm, voids are likely to occur during filling, and the filling property is lowered. Further, the average particle diameter is more preferably 3 to 1 〇 M m. (Position of a positive electrode for a lithium ion battery and a lithium ion battery using the same) The positive electrode for a lithium ion battery according to the embodiment of the present invention has a structure in which a positive electrode active material for a lithium ion battery and a conductive auxiliary agent having the above-described configuration are mixed. The positive electrode mixture prepared by using a binder is provided on one side or both sides of a current collector formed of an aluminum box or the like. Further, a lithium ion battery according to an embodiment of the present invention includes the positive electrode for a lithium ion battery having the above configuration. (Manufacturing Method of Positive Electrode Active Material for Clock Ion Battery) 201242156 l = A method of producing a positive electrode active material for a clock ion battery according to an embodiment of the present invention will be described in detail. First, a metal salt solution is prepared. The metal is Ni and is selected from the group consisting of Sc, Ti, V, Cr, Μη, Fe, r ^ C 〇, Cu, Zn, Ga, Ge, A1, Bi, Sn,

One of Ca, B, and Zr is connected, and L _ is more than one type. Further, the metal salt is a sulfate, a vapor, a tribasic acid salt, an acetate or the like, and particularly preferably a sulfate. The reason for this is that even if the towel is fired in the form of an impurity, it can be directly burned, so that the washing step can be omitted; the nitrate functions as an oxidizing agent and has a function of promoting oxidation of the metal in the firing raw material. The metal contained in the metal salt is adjusted in advance to have a desired molar ratio. Thereby, the molar ratio of each metal in the positive electrode active material is determined. Next, lithium carbonate was suspended in pure water, and then a metal salt solution of the above metal was introduced to prepare a metal carbonate solution slurry. At this time, lithium carbonate containing fine particles is precipitated in the slurry. Further, at this time, &amp;&gt; mixing lithium carbonate with a metal salt solution and stirring, and (4) the more the granules are, the smaller the granules are, and the better the reaction is, and the unreacted The amount of lithium carbonate is reduced, whereby the carbon content in the produced lithium salt composite (precursor for lithium ion battery positive electrode material) can be suppressed. The stirring condition is to stir the solution by using a stirring blade of a specific size at a rotation number of about 25 rpm. In the case where the compound is not reacted during the heat treatment of the sulfate or the vapor of the metal salt, the salt is washed with a saturated lithium carbonate solution and then separated by filtration. For example, when the nitrate compound or the acetate compound is reacted as a lithium raw material during the heat treatment, it may be directly separated by filtration and dried without being washed, thereby being used as a precursor of 8 201242156. Next, the powder of the lithium salt complex (precursor for the lithium ion pool positive electrode material) is obtained by drying the filtered 椹 π 々 々 々 人 人 人 人 人 3 3 3 3 其次 其次 其次 其次 其次A firing vessel having a specific amount of . ^ ^ ' is filled with a lithium ion battery in the baked grain, and is a powder of a precursor for the battery positive electrode material. The person-person moves the calcination barn filled with the powder of the precursor of the positive electrode material of the positive electrode material to the calcining furnace to carry out the crucible. / Fancheng is made by heating in an oxygen atmosphere for a specific period of time. When the firing is carried out under pressure of 1 202 1 to 202 KPa, it is preferable because the amount of oxygen in the a-addition composition is further reduced. Then, the crucible is taken out from the baking container, and the unfinished material is taken out, and pulverized by using a commercially available pulverizing apparatus or the like to obtain a powder of the positive electrode material. The pulverization at this time is carried out in such a manner that fine particles are not formed, 敕, &amp; a h , and the appropriate pulverization strength and pulverization time are obtained. Specifically, by the smashing of the field, the D90 is set to the point where the cumulative curve becomes 90%, and the ancestors are in the melon (# m), and D10 is set as: the cumulative curve becomes 1〇%. At the point of the particle diameter (heart), (D9〇-D10) /2 can be adjusted to "below". It is better to adjust (d9〇_di〇) /2 to the following. In the case where the pulverization property is preferred, the occurrence of fine powder is less, and the coarse and private bodies are less likely to be inferior, so that D9 〇 becomes a relatively small value and becomes: a larger value. In particular, in the case of the material cracking, the grain size and the region of the J are likely to be in a state of pulling out the long hem (the tail appears), and if it is 'this case', the DH) becomes relatively small, and the result is Said - m〇) is not big. That is, (D90 - D10)/2 can be said to be an indicator indicating that the granularity is less uneven. 9 201242156 In the present invention, by suppressing the above-described pulverization, the surface area of the powder of the occurrence of the parent volume e + Τ &lt; Μ powder can be reduced, so that the amount of lithium hydroxide on the surface of the particles can be suppressed. Bait on the surface

