TW552240B - Preparation of cathode materials for lithium ion secondary batteries - Google Patents

Abstract

The present invention relates to a novel technique of using a microscopic emulsion method to synthesize a lithium transitional metal oxide ceramic powder for lithium ion secondary batteries. The technique comprises adding an aqueous solution containing lithium ions and transitional metal ions into an organic solvent containing a surfactant or a surfactant and a co-surfactant at the same time; mixing or blending the mixture so that the aqueous solution is uniformly dispersed in the organic solvent to form a microscopic emulsion; and performing a drying and a thermal treatment to synthesize a lithium transitional metal oxide powder. The present invention relates to a lithium transitional metal oxide powder prepared by the above technique, a cathode of an electrochemical battery containing the lithium transitional metal oxide, and a lithium ion secondary battery containing the cathode. The invented method can be used to obtain submicron and nano-meter lithium transitional metal oxide ceramic powder which can be applied on lithium ion secondary batteries and lithium polymer batteries.

Description

552240 A7 _B7_ V. Description of the invention (1) Field of invention (please read the precautions on the back before i) The present invention discloses a novel synthesis method of lithiated transition metal oxide ceramic powder and the lithiated transition prepared by the above method Metal oxide powder, cathode for electrochemical cell containing the lithiated transition metal oxide, and lithium ion secondary battery containing the cathode. The method is to add an aqueous solution containing lithium ions and transition metal ions to an interface containing an interface The active agent or an organic solvent containing both a surfactant and a co-surfactant is mixed or stirred so that the aqueous solution is uniformly dispersed in the organic solvent to form a microemulsion, followed by drying and heat treatment. To synthesize powders of lithiated transition metal oxides. The method of the present invention can control submicron and nano-meter lithiated transition metal oxide ceramic powders by controlling the microemulsion colloid. The powder has excellent charge and discharge characteristics and can be applied to lithium secondary batteries. BACKGROUND OF THE INVENTION With the development of portable electronic products in the direction of lightness, thinness and shortness, and the increase in consumer demand for portable products, the small, lightweight, and high-energy-density batteries have become portable electronics. One of the important keys in product promotion and application. Under the trend of emphasizing "thin, light and short", the "lithium ion secondary battery" has become a new modern favorite with its excellent characteristics such as high energy density, high output power, fast charging and no pollution. And its characteristics have also been affirmed by 3C electronics industry. It is also an indispensable equipment for portable electronic products such as laptops, big phones, cameras, etc. -4- This paper standard applies to China National Standard (CNS) A4 specifications (210X 297 mm) 552240 A7 B7 V. Description of the invention (2) The ion secondary battery is generally considered to have the advantages of high operating voltage, high energy density, stable discharge voltage, and high cycle number at room temperature. Its structure includes three major Parts: (1) lithiated transition metal oxide of cathode material; (2) carbon material of anode; and (3) electrolyte. 9 cathode material during charging Lithium ions enter the anode through the electrolyte, and during discharge, the ions in the anode return to the cathode through the electrolyte, so it is also called a rocking chair battery. Recently, in order to make lithium ion secondary batteries further thin and short, the electrolyte part Lithium polymer batteries that have been changed to polymers have also been greatly valued. On the one hand, they have reduced the battery thickness, and on the other hand, they have increased safety and manufacturing convenience. However, whether in a clock ion secondary battery or a lithium polymer battery, the cathode All transition metal oxide materials play a very important role. 'It is the key core that determines the energy density and charge and discharge characteristics of the battery. The cathode materials used in lithium ion secondary batteries or lithium polymer batteries are lithium ions and at least one transition metal ion. The structure of the lithiated transition metal oxide formed is mainly divided into two categories, one is a layered structure material, and the space group is R 3m, such as LiCo〇2, LiMn〇2, LiNi〇2, Central Standards Bureau of the Ministry of Economic Affairs Printed by employee consumer cooperatives (please read the precautions on the back before this page)

LiCCOhxNiJC ^ (0 幺 x 幺 1); the other is a spinel structure material whose space group is Fd3m, such as LiMn204. In order to improve the characteristics of various lithiated transition metal oxides, the stoichiometric ratio of lithium ions to transition metal ions is generally adjusted, and the non-stoichiometric ratio is 0 to 30%; or a trace amount of one or more other metal ions is added , Such as Mg, Ca, Sr, Ba, A1, Ti, V, Co, Cr, Ni, Mη, Fe, the addition amount of which is 0 to 10%; or both of the above methods, while adjusting the lithium ion and The non-stoichiometry of the main transition metal ions, and the paper dimensions are added to the Chinese National Standard (CNS) A4 specifications (210X 29 < 7 mm) 552240 A7 B7 5. Description of the invention (3) Add trace amounts of other metal ions.

