TW201235302A - Lithium nickel manganese oxide composite material, method for making the same, and lithium battery using the same - Google Patents

Abstract

The invention relates to a lithium nickel manganese oxide composite material including a positive material grain and an aluminum phosphate layer coated thereon. The material of the positive material grain is represented by a formula LixNi0.5+y-aMn1.5-y-bMaNbO4, wherein x is equal to or smaller than 1.1, and equal to or larger than 0.1, y is smaller than 1.5, and equal to or larger than 0, a-y is smaller than 0.5, and equal to or larger than 0, and b+y is smaller than 1.5, and equal to or larger than 0, M and N are selected from the group consisting of an alkali metal, an alkaline-earth metal, a Group 13 element, a Group 14 element, a transition element, a rare earth element, and combinations thereof. The invention also relates to a method for making the lithium nickel manganese oxide composite material, and a lithium battery.

Description

201235302 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a secret ship composite material and a preparation method thereof, and a lithium ion battery. [Prior Art] [0002] For the ionic battery, the _f_(four) surface material is used to form a coating, which is a common method for modifying the positive electrode active material. For example, 'coating on the surface of Wei Tie _ particle can effectively solve the problem of low conductivity of the lining, so that it has good conductivity in the coated (10) _ acid iron. In addition, the prior art has shown that it is difficult to surface coating in cobalt acid or other sparse active materials. The thermal stability of the positive electrode of the ion battery can be improved (please refer to the literature "C (4) Hearttion between A1P〇4 staff (1)...c〇ati Called thickness on LiCoO ra+iu 2cath〇de and thermal stabmity” J.Ch., Electroc〇chimica “ _ pre-and patents, (four), US patents for rights) ° 前I pre-technical coating with acid filling The method of the positive active material is to prepare a dispersion formed by dispersing the disc acid in the water, and adding the positive active material particles to the dispersion of the (4) acid granules, and absorbing the sage On the surface of the positive (4) large particle, the water in the dispersion was evaporated to dryness and heat-treated at 70 CTC to form a positive electrode active material having aluminum phosphate particles on the surface. [0004] However, because the Wei material is soluble in water, Wei (four) particles Agglomeration can be formed when dispersed in water, and when a large amount of positive active material is added to the composition of the acid positive 100133405 Form No. A0101 Page 4 / Total 41 page 1002056727-0 201235302, the positive active material adsorbed first The amount of aluminum phosphate particles, after the addition of the positive electrode active material particles may not adsorb enough aluminum phosphate particles. Referring to Figure 17, even if it can be well coated, the above method determines that the product 20 is microscopically aluminum phosphate. The morphology of the small particles 22 is distributed on the surface of the large active material 24 of the positive electrode active material, and is not a uniform phosphoric acid layer. Therefore, the aluminum phosphate coating layer formed on the surface of the positive electrode active material by the above method is not uniform enough to ensure each positive active material. The surface can be evenly coated with a layer of aluminum phosphate, so that the lithium ion battery with the positive electrode active material has poor cycle performance, which makes the method difficult for large-scale industrial application. The method for forming a uniform aluminum phosphate coating on the surface of the H-type hetero-oxide lion, and the lithium-recorded oxide composite material having the aluminum phosphate coating layer, and the application of the chain oxide composite material A lithium ion battery is necessary. - A recorded oxide composite material comprising positive electrode active material particles and coated on the positive electrode The surface of the material particles (4) acid material, the positive electrode 1.5-y-bMaNb〇4 is a-y<5, and the active material particles are represented by the chemical formula Li Ni Μπ x 0 · 5 + y - a, wherein 0. L^x^l. Buddy $γ<1 5,〇

Sb+y<l. 5, Μ and Ν are _ species or plural species of an alkali metal element, an alkaline earth metal element, a u-th element, a group 14 element, a transition element, and a rare earth element. A method for preparing a lithium nickel manganese oxide composite material, comprising: providing a nitrate solution; adding a positive electrode active material to the acid solution to form a mixture of the cathode active material is formed by the form number A0101 5 pages/total 41 pages 1002056727-0 [0007] 201235302

