Doped spherical LiMn2O4 (manganese acid lithium) and preparation method thereof

Abstract

The invention relates to doped spherical LiMn2O4 (manganese acid lithium) and a preparation method thereof, belonging to the technical field of new energy materials. The preparation method comprises the following steps: reaction is carried out on water-soluble manganese salt