(Please read the precautions on the back before printing by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. In order to obtain the best electrochemical characteristics of lithium-ion secondary batteries, it is important to prepare the cathode material lithiated transition metal oxide ceramic powder. Technology. The particle size, purity, microstructure and composition of the prepared ceramic powder directly affect the characteristics of lithium ion secondary batteries. In the traditional solid-phase reaction process, the solid compounds of lithium and the solids of transition metals are used. Compounds such as oxides, carbonates, oxalates, nitrates, etc. are mechanically mixed and then subjected to the sintering reaction. Because mechanical stirring is not easy to mix uniformly, and the reactant has a large particle size and low reactivity, it needs high temperature Sintering reaction. Under high temperature reaction, it is easy to make the lithium component volatilize and cause the ceramic powder to deviate from the stoichiometric ratio. Because of the effect of high temperature sintering, the particles grow violently, so that the specific surface area of the ceramic powder is reduced, which is unfavorable for lithium ion insertion and Extrusion reaction. In the preparation by precipitation method, because lithium ions cannot be co-precipitated with other ions, the stoichiometric ratio cannot be accurately controlled. In addition, when it is prepared by the sol-gel method, if the metal alkoxide is used as the raw material, the raw material is prone to hydrolytic reaction, so it is extremely unstable, and because of the high price of the raw material, it is not suitable for industry. Mass production. When synthesizing bell-shaped transition metal oxide ceramic powders by the general latex method, due to the lack of latex stability, it is impossible to store and use the latex solution for a long time, which easily causes the oil phase to separate from the water phase, resulting in powder The body composition has local unevenness, and the particle size of the latex is large and the distribution is relatively uneven, so that the particle size of the synthesized ceramic powder is large and the microstructure is not easy to be uniform. In order to solve the above problems, the inventor of this case After dedicating to a series of research experiments, I first discovered that if a specific microemulsion synthesis method of specific lithiated transition metal oxide ceramic powder materials is used-6- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 (Mm) 552240 A7 B7 5. Description of the invention (4), not only can obtain single-phase lithiated transition metal oxide ceramic powder and submicron and nanoscale The present invention has been completed with ultra-fine lithiatized transition metal oxide ceramic powder without the disadvantages of the prior art described above. SUMMARY OF THE INVENTION The object of the present invention is to provide a lithiatized transition metal oxide for preparing a lithium ion secondary battery cathode material. Method for producing ceramic powder, which is an aqueous solution containing lithium ions and transition metal ions is added to an organic solvent containing a surfactant or both a surfactant and a co-surfactant to be mixed or stirred to make the aqueous solution Evenly dispersed in the organic solvent to form a microemulsion, followed by drying and heat treatment to synthesize a powder of lithiated transition metal oxide. The volume ratio of the aqueous solution to the organic solvent is 0.01 ~ 1.8, The volume ratio of the surfactant to the organic solvent is 0.01 to 1.2, and the volume ratio of the co-surfactant to the organic solvent is 0 to 1.1. Another object of the present invention is to provide a lithiated transition metal oxide ceramic powder synthesized by the above synthesis method. The method of printing the present invention by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs can produce a high-purity lithiated transition metal oxide ceramic powder, and since the microemulsion synthesis method is used, the resulting lithiated transition metal oxide ceramic powder is obtained. The body size can be reduced to sub-micron to nano-level, and the particle size distribution is uniform, the microstructure is uniform, and the powder has excellent charge and discharge characteristics. Schematic description