---, -bMaNb〇4 means 'where 〇. IN is a metal or a metal element, a 13th element, a (10)-, a transitional element, and a rare earth element; A squary acid 70 salt solution is added to the mixture to form a reaction, and a surface of the positive electrode active material is formed on the surface of the positive electrode active material; and a positive electrode active material particle having a phosphate layer on the surface is heat-treated. [0008] A lithium ion battery, which consists of 蛀τ & —τ, which also includes a positive electrode comprising the above-described choline manganese oxide composite material. _] Compared with the pre-S technology, the present invention avoids uneven adsorption due to solid-solid mixing, resulting in uneven coating of aluminum phosphate, and is suitable for large-scale industrial applications. Further, the present invention can form a layer thickness on the surface of the positive electrode active material particle and continuously_acid_, instead of depositing phosphoric acid particles on the surface of the positive electrode active material particle, thereby having better electrochemical performance. [Embodiment] _ 〇 下面 下面 下面 下面 下面 下面 下面 下面 下面 下面 下面 钟 钟 钟 钟 钟 钟 钟 钟 钟 钟 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 [0011] Referring to FIG. 1, an embodiment of the present invention provides a positive electrode composite material ι 〇 comprising a positive electrode active material·12 and phosphoric acid _14 coated on the surface of the positive electrode active material particle. The phosphoric acid-14 has a mass percentage of 1% to 3% in the positive electrode composite particles U). The thickness of the dish acid layer 14 is preferably from 5 nm to 2 nm. The rhyme layer 14 is formed in situ on the surface of the positive electrode active material particle 12. The dish (10) layer 14 is a continuous layer of aluminum phosphate material having a thickness of 1002056727-0 201235302. All surfaces of the positive electrode active material particles 12 are covered by the continuous aluminum phosphate layer 14. Further, an interface diffusion may be formed at the interface between the aluminum phosphate layer 14 and the positive electrode active material particle 12 to diffuse cobalt atoms into the aluminum phosphate layer 14 [0012] The material of the positive electrode active material particle 12 may be a layered lithium cobalt oxide structure or a nickel-doped spinel lithium manganate structure, specifically by a chemical formula

LixcVzMzVtu 八5+7 >1 5 y bMaV4 means that 1~x-1· 1 * 〇^y<1.5 » 0^a-y<0. 5 » j_〇^ b+y<l. 5, And each Z<1. Each of M&N is selected from the group consisting of an alkali metal element alkaline earth metal element, a cerium (four) element, a lanthanum 14 group element, an over (four) element, and a rare earth lanthanide or a plurality of species 'preferably, selected from the group consisting of Cr, c〇, v, 1 At least _ of Fe Ga and Mg. Wherein the range of y is preferably hy<〇.1. Specifically, the material of the material of the positive electrode active material particle 12 may be LiCoO or LiNi Μ 2 ^ 2 〇 · 5Μηΐ. 504. The particle diameter of the positive electrode active material particles 12 is preferably from nanometer to micrometer, more preferably from micrometer to 20 micrometer. [0016] [0016] [0016] 100133405 Step one, providing an aluminum nitrate solution; Step two, the liquid to be coated, forming a mixture of positive electrode active material particles plus the nitric acid solubilized =, will The salt solution is added to the present compound to carry out the reaction. The surface of the material particle is formed into a dish of the acid layer. The number of the table is the same as that of the page. The page is made up of: page 1002056727-0 201235302 [0017] Step 4 'heat treatment the surface has Wei Ming The positive electrode active material particles of the layer were obtained as positive electrode composite particles. [0018] The aluminum nitrate solution includes a liquid phase solvent and aluminum nitrate dissolved in the solvent. It is understood that the solvent is selected such that the nitrate (4) can be dissociated from the solvent of 3+. Therefore, the solvent is not limited to water, and may be a volatile organic compound. Preferably, the solvent is one or a combination of ethanol, propylene mesh, dioxane and gas. When the solvent is used as a solvent, an organic solvent such as ethanol is used as a solvent to prevent the positive electrode active material particles from reacting with water to lower the performance of the positive electrode active material. [0019] In the above step two, the positive electrode active material particles are insoluble in the aluminum nitrate solution, and the two materials are mixed with solid and liquid, and the surface of the positive electrode active material particles is uniformly attached to the layer A13, and the ai3+ exists in the form of ions. , the surface of the positive active material particles can be uniformly formed on the surface of the positive active material particles to form an atomic coating. Further, the amount of the positive active material added may be controlled. The ratio of the positive active material particles to the nitrate solution may be (4) such that the nitrate (4) can cover the surface of the positive active material particles, so that The mixture is in the form of a slurry. The purpose of forming a mud-like mixture is mainly to control the amount of the acid solution to be just enough to form an aluminum phosphate coating on the surface of the positive electrode active material particles. Specifically, the volume ratio of the volume of the aluminum nitrate solution to the positive electrode active material particles is about 1:10 to 1:4 Torr. The particle size of the positive electrode active material f is preferably less than 20 μm. The amount of the aluminum nitrate solution added can be determined by the mass percentage of the aluminum phosphate coating layer to be formed in the positive electrode composite material particles. Preferably, the mass percentage of the aluminum phosphate coating layer in the coarse electrode of the positive electrode composite material is 〇 1% to 3%. 100133405 Form No. A0101 No. 8 1/Total 41 1 1002056727-0