[Examples J and 2] Embodiments for better understanding of the present invention and its advantages are not limited to the embodiments. (Examples 1 to 1 5) The carbonic acid clock of the input amount described in Table 1 was suspended in pure water, 3.2 liters of a metal salt solution. Here, the metal salt solution is adjusted to be a hydrate of the acid salt, and each metal is made into the table &quot;==2, and the total metal molar number is adjusted to 14 moles. The mixing system (4) machine is used to perform the drop at a rotation number of 25Grpm. Furthermore, the amount of lithium carbonate suspended is Li J σ r fine contact v xiNll-yMy 〇 2+ α represents the primary battery positive electrode material, 卩卩if β U· 夕 “θ (four) is the positive active material) and χ The S which is the value of Table 1 is calculated by the following formula: WC g) = 73.9χ14χ ( 1 + 〇.5χ) 预先 In advance, “Α” is used to float in addition to the amount necessary for the precipitation reaction. Subtracting the value of the chemical::: multiplied by the residual carbonic acid in the filtered material, "A", such as the case where nitrate or acetate is reacted in the chain salt raw material, such as sulfate or vaporized The reaction as a raw material for baking was 10. The lithium carbonate containing the small particles is precipitated, and the precipitate is separated by filtration. Then, the precipitate was dried to obtain a clock-containing carbonate (precursor for the positive electrode material of the battery ion 201242156 battery). Write the inside of the L to prepare the firing vessel 'fill the lining carbonate in the firing capacity table 1;:, put the firing vessel into the oxygen atmosphere furnace at atmospheric pressure; get 1: firing temperature to keep it cold After that, carry out one

Next, a powder of a positive electrode material for a clock ion secondary battery was obtained by using a small pulverizer (hosokawamicron ACM-2E to pulverize the obtained oxide into a fine particle of a specific particle size to a specific particle size distribution). 1 6) In Example 16, the metal of the raw material is a composition shown in Table 1, and the metal salt is a chloride, and after the precipitation of the clock-containing carbonate, the solution is washed with a saturated carbonate solution, and ??? The same treatment as in the examples was carried out. (Example 1 7) Example 17 was such that each metal of the raw material had the composition shown in Table j, and the metal salt was a sulfate, and after the lithium-containing carbonium salt was precipitated, saturated carbonic acid was used. The lithium solution was washed, filtered, and the same treatment as in Example 15 was carried out. (Example 18) Example 8 was such that the metals of the raw materials were the compositions shown in Table 1, not The same treatment as in Examples 1 to 15 was carried out except that the air was burned under a dust of 12 kPa KPa. (Comparative Example ～3) Comparative Examples 1 to 3 were used as raw materials. Each metal is shown in the table], and 201242156 The stirring condition in the reaction of the acid with the metal salt solution is such that the number of rotations of the stirring blade is 15 rpm, and the pulverization of the last oxide is not adjusted as in the first to the first embodiments, except that The same treatments as in Examples ι to ΐ5 (Comparative Examples 4 to 6) Comparative Examples 4 to 6 were such that the metals of the raw materials were of the composition shown in Table i, and were not in an oxygen atmosphere furnace but in an air atmosphere furnace. The firing step was performed in the same manner as in Comparative Example 1. (Evaluation) - Evaluation of composition of positive electrode material - Metal content in each positive electrode material was determined by inductively coupled electro-polymerization emission spectrometer (ICP) - OES) The composition ratio of each metal (mole ratio) was calculated, and the oxygen content was measured by the LEC0 method and α was calculated. The results were confirmed as shown in Table 1. - Evaluation of average particle diameter The powder of each positive electrode material was collected, and the average particle diameter was measured by a laser diffraction type particle size distribution measuring apparatus (Microtrack ΜΤ3300 ΕΧΙΙ). - Evaluation of carbon amount The amount of carbon in the positive electrode material was determined in accordance with JIS G1211 and jIS G1215. 'Measurement by the LEC0 method. That is, each positive electrode material powder of 〇丨~〇坫 is collected, and 2 g of a carbon-free combustion-supporting material is added and placed in a ceramic crucible, and then a high-frequency melting furnace is used. The amount of carbon is determined by using an infrared detector to detect the components during combustion and quantifying the amount of carbon. The evaluation of the amount of hydrogen peroxide 1 201242156 The amount of lithium hydroxide on the surface of the particles using hydrochloric acid as the titration solution. Determination and titration to determine the positive electrode material - evaluation of battery characteristics -, ratio # 1: each JL pole material, conductive material and bonding