Figure 1 is the X of LiCo02 powder obtained by the microemulsion synthesis method. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 > < 297 mm). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 552240 A7 _B7_ 5. Description of the invention (5) Ray diffraction pattern. Fig. 2 is a transmission electron microscope photograph of LiCo02 powder obtained by a microemulsion synthesis method. Fig. 3 is an X-ray diffraction pattern of LiNi02 powder obtained by a microemulsion synthesis method. Fig. 4 is a transmission electron microscope photograph of LiNi02 powder obtained by a microemulsion synthesis method. Fig. 5 is an X-ray diffraction pattern of LiCo〇2Ni〇.802 powder obtained by a microemulsion synthesis method. Fig. 6 is a transmission electron microscope photograph of LiCo0.2Ni〇.802 powder obtained by a microemulsion synthesis method. Fig. 7 is an X-ray diffraction pattern of LiMn204 powder obtained by a microemulsion synthesis method. Fig. 8 is a transmission electron microscope photograph of LiMn204 powder obtained by a microemulsion synthesis method. Figure 9 is a graph showing the relationship between the discharge capacity of LiCo02 powder obtained by the microemulsion synthesis method and the number of charge and discharge cycles. Figure 10 is a graph showing the relationship between the discharge capacity of LiMn204 powder obtained by the microemulsion synthesis method and the number of charge-discharge cycles. DETAILED DESCRIPTION OF THE INVENTION The present invention is the first to synthesize a lithiated transition metal oxide using the microemulsion method. The present invention utilizes the concept that the water phase and the organic phase (oil phase) are incompatible with each other, and an aqueous solution containing lithium ions and an aqueous paper containing transition metal ions (such as manganese ions, cobalt ions, nickel ions, etc., but not limited thereto). Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the precautions on the back before this page), τ 552240 A7 B7 V. Description of the invention (6 (Please read the precautions on the back on the next page) ) After the solution is mixed, prepare a homogeneous aqueous solution, and then place the aqueous solution in an organic solvent (such as benzene, toluene, xylene, hexane, heptane, octane, nonane, decane, cyclohexane, cycloheptane (Butane, cyclooctane, cyclononane, cyclodecane, etc., but not limited to this), because the water phase and oil are incompatible with each other, a two-layer solution will be formed. In order to uniformly disperse the aqueous phase solution in an organic solvent, Therefore, the surfactant is added or both the surfactant and the co-surfactant are added to the organic solvent. After mixing or stirring, the aqueous solution is dispersed into microscopic droplets or cells, and is stably dispersed in the continuous phase (oil phase ) And form Microemulsion. Because the size of each droplet is between nanometer and submicron, and each droplet is an independent reactor, the particle size of the synthetic powder can be greatly reduced. Microemulsion droplets contain the same ion concentration, so the chemical composition of the powder can be refined and controlled 9 after drying, and because the microemulsion droplets become smaller, the difference in segregation during drying can be reduced. Central Bureau of Standards, Ministry of Economic Affairs The microeniulsion formed by the employee consumer cooperative is very different from the ordinary emulsion. Generally, the droplet size is between i nanometer (10_9m) to about 100 nanometers (10-7m). , The size of the latter is between 100 nanometers and 10,000 nanometers (10-5m). The former solution has small droplets and the light is easy to penetrate, so it is translucent or transparent; the latter is difficult to penetrate due to the large droplet size. Therefore, the solution appears milky white. The microemulsion solution is close to the thermodynamic stable state, and the water phase and the oil phase are not easily separated, so it can be stored or used for a long time; but the latex solution is not thermodynamically stable. After a certain period of time, the oil phase and the water phase are left Easy to separate, Therefore, it is not possible to maintain a uniform mixture of the oil phase and the water phase for a long time. In addition, the droplet size of the microemulsion solution is uniform, and the size distribution of the latex droplets is wide. Therefore, there are two different forms.