201235302 [観0J In the above step three, the phosphate solution includes water as a solvent, and a soluble phosphate such as an ammonium phosphate dissolved in the solvent. The wall acid salt includes a mixture of one or more of ammonium dihydrogen phosphate (NHP0J, diammonium phosphate 4 ft ((ΝΗ4:)2ΗΡ〇4) and triammonium phosphate CCNWPOp. Acid ion. The acid ion of the dish may be one of orthophosphate ion (P〇43_), dihydrogen phosphate ion (H p〇-), and 2 4 Ο 峨 acid-hydrogen ion (HP〇42-) or When the phosphate solution is added to the slurry mixture, the phosphate ion reacts with Al3 + attached to the surface of the positive electrode active material particle to form a uniform aluminum phosphate in situ on the surface of the positive electrode active material particle. Preferably, the phosphate solution may be added dropwise to the slurry mixture and stirred to allow the phosphate ion to react uniformly with the A13+ on the surface of the positive electrode active material particle. Similarly to the aluminum nitrate solution, The amount of the disc acid solution can be determined by the mass percentage of the positive composite particles required to form the acid coating layer. [0021] ❹ In the above step four t 'the purpose of the heat treatment is to make the acid The polar active material is better combined at the interface to form a composite material, and the residual solvent and the ammonium amicate formed by the reaction are removed. The heat treatment may form an interface diffusion between the phosphoric acid and the positive active material interface to make the positive electrode active material The metal atom diffuses to the __ layer. (IV) The treatment temperature may be from 4 to 8. The heat treatment time is preferably from 05 to 2 hours. [0022] 100133405 Since the square wire adds the positive active material to the general solution The ΓΓ_ contained in the liquid can be reacted with the ionic ions to form a phosphate solution, so that the surface number of the positive active material particles is generated in situ. Α0101 Page 9 / Total 41 pages 1002056727-0 201235302 The phase of the positive acid active material f particles of the solid phase of the slick acid slab is mixed, which can be called to cover the surface of the mixture, and (4), the phosphorus formed by the ionic ions after the pure reaction It can also be more (9) and continuously coated on the entire surface of the positive (four) particles of the positive electrode. Compared with the method of first synthesizing the shot (four) particles, and then adsorbing the surface of the positive electrode (four) particles by the adsorption of the acid (four) particles. The method avoids the phenomenon of uneven adsorption caused by solid-solid mixing, resulting in uneven coating, discontinuity or incomplete coating of the dish, which is suitable for large-scale industrial application, and the method can be used in the positive active material particles. The surface generates a thickness of m and a continuous phosphoric acid inlaid layer, and the non-acid is deposited on the surface of the positive electrode active material particle. The aluminum phosphate layer can pass ions while injecting electron migration between the electrolyte and the active material. Thereby, the electrolyte is prevented from decomposing at a higher voltage while completing the introduction and removal of the rotor, so that the positive active material can have better battery electrochemical performance and capacity retention performance at a higher voltage. [0024] The positive electrode composite material particles are prepared by coating the positive electrode active material particles with a bowl of acid, and the positive electrode is recovered by using the above method. The material particles were used in a plasma battery for performance testing. Example 1: Aluminum phosphate to lithium cobaltate composite material In the present embodiment, the positive electrode active material particles are drilled acid particles, and the chemical formula is [1(:〇〇2). The aluminum phosphate-cobaltate composite material includes lithium cobaltate. The granules and the aluminum phosphate layer coated on the surface of the 5H lithium cobalt oxide particles. The preparation of the _]纟__(tetra) lithium acid composite material is 100133405 Form No. 1010101 Page 10/Total 41 Page 1002056727-0 201235302 Nitric acid The solution formed in ethanol is 1 liter, and the molar concentration is 0.16 mol/liter. The addition of the acid clock particles is 1 〇〇g ° _ the acid solution is (10) 4) 2_4 aqueous solution. In the temperature, the temperature is respectively. . , 5_ and 6〇〇. . , Wei Ming layer accounted for; mass percentage (four) prepared under the conditions of three series: = composite material followed. ", she is exhausted. The acid-sand layer accounts for the mass percentage of the total mass y_gas, r Λ • the composite material (four)..:: prepared under the condition _ material sample ° °. Please refer to Figure 2 and Figure 3, of