The agent 'dissolves the binder in an organic solvent (N-Methyl sulfonate), and then mixes the positive electrode material material into the slurry to be applied to the Α1 ϋ and dried. The positive electrode was produced by making a house. Then, a 2032 type coin battery (C〇in Cel1) for which the opposite electrode was Li was prepared, and 1 M-LiPF6 was dissolved in EC-DMC (1: i) as an electrolytic solution, and the current density was measured at 2 C. Discharge capacitor. Further, the ratio characteristic was obtained by calculating the ratio of the discharge electric valley of the battery capacity at the current density 2C to the current density C 2C. Further, the capacitance retention ratio was measured by comparing the initial discharge capacitance obtained by discharging a current of 1 C at room temperature with the discharge capacitance after the 〇〇 担 ring. The results of these are shown in Tables 1 and 2. 13 201242156 After smashing (D90-DIO) /2 (//m) (N CN wS ON inch · ro — vd uS O) — vd 00 v〇 inch · Bu (N v〇v〇v〇&lt;N v 〇00 vd Os v〇 inch l—M 00 00 On 00 VO 00 00 x&gt; d CS oo inch o b o OS ogo bdmo PH o cn 〇r—H o &lt;N 〇gd cn odoo ΓΛ (N o 00 o Os 〇oor—^ o [-0.011 ood X oooo 10.025 1 V) odoooooo 〇oooooooooooqo ^ 〇looo I 1000 [looo I | looo | o ON o V&quot;&gt; 〇\ | looo | o &lt;N On oo § Ogogogogo I looo I 1 1000 o »n Os 1000 o (N oo 00 ogogog 1 removes the composition ratio W of each metal in all metals of Li CN cs &lt; »n 5 ο »n tn CS (N 1 m rr; m cn acn m ... cn ci ci ΓΛ m acn cn (T; cn m CO »〇(S &lt;N omm ΓΛ &lt;ri CO m cn cn &lt;ri CO m (N oo CO a cn m CO en ... m cn ... CO r^! m ΓΛ a CO m CO mr*H iTi o vn v*&gt; l〇»-H m a to one mm a ΓΛ CO in oo 2 ΓΛ ri m CO ci m a cn co a m a cn ΓΛ cn ssggggg CO cn cn m ... cn ... mm ... ms § g § § Lithium carbonate suspension (g) m On cn 1393 CO Os m ro ON m 1442 m On m CO ON CO Os cn ΓΛ ON ΓΛ CO On fO 〇&gt; ΓΛ m On mm ON r*M m Os 1-H cn 〇\ m (7) On CO »—H 1393 1393 cn On cn Os cn ΓΛ 〇\ m os rn cn OS mr*H Os m Example 1 Example 2 Example 3 Example 4 Example 5 | Example 6 I Example 7 Example 8 | Example 9 1 Example 10 Example 11 Example 12 | Example 13 I Example 14 | Example 15 1 Example 16 | Example 17 1 Example 18 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Inch 201242156 [Table 2] Capacitance retention ratio (%)

Evaluation) Examples 1 to 18, in which the battery characteristics are compared with the salt as the nitrate, Examples 1 to 5, and 8: Good: 'The metal of the raw material is stepped on' is not performed at atmospheric pressure::: particularly good . The fired Example 18 had the best battery characteristics.疋 加压 加压 加压 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然 虽然In Comparative Examples 4 to 6, the composition of the metal as a raw material was outside the range of the present invention, and battery characteristics were further deteriorated due to stirring conditions and pulverization conditions. [Simple diagram description] None [Main component symbol description] None 16

Claims (1)

201242156 VII. Patent application scope: 1. A positive electrode active material for lithium ion batteries, which is represented by the following group: LixNi, -yMy〇2+ a (in the above formula, 'M is selected from Sc, Ti, V, Cr , Μη, Fe, Co, Cu, Zn, Ga, Ge, A, Bi, Sn, Mg, Ca, B, and Zr The amount of carbon measured by the LECO method is 〇4〇 mass. And the surface of the particle measured by the drip is the carbonic acid 〇. 7 % or less. 2. In the case of the positive electrode active material for the ion battery of the patent scope, the amount of carbon measured by the LECO method is 〇·2〇% by mass or less, the amount of lithium carbonate, which is the residual alkali on the surface of the particles measured by the sputum, is 0.60% by mass or less. Ma 3. For the first part of the patent scope, (4) Positive electrode active material for sub-cells In the above formula, the ruthenium is one or more selected from the group consisting of Mn & c. 4. The positive electrode active material for lithium ion batteries of the first or third object of the patent application range is 'in the composition formula, α> 〇 15. 5. If the positive electrode active material for lithium-ion battery is applied for in the fourth patent scope, 'In the composition formula, 'α> 〇.:2〇. ^(4) Positive electrode for ion battery, which uses a positive electrode active material for lithium ion batteries, which is a patented model. Le 7·-Lithium-ion battery Use positive electrode with Shen ion battery. Month Patent No. 6 clock 17