552240 A7 B7 V. Description of the invention (7) The characteristics of latex synthetic powders are quite different. The particle size of the powder synthesized by microemulsion can be effectively controlled to the nanometer range 9 and the particle size distribution is narrow. 9 The shape of the powder is uniform; and the particle size of the conventional traditional latex synthetic powder is smaller than that of the microemulsion synthesized powder. It is larger than 1 to 2 orders, and the particle size distribution is wide, and the powder shape is not easy to be uniform. The lithium ion and transition metal ion aqueous solutions of the mixed solution of the present invention each have an independent concentration of 0.01 to 10 Μ, and a preferable concentration of each of the independent solutions is 0.1 to 5 Μ. The metal salt or compound used is not particularly limited as long as it is soluble in water, and may be, for example, nitrate, acetate, sulfate, oxalate, gaseous, and the like. In the microemulsion solution after the emulsification process, each droplet of the aqueous solution can be regarded as a separate reactor. The size of the powder obtained after drying is directly affected by the size of the droplets in the microemulsion solution. Therefore, after reducing the size of the droplets, nano- to sub-micron-level powders can be obtained. The method of drying the latex to form a dry powder (precursor) is not limited, and the conventional drying method may be used. For example, the microemulsion can be dried at a temperature slightly higher than room temperature, and then the temperature can be dried. Raise to dry completely. Alternatively, dry powder can be prepared by distillation under reduced pressure or spray drying. The precursor powder obtained by the microemulsion method is subjected to heat treatment, and the heating process may be, for example, heating to 500 ° C ~ 1000 ° C at a temperature increasing rate of 1 ° C to 50 ° C per minute, and its highest temperature is The temperature holding time is from zero (high-temperature quenching) to 12 hours, which is preferably 30 minutes to 8 hours to prepare a lithiated transition metal oxide powder. During the heating process, oxygen and nitrogen can be controlled to promote thermal decomposition and powder reaction, and control the formation of defects in the cathode material. The condition of heat treatment is that those who are familiar with the relevant technology can apply the Chinese National Standard (CNS) A4 specification (210X 297 mm) according to this paper size. (Please read the notes on the back first

Discarded-Ben 100 C, τ printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 552240 A7 B7 V. Invention Description ((Please read the precautions on the back, then experience and simple tests to optimize it 9) Therefore, the present invention is not Limited to heat treatment procedures. The ions in the aqueous phase can have a layered structure (such as

LiCo02 ^ LiMn02 ^ LiNi02 ^ Li (C〇1.xNix) 02 (0 < X S1)) or spinel structure (such as UMn2 () magical lithium transition metal oxide ingredients. Formulated to further improve each lithium When changing the characteristics of transition metal oxides, the stoichiometric ratio of lithium ions to transition metal ions can be adjusted, and its non-stoichiometric ratio is 0 to 30%: or a trace amount of one or more other metal ions, such as Mg , Ca, Sr, Ba, Ah Ti, V, Co, Cr, Ni, Mη, Fe, the addition amount of which is 0 to 10 /., Or both of the above two methods 9 to adjust the ion and the main transition metal at the same time The non-stoichiometry of ions, and the addition of trace amounts of other metal ions. The organic solvent used in the method of the present invention may be any organic solvent that is immiscible with water, and its type is not limited. The commonly used organic solvents are , Xylene, hexane, heptene ^, octane, nonane, decane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, and alkane derivatives, etc. are preferred. The organic solvent used may be a mixture of the above, wherein the aqueous solution and the organic solvent The volume ratio of the solvent ranges from 0 to 01 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, and the volume ratio of the preferred aqueous solution to the organic solvent ranges from 0 to 0.5 to 1. The interface used in the method of the present invention The active agent is only required to make the water phase and the oil phase used to form a microemulsion after mixing and stirring, and its type is not limited. The commonly used commercially available surfactants are Span 2,0, Span 40 , Span 60, Span 80, Span -11- 552240 A7 B7 V. Description of the invention (9) 85, 〇 ·· １〇 (polyoxyethylene octyl phenyl ester p〇ly〇xyethylene (10) octylphenyl ether) (the above is The trade names of Wako Pure Chemical Industries Ltd. Japan can be easily purchased on the market with certain ingredients), Tween 20, Tween 40, Tween 60, Tween 65, Tween 80, Tween 85 (the above are the products of Fluka Chemie AG, Switzerland) Name, can be easily purchased on the market and its composition is certain), Brij 30, Brij 35, Brij52, Brij56, Brij 58, Brij 72, Brij76, Brij 78, Brij92, Brij 97, Brij 98, Span83, CTAB, Igepal CA- 210, Igep al CA-520, Igepal CA-720, Igepal CO-210, Igepal CO-520, Igepal CO-720, Igepal CO-890, Igepal CO-990, Igepal DM-970 (The above are Aldrich Chemical Company. Inc., USA · The product name can be easily stated on the market and its composition is certain), NP5, NP9 (the above are Albright and Wilson Asia Pte. Ltd. ·, the product name of Singapore is easily available on the market and its composition is certain), AOT (The above are the trade names of Sigma Chemical Company, USA, which can be easily purchased on the market with certain ingredients), NP4, DP6 (the above are the trade names of Phone-Poulenc Inc., which can be easily purchased on the market with certain ingredients) , Triton X-100, Triton X-114, Triton X-305, Triton X_405 (the above are the trade names of Nacalai Tesque, Inc., Japan, which can be easily purchased on the market with certain ingredients). The surfactant used may be a mixture of the above. The volume ratio of surfactant to organic solvent is in the range of 0.01 to -12. This paper size is applicable to China National Standard (CNS) A4 specifications (210X 297 mm) (Please read the precautions on the back page first) Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards 552240