The uniform coating of 'Wei (4) in the sample on the surface of the cobalt acid (tetra) was observed by high-magnification transmission electron microscopy. It can be clearly seen that the acid-like layer covers the surface of the surface of the granule in the form of a layer of a uniform thickness. The four samples are uniformly mixed with a proportion of the conductive agent and the dry agent to form a positive electrode on the surface of the positive current collector, and the gold sample is used as a negative electrode. The positive electrode and the negative electrode are separated by a separator and are impregnated with an electrolyte. Chengzhong ion battery, conducting audio-visual testing. In this embodiment, the conductive agent is acetylene black, the binder is polyvinylidene fluoride, and the mass ratio of the positive active material to the conductive agent and the lining agent is 8:1:1. The solution is a microporous polypropylene film, and the electrolyte is a 1 mol/L LiPF6/EC + DEC (1:1) solution. Just coated with Gu (four) positive (four), (4) the role of the coating of phosphoric acid to improve the positive structure of the material, although the silk surface structure, to provide a platform for the clock ions, while playing a barrier role, effectively inhibiting four The reaction of the valence ion with the electrolyte stabilizes the structure and improves the electrochemical cycle performance. 5伏。 From the ® can be found in the above-mentioned four kinds of samples in the 〇, 5 (: current under constant current charge and discharge cycle test, the cutoff voltage of the charge is 4. 5V' discharge cutoff voltage is 2. 7V. , using 100133405 Form No. A0101 Page 11 / Total 41 Page 1002056727-0 201235302 The sample of the method of the present invention, because the aluminum phosphate can uniformly coat the cobalt acid granules, can still have a higher charging at a higher voltage. Capacity and stable capacity retention rate, the capacity retention rate after 50 cycles is above 90%' specific capacity is l6〇mAh/g to i75mAh/g. And, as the heat treatment temperature increases, the capacity of the battery increases. The change in the percentage of aluminum phosphate has little effect on the battery capacity. [0028] Comparative Experiment 1 [0〇29] is prepared by comparing the particles of the positive electrode composite prepared in Example 1 of the present invention with the prior art method. Another comparative sample, the specific steps are: [〇〇3〇] mixing (nh4) 2hp〇4 aqueous solution with nitrate aqueous solution to form aluminum phosphate particles in water to form a dispersion; [〇〇31] lithium cobaltate particles Invest in the dispersion The aluminum silicate particles are adsorbed on the surface of the lithium cobaltate particles by the action of adsorption; and [0032] the acid clock particles adsorbed with the acid-filled particles on the surface are heat-treated at 600 ° C to obtain the comparative sample. Referring to Figures 5 and 6, in the comparative sample prepared by the prior art method, the morphology of the 'aluminum phosphate-based particles aggregated on the surface of the lithium cobaltate particles, and the aluminum phosphate particles agglomerated to make the coating uneven. [0033] 100133405 The comparative sample was replaced with the lithium aluminum phosphate-cobaltate composite material of Example 1 to assemble a battery under the same conditions as in Example 1 to perform charge and discharge performance tests. Further, a sulphate chain particle not coated with any material was also used. The positive electrode active material was assembled into lithium ion electricity under the same conditions as in Example 1, and the charge and discharge performance test was also performed. The above Example 1 differs from the comparative experiment only in that the positive electrode active material 'other battery conditions and test conditions are the same. ^02056727-0 Form No. A0101 Page 12 of 41 201235302 [0034] 1 Participation 7 'The comparison sample and uncoated lithium cobalt oxide particles sample The capacity retention rate after the 50th cycle is less than 85% 'this is mainly due to the uneven coating or uncoated of lithium cobaltate particles', so that lithium cobaltate reacts with the electrolyte when charging under the same pressure. [0035] (9) Example 2: Wei Ming ~ Zhong Nickel Oxide Composite [0036] In the embodiment, the positive active material particles are spinel-type lithium nickel oxide oxide particles, the chemical formula is LiNi.5〇4 » The phosphoric acid-chain nickel oxide composite material comprises lithium nickel manganese oxide particles and a Weiming layer coated on the surface of the lithium nickel oxide oxide particles. The preparation method of the yttrium-doped yttrium-yttrium oxide composite material is the same as the preparation method of the composite material particle of the above-mentioned example i, and the heat treatment temperature is selected to be 600 ° C, and the difference is only in the positive electrode active material. 5%。 The material of the particles is lithium hetero-oxide, the mass percentage of the dish S-Ming layer to the total mass is 〇. 5%. The acid-filled sulphur oxide composite material was replaced with the acid-filled acid-time composite material of Example 1, and assembled into a nano battery under the same conditions as in Example 1. The lithium ion battery was subjected to a constant current charge and discharge cycle test at a current of 0.2 C. The cutoff voltage of the charge was 5 V, and the cutoff voltage of the discharge was 3 V. The capacity retention rate of the battery after the 5〇 times of the ring was above 95%. The specific capacity is about 138 mAh/g. In addition, please refer to FIG. 8 , the lithium ion battery is subjected to a constant wire discharge (4) ring at 1 (current), and the capacity retention rate of the battery can still reach 95% after 5G cycles at 1 C, and the specific capacity is about 132 mAh. /g 100133405 Form No. A0101 Page 13 of 41 1002056727-0 201235302 [Comparative Experiment 2 [0038] Uncoated LiNin, 0, particles were used as the positive electrode active material under the same conditions as in Example 1. The lithium ion battery was assembled and tested for charge and discharge performance. The test results were compared with the test results of Example 2 in Fig. 8. It was found that the uncoated LiN% 5〇4 particles were used as the lithium ion of the positive electrode active material. The battery has a capacity retention rate of about 86% and a specific capacity of about 118 mAh/g after 50 cycles of 1 C current. [0039] Example 3: Aluminum phosphate-spherical lithium nickel manganese oxide composite [0040] This embodiment In the example, the spherical lithium nickel manganese oxide is first synthesized by controlled crystallization, and then the spherical lithium nickel manganese oxide is coated with aluminum phosphate. The chemical formula of the spherical lithium oxide oxide is LiN% 5〇4. Ming-spherical lithium nickel manganese oxide composite package A spherical lithium nickel manganese oxide and an aluminum phosphate layer coated on the surface of the spherical lithium nickel manganese oxide. [0041] The controlled crystal synthesis method for preparing the spherical lithium nickel manganese oxide comprises the following steps: [0042] providing soluble a manganese source compound and a nickel source compound, the soluble manganese source compound and the nickel source compound are dissolved and mixed in a stoichiometric ratio in a solvent to form a nickel manganese mixed solution; [0043] providing a carbonate having carbonate or bicarbonate a solution, the nickel manganese mixed solution and the carbonate solution are simultaneously input into a controlled crystallization reactor for mixing and stirring, and the pH in the kettle is controlled to be 8-10, and the temperature in the controlled kettle is 40 ° C - 60 ° C. The reaction product is obtained; [0044] The reaction product is subjected to solid-liquid separation and dried to obtain a spherical powder; 100133405 Form No. A0101 Page 14 of 41 page 1002056727-0 201235302 LUU4bj [0046] [0048]

[0050] The spherical powder is mixed at 40 (TC-60 (TCT heat treatment for 4 hours and 1 hour; the spherical powder after heat treatment) is mixed with the lithium source compound, and is immersed in (10)t Burning for 8 hours to 20 hours 'to obtain the ball-based oxides. In the step, the source compound and the nickel source compound are in the stoichiometric ratio of the nickel in the nickel oxide, in this embodiment, the nickel The catastrophe oxide is LiNifl 5 ά, and the molar ratio of nickel to manganese in the slit compound and the source compound is 1:3. The catastrophic compound may be MnS〇4.H2〇, Mn(CH3C〇〇)2.4H2〇 And one or more of Μη(Ν〇3)2·4Η2〇, the source compound may be NiS〇4-6H2〇^Ni(CH3COO)-4H?O^Ni(NOq)·6Η90t u ^ 〇2 The MnS 〇 Η Η ' ' ' 锰 锰 锰 锰 锰 锰 锰 锰 锰 锰 〇 〇 〇 〇 〇 〇 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 〇4.6H2〇, dissolved in 2L of deionized water, fully stirred until completely dissolved, to obtain a mixed solution of nickel and manganese. In this example, the carbonate solution is 42.4g Na2C〇3 dissolved in 2L of deionized water, charged After the mixture is completely dissolved, the carbonate solution and the nickel-manganese mixed solution are separately input into the process of controlling the crystallization reaction dad, and the feed flow rate of the Zhenmao mixed solution can be controlled to 2 mL/min. The feed flow rate of the solution can be controlled to 2.2 mL/min. The temperature of the temperature in the reactor has a certain influence on the reaction in the reactor, and also affects the crystallization process. Therefore, the temperature in the kettle should not be too low. Too low a temperature is not conducive to the reaction; and if the temperature is too high, it is difficult to form crystals. In this embodiment, the temperature in the autoclave can be maintained at 45. (:, 100133405 Form No. A0101 Page 15 / Total 41 Page 1002056727-0 201235302 The pH value in the autoclave is maintained at about 8. In addition, the stirring speed has a great influence on the shape of the formed particles, and the stirring speed of the ball can be maintained at UOO rpm/Wn during the stirring and mixing. The chemical formula of the spherical body is N1〇& 5(C〇3)2, xH2〇. 4 [0051] in the step of treating the spherical powder at 40 ° C - 60 (TC under heat treatment) The heat treatment temperature can be 420t. After the powder was' in excess of 1.5% and mixed Μ compound, the compound (iv) may be