1 · 2 ', among which the preferable volume ratio ranges from 〇04 to 〇9. In order to increase the stability of the microemulsion, a co-interface solvent may be additionally added, as long as the co-interface solvent can form a microemulsion, and the type is not limited. Commonly used co-interface activities are generally related to alcohol derivatives, Such as propanol, butanol, methanol, hexanol, heptanol, propylene alcohol, isobutanol, isoamyl alcohol and so on. The co-interfacial activity can be a mixture of the above. If the degree of microemulsion is sufficient, it is not necessary to add a co-interface solvent. The volume ratio of the co-surfactant to the organic solvent ranges from 0 to 1.1, and the preferred volume ratio ranges from 0 to 0.9. Hereinafter, the present invention is illustrated by examples, but the present invention is not limited to these examples. Example 1 Lithium oxalic acid and nitric acid were first dissolved in water to prepare an aqueous solution having a lithium ion concentration of 1 M and a cobalt ion concentration of 丨 M. The lithium ion and cobalt ion concentration ratio was controlled to be 1: 1, which is in line with lithium cobalt oxide. (Lic002) ^ Stoichiometry. Then add cyclopentane and co-surfactant hexanol to cyclohexane, take the aqueous solution and cyclohexane at a ratio of 1:10 by volume 7 and mix and stir to obtain stable and stable solution. Microemulsion solution. The microemulsion solution was dried to obtain a precursor of lithium cobalt oxide. Place this precursor at 800. (: Sintered for 2 hours, X-ray diffraction analysis is performed, and the results are shown in Figure 1. As shown in Figure 丨, the obtained powder is a pure phase ceramic powder of lithium cobalt oxide, and is wound by χ line The comparison of the radiogram and the standard spectrum shows that the compound has a layered structure. The transmission electron microscope photograph of the obtained powder is shown in Figure 2, and it can be seen from Figure 2 that the particle size of the synthesized lithium cobalt oxide powder is nano Grade, powder morphology, powder-13-This paper size applies Chinese National Standard (CNS) A4 specification (2Η) χ 297

(Please read the caution page on the back)

A Consumption cooperation with employees of the Central Bureau of Standards, Ministry of Economic Affairs, Du Duan 552240 A7 B7 V. Description of the invention (11 volume is well dispersed. This example demonstrates that by using microemulsion synthesis, nano-scale and single-phase layered lithium can be prepared Example 2 Cobalt oxide. Lithium nitrate and nickel nitrate were dissolved in water to prepare an aqueous solution of 1 M lithium ion and 1 M cobalt ion. The concentration ratio of lithium ion to nickel ion was controlled to be 1: 1, which is in line with lithium nickel oxide. (LiNi02) stoichiometry. Then add the surfactant OP-10 and co-surfactant hexanol to cyclohexane, take the aqueous solution and cyclohexane at a volume ratio of 1:10, mix and stir A stable microemulsion solution was prepared. The microemulsion solution 9 was dried to obtain a precursor of lithium nickel oxide. The precursor was calcined at 800 ° C for 2 hours, and X-ray diffraction analysis was performed. In Figure 3. As shown in Figure 3, the obtained powder is a pure phase ceramic powder of lithium nickel oxide, and by comparing the X-ray diffraction pattern with the standard pattern, it can be known that the compound has a layered structure. Photograph of the transmission electron microscope of the powder is shown in Figure 4 Figure 9 shows from Figure 4 that the particle size of the synthesized lithium nickel oxide powder is nanometer, the powder has a uniform morphology, and the powder is well dispersed. This example demonstrates that micron latex synthesis can be used to produce nanometer and single-phase particles. Layered structure of lithium nickel oxide. Example 3 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before this page). Lithium nitrate, cobalt nitrate and nickel nitrate are dissolved in water to prepare lithium ions. It is an aqueous solution of 1 M, cobalt ion 0.2 M, and nickel ion 0.8 M. The concentration ratio of lithium ions, cobalt ions, and nickel ions is controlled to 1: 0.2: 0 · 8 to comply with lithium cobalt nickel oxide (LiCo〇2NiG 802) stoichiometry. Then add the surfactant OP-10 and co-surfactant hexanol to cyclohexane, take the water phase solution and cyclohexane at a ratio of 1: 10 by volume -14. Standard (CNS) A4 specification (210X 297 mm) 552240 A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. In the case of the invention (l2), after mixing and stirring, a stable microemulsion solution is prepared. Drying The microemulsion solution A precursor of lithium cobalt nickel oxide was obtained. The precursor was calcined at 800 ° C for 2 hours, and X-ray diffraction analysis was performed. The result is shown in Fig. 5. As shown in Fig. 5, the obtained powder was A pure phase ceramic powder of lithium cobalt nickel oxide, and by comparing the X-ray diffraction pattern with the standard pattern, it can be known that the compound has a layered structure. The transmission electron microscope photograph of the obtained powder is shown in FIG. 6 It can be seen from FIG. 6 that the particle size of the synthesized lithium cobalt nickel oxide powder is nanometer, the powder is uniform in shape, and the powder is well dispersed. This example demonstrates that micron latex synthesis can be used to prepare nanometer and single-phase particles. Layered structure of lithium-cobalt-nickel oxide. Example 4: Lithium nitrate and manganese nitrate were dissolved in water to prepare an aqueous solution of 1 M lithium ion and 2 M manganese ion. The concentration ratio of lithium ion to manganese ion was controlled to 1: 2 , In line with the stoichiometry of lithium manganese oxide (LiMn204). Then add the surfactant OP-10 and co-surfactant hexanol to cyclohexane, take the aqueous solution and cyclohexane at a volume ratio of 1: 10, mix and stir, and obtain stable microemulsion. Solution. The microemulsion solution was dried to obtain a precursor of lithium manganese oxide (LiMn204). This precursor was sintered at 700 ° C for 1 hour, and X-ray diffraction analysis was performed. The results are shown in FIG. 7. As shown in Fig. 7, the obtained powder is a pure phase ceramic powder of lithium manganese oxide, and by comparing the X-ray diffraction pattern with the standard pattern, it can be seen that the compound has a spinel stone structure. A transmission electron microscope photograph of the obtained powder is shown in FIG. 8. It can be seen from FIG. 8 that the synthesized lithium manganese oxide powder has a nanometer-sized particle size, a uniform powder morphology, and good powder dispersion. Therefore, this example demonstrates the use of display -15-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before this page) 燊 · 552240

The micro-emulsion synthesis method can produce nano-scale and single-phase W-structure short oxides. Example 5 In order to test the charge and discharge behavior of the synthesized powder, a synthetic osmium oxide (UC00) powder system was used as the cathode electrode piece. First, the synthesized powder is mixed with carbon powder and polyvinylidene fluoride in a weight ratio of 87%: 8%: 5%, and then an appropriate amount of n-methylpyrrohydrone is added. The solvent was stirred into a homogeneous slurry. The slurry was then coated on a trowel and dried to form a cathode electrode sheet. The battery uses bell metal as the anode pole piece, and the electrolyte uses a solution of 1M LipF6i ethylene carbonate and dimethyl carbonate (its volume ratio is 1: 1). The cathode electrode piece and the anode electrode piece were assembled in a test cell, and after adding an electrolyte solution, electrochemical characteristics were analyzed by a charge-discharge meter. Its current density is 0 2 mA / cm2 and its cut-off voltage is 3V ~ 4.3V. The test results are shown in Figure 9. It can be seen from the figure that the synthesized lithium-cobalt oxide cathode material has excellent electrical properties. Its first discharge capacity is as high as 1; 37 mAh / g, and after 10 charge-discharge cycles, it still has a stable capacity. Can meet the needs of clock ion secondary batteries. Example 6