Ll2C〇3, Ll2C〇3 over-theft system to compensate for the loss of chain during the calcination process The calcination step can be carried out in a muffle furnace, the calcination temperature can be ° ° C, and the calcination time can be 16 hours. 5〇 [_❹图9' The core particle size before heat treatment synthesized by the controlled crystallization method is between 5 μm and 30 μm. Please refer to Figure 1〇. After the ^c wc treatment, the spherical ίιΝν5ΜηιΛ teaching is still a spherical shape' but the sphere has contracted, and the spherical LiNi"Mn" [0053] 100133405 step by step 'the method of phosphoric acid coating the spherical lithium manganese oxide is: weigh the appropriate amount of M (N〇3) 3.9H2 〇 dissolved in ethanol to prepare 100g / L Alcohol solution. An appropriate amount of (NH4)2Hp〇4 was weighed and dissolved in deionized water to prepare an aqueous solution of 100 g/L. Weigh the manganese oxide in the i gram sphere, add the ai(n〇3)3 alcohol solution to the spherical (four) mascara oxide, and then slowly add (10) hydrazine and the aqueous solution while stirring. The solution turned into a muddy state. The molar ratio of AKN〇3)3 to (nh4)2hp〇4 is i: Put the mud-like trajectory into the oven at 3 to 12 °C and dry it into the muffle furnace. Slightly burn for 2 hours to obtain a spherical slat oxide coated with A1P04. Among them, the sister layer accounts for the number of grasses, and the number of masses is 1%. The total mass of the acid-aluminum-spherical lithium-nickel-manganese oxide composite is 1%, and the temperature of the simmering temperature is 400°C. Sample 1 was obtained, and the calcination temperature was selected to be 700 ° (: Sample 2 was obtained. Further, at 700 ° C for the calcination temperature, two different samples were prepared by changing the coating amount of the aluminum phosphate layer, wherein, in the aluminum phosphate The sample 3 was prepared under the condition that the mass percentage of the total mass of the aluminum phosphate-spherical chain recording oxide composite material was 2%, and the sample 4 was prepared under the condition of 3% by mass. f\ [0055] Referring to Figure 11, the curve (a) in Fig. 11 is an uncoated spherical LiNin Jni.50, the curve (b) is a sample 1 having a calcining temperature of 400 ° C, and the curve (c) is a calcining temperature of 700 ° C. Sample 2. In the spectrum of spherical 0N_5 1.5 4 LiN^ 5Μηι 5〇4, which is coated with aluminum phosphate, is compared with spherical LiNin, Μη, ^(^, which is not coated with aluminum phosphate, The position and intensity of the diffraction peaks are basically unchanged, and there is no Α1Ρ0, and the diffraction peak appears, indicating that the coated Α1Ρ0, 4 4 layer is not present. Shape, △1?〇4 and 1^心()5〇4 also did not react 〇〇[0056] Please refer to Figure 12, the sample 2 was observed by transmission electron microscopy, you can see Α1Ρ0, uniform coating And the thickness is about 10 nm. [0057] The aluminum phosphate-spherical lithium nickel manganese oxide composite material was replaced with the aluminum phosphate-lithium cobaltate composite material of Example 1, and assembled under the same conditions as in Example 1. A lithium ion battery was subjected to a charge and discharge performance test. [0058] Comparative Experiment 3 [0059] A spherical LiN, 5Μηι 5〇4, and an uncoated spherical LiNi.5Μηι were synthesized by the same controlled crystallization method as in Example 3. 5〇4为100133405 Form No. A0101 Page 17 of 41 1002056727-0 201235302 A positive electrode active material was assembled into a lithium ion battery under the same conditions as in Example 3, and subjected to charge and discharge performance tests. [0060] 13 and FIG. 13 are first charge and discharge curves of a constant current charge and discharge at a rate of 0.5 C times 0.5 1.54 for a lithium ion battery assembled using the sample 3 of Example 3 and the uncoated spherical LiNin Jn, respectively. Charge and discharge of 2 lithium ion batteries Station about 4. 7V, employing uncoated spherical

LiNin κΜη, the same lithium-ion battery. The lithium-ion battery of sample 3 has a first charge specific capacity of 135. 9 mAh/g and a discharge specific capacity of 126.2 mAh/g. Compared with the uncoated spherical LiNin Jn, /, U. 5 1 . 5 4 lithium ion battery, it was found that the coating increased the specific capacity of the positive electrode active material because the coated ruthenium/layer effectively By blocking the action of the electrolysis liquid 4, the HF generated by the decomposition reaction of the electrolyte under high pressure is prevented from corroding the positive electrode material, resulting in partial capacity loss. Referring to FIG. 14, FIG. 14 is a cycle performance curve of constant current charge and discharge at a 1C, 3C, and 5C magnification for a lithium ion battery of Sample 3 of Example 3 and uncoated spherical LiNin Jn, respectively. As can be seen from Figure 14, the uncoated spherical LiNi. With the increase of charge and discharge rate, the 5 〇 4 ionic battery decays rapidly, and the specific discharge capacity at the 5C rate is almost zero. The first discharge specific capacity of the lithium ion battery of sample 3 is slightly lower than that of the uncoated battery. However, as the number of cycles increases, the specific capacity does not decrease, but slightly increases. As the magnification increases, the specific capacity decreases. It is significantly smaller than the battery using uncoated spherical LiN, 5Mni 5〇4. In addition, when the lithium ion battery using sample 3 was discharged at a rate of 5 C, the specific capacity decreased first, and then increased with the number of cycles, which was because the AlPC^ coating was in the spherical LiNin. (^ Surface will increase by 4 0.5 1.5 4 100133405 Form number Α 0101 Page 18 / Total 41 page 1002056727-0 201235302 The resistance of large materials, so that the beginning of the ion intrusion and the escape (4) is difficult, but with the cycle read Increase, after the ion channel is established, the ions can move smoothly in the channel, so the capacity will also increase. Just refer to Figure 15 and Figure 16, Figure 15 is the sample 2_4 of the clock ion battery at the ^ rate The first charge and discharge curve ranges from 3.5V to 4.9V. Figure 16 shows the cycle performance curve of the lithium ion battery of sample 2-4 at 1 (: magnification, voltage range of 3.5V-4.9V. _15 can be seen, sample (4) The capacity of the neon is higher. The specific capacity of the battery of sample 4 decreases, indicating that when the amount of α1Ρ〇4 is too high, the 'over-thick coating layer will cause obstacles to _ sub-embedding and detachment, resulting in lower capacity. As can be seen from Fig. 16, the battery of sample 3 has the best cycle performance, and after 20 cycles, the capacity is also 113 6 mAh/g. [_] Xiang Zong said that the invention has indeed met the invention patent. Essentials, 提出 file a patent application according to law. However, the above mentioned only The preferred embodiment of the present invention is not intended to limit the scope of the patent application of the present invention. Any equivalent modifications or variations made by those skilled in the art of the present invention in the spirit of the present invention should be included in the following claims. BRIEF DESCRIPTION OF THE DRAWINGS [0064] FIG. 1 is a schematic view showing the structure of an active material of a phosphoric acid-coated positive electrode according to an embodiment of the present invention. [0065] FIG. 2 is a scanning electron micrograph of a lithium aluminum phosphate coated lithium cobaltate according to an embodiment of the present invention. [00661] FIG. 3 is a transmission electron micrograph of an aluminum phosphate coated lithium cobaltate according to an embodiment of the present invention. [0067] FIG. 4 is a performance test of a lithium phosphate coated lithium cobaltate according to an embodiment of the present invention 100133405 Form No. Α0101 19 pages/total 41 pages 1002056727-0 201235302 Curves [0068] Figure 5 is a scanning electron micrograph of a high-amplification aluminum phosphate coated lithium cobaltate for a comparative experiment. [0069] Figure 6 is a low-magnification phosphoric acid of a comparative experiment. A scanning electron micrograph of aluminum-coated lithium cobaltate. [0070] Figure 7 is a cycle performance test curve of an aluminum phosphate-coated positive active material of a comparative experiment. [00] Figure 8 is an aluminum phosphate coated embodiment of the present invention. Lithium nickel manganese FIG. 9 is a scanning electron micrograph of spherical powder particles before heat treatment synthesized by controlling the crystallization method according to an embodiment of the present invention. [0073] FIG. 10 is a scanning electron micrograph of a spherical lithium-recorded oxide synthesized by controlling a crystallization method according to an embodiment of the present invention. [0074] FIG. 11 is a view showing an aluminum phosphate-coated spherical lithium nickel manganese oxide according to an embodiment of the present invention. XRD analysis of the coated spherical lithium nickel manganese oxide. 12 is a transmission electron micrograph of a spherical lithium nickel manganese oxide coated with aluminum phosphate according to an embodiment of the present invention. Figure 13 is a graph showing the first charge and discharge curves of a lithium ion battery of an aluminum phosphate-coated spherical lithium nickel manganese oxide and a comparative test uncoated spherical lithium nickel manganese oxide according to an embodiment of the present invention. 4 is a lithium ion battery coated with aluminum phosphate coated spherical lithium nickel manganese oxide and a comparative test uncoated spherical lithium nickel manganese oxide according to an embodiment of the present invention, not 100133405 Form No. A0101 Page 20 / Total 41 pages 1002056727-0 201235302 Cycle performance curves at the same rate. 15 is a first charge and discharge curve of a lithium ion battery of a spherical aluminum lithium manganese oxide coated with different amounts of aluminum phosphate according to an embodiment of the present invention. 16 is a cycle performance curve of a lithium ion battery of a coating amount of aluminum phosphate coated spherical lithium nickel manganese oxide according to an embodiment of the present invention. 17 is a schematic view showing the structure of a prior art aluminum phosphate-coated positive electrode active material. [Main component symbol description] [0081] Positive electrode composite material particle: 10 [0082] Positive electrode active material particle: 12 [0083] Aluminum phosphate layer: 14 [0084] Product: 20 [0085] Small particle: 22 [0086] Large particle :24 〇1002056727-0 100133405 Form No. A0101 Page 21 of 41