In order to test the charge and discharge behavior of the synthesized powder, a synthetic bell oxide (LiMn204) powder system was used as the cathode electrode piece. First, mix the synthesized powder with carbon powder and polyvinylidene fluoride in a weight ratio of 87%: 8%: 5%, and then add an appropriate amount of n-methyl 2-tetrahydropyridone to the solvent to form a homogeneous polymer. . The polymer material was coated on a baking box and dried to form a cathode electrode sheet. Lithium metal is used as the anode pole piece in the battery, and the electrolyte is 1M -16- This paper size applies to Chinese national standard (cys) A4 specification (210X297 mm) (Please read the note on the back first) Central Standards Bureau of the Ministry of Economic Affairs Printed by employee consumer cooperatives 552240 A7 B7 V. Description of invention (l4)

LiPF6 solution of ethylene carbonate and dimethyl carbonate (its volume ratio is 1: 1). The cathode electrode piece and the anode electrode piece were assembled in a test cell, and after the electrolyte was added, the electrochemical characteristics were analyzed by a charge-discharge meter. Its current density is 0.2 mA / cm2 and its cut-off voltage is 3V ~ 4.3 V. The test results are shown in Figure 10. It can be seen from the figure that the synthesized lithium manganese oxide cathode material has excellent electrical properties. Its first discharge capacity is as high as 110 mAh / g, and after 10 charge and discharge cycles, it still has a stable capacity, which can meet the lithium ion. Demand for secondary batteries. The method and features of the present invention will be more obvious through the above-mentioned examples. It should be understood that any modification or change without departing from the spirit of the present invention belongs to the intention protector of the present invention. (Please read the precautions on the back of this page and then on this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is sized for the Chinese National Standard (CNS) A4 (210X 297 mm)

Claims (1)

552240 • Λ 8 Β8 C8 --- ~ ---- D8 Patent application range 8. Application scope, one method, in which the surfactant is produced by Span 20, an c, P η 40, Span 60 , Span 80, Span83, Please read in the face Bnj56, Brij 58, Brij 72, Brij76, Brij 78, Ruyang, Bnj 97, Bnj 98 'CTAB, NP4, NP5, NP9, AOT, ^ 6, plus 01 ^ _1〇〇, plus 〇1 ^ _114, plus 〇 At least one of a group consisting of 1 ^ -3305 and nton X_405, or a mixture thereof. The method of claim 1 in the patent scope since 9f, wherein the surfactant is selected from :: 40, Span 60, Span 80, Ye Ye, -M, Tween 40, Tween 60. Τλν66η 65 ^ Tween 80, ween 85, CTAB, Νρ4, Νρ5, Νρ9, α〇τ, Dp6, ^ 1 of 0 in group n ==. 114 and-™ is a method of specifically enclosing item 1, wherein the common interface Active alcohol: "Butanol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol. At least one of the group consisting of or mixture thereof. Employees of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China Cooperative Society ¾ Select 1 from 1 Kang: Method of applying for the first item in the patent scope, wherein the transition metal is a group consisting of r, titanium, hafnium, chromium, ferrite, and iron. At least one of the methods is 1 oxygen 2 = 'please patent scope item 1, wherein the lithiated transition gold 13 = A) 02, and the range of X is 0 belongs to two? : The method according to item 1 of the patent, wherein the chemical transition metal emulsion is LiMn204.根据. According to the method of patent application, the bell-shaped transition gold -19- The paper size is suitable for Sichuan China National Fengfeng (CNS) Λ4 specification (210χ 2 (; 7 public office 552240) The average particle size of oxide-based powders is from nanometers to b micrometers. 15. If the lithiated permetal oxide powder system according to the scope of patent application No. 丨, 12 or 13 is used as the method, its synthesis. Use of cathode materials for electrochemical dry batteries * Please read the / 1 back Μ Printed by cooperatives of employees of the Central Bureau of Standards, Ministry of Economic Affairs • 20-wood paper suitable for household materials (CNS) Λ4 specifications (2Π) χ 297 public fantasy