Claims (1)

201235302 VII. Patent Application Range: 1. A nickel-manganese oxide composite material comprising positive electrode active material particles, the improvement comprising further comprising an aluminum phosphate layer coated on a surface of the positive electrode active material particle, the positive electrode active The material of the material particles is represented by the chemical formula Li Ni Μη ,, wherein 0.1 Sx S 1. 1, 0Sy < 1.5, OSa-y < 0.5, and 0Sb + y < 1.5, M and N are metal elements, alkaline earth metals One or more of the element, the Group 13 element 'Group 14 element, the transition group element, and the rare earth element. 1%至3%。 The lithium nickel manganese oxide composite material in the mass percentage of the lithium nickel manganese oxide composite material is 0.1% to 3%. 5 %。 The mass percentage of the mass of the lanthanum oxide composite material is 0.5%. 4. The lithium nickel manganese oxide composite material according to claim 1, wherein the aluminum phosphate layer has a thickness of from 5 nm to 20 nm. 5. The lithium nickel manganese oxide composite material according to claim 1, wherein the aluminum phosphate layer is formed in situ on the surface of the positive electrode active material particle 〇6 as described in claim 1 A lithium nickel manganese oxide composite material, wherein the aluminum phosphate layer has a uniform thickness and is continuous. 7. The lithium nickel manganese oxide composite material according to claim 1, wherein the range of y is 0 Sy < 0.1. 8. The lithium nickel manganese oxide composite material according to claim 1, wherein the household is selected from the group consisting of Cr, Co, V, Ti, Al, Fe, Ga, and Mg to 100133405. Form No. A0101 Page 22 of 41 Page 1002056727-0 201235302 One less. 9. The (four) sulphur oxide composite material according to claim 1, wherein the positive electrode active material particles have a chemical formula of UNi. 'I. The invention relates to a bell recording oxide composite material according to claim 1, wherein the positive electrode active material particles have a particle diameter of from 1 nanometer to 1 micrometer and 11 micrometers. The recorded smear oxide composite material according to the item 10, wherein the positive electrode active material particles have a particle diameter of from 丨micron to 2 〇micrometer. A method for preparing 12 kinds of bell oxide composite materials, comprising: providing an aluminum nitrate solution; suppressing a禝〇13 14 100133405 /' material particles are added to the nitrate solution, thereby increasing/forming a compound, Herein, the material of the positive electrode active material particles is represented by a chemical formula of Li Ni u χ 0·5 + a amni.5-y-bMaNb 〇 4, wherein -xl.l >〇^y<i.5 , 〇^a-y<〇> 5 . j_〇^ A 1· 5 ' _ is a metal element, a soil metal element, a 13th element, a 14th element, a transition element, and a rare earth element. One or more kinds; a disc salt solution is added to the mixture to carry out a reaction, an aluminum phosphate layer is formed on the surface of the positive electrode active material particles; and the positive electrode recording material particles having the surface layer are heat-treated. For example, in the preparation method of the 12th item (4) Miwei oxide composite material, in which the cathode active material particles to be coated are added to the Jingshen solution, ^ further control the cathode active material The amount added is such that the mixture is in the form of a slurry. For example, the invention relates to the preparation of the lithium-ride oxide composite material according to Item 12, the _axis solution includes _ and the form number dissolved in the solvent ^ 23 41 1002056727-0 201235302 aluminum nitrate, the solvent is Ethanol. The method for producing a lithium nickel manganese oxide composite according to claim 12, wherein the phosphate solution comprises water and an ammonium phosphate salt dissolved in water, the ammonium phosphate salt comprising ammonium dihydrogen phosphate, Mixing one or more of diammonium hydrogen phosphate and triammonium phosphate. The method of producing a lithium nickel manganese oxide composite according to claim 12, wherein the heat treatment temperature is from 400 ° C to 600 ° C. The method for producing a lithium nickel manganese oxide composite according to claim 12, wherein a volume ratio of the volume of the aluminum nitrate solution to the positive electrode active material particles is 1:10 to 1:40. A lithium ion battery comprising a positive electrode, the improvement comprising the lithium nickel manganese oxide composite material according to claim 1. The lithium ion battery according to claim 18, which has a capacity retention ratio of 95% or more after performing a constant current charge and discharge cycle for 50 times in a range of a charge cutoff voltage of 5 V and a discharge cutoff voltage of 3 V. 100133405 Form No. A0101 Page 24 of 41 1002056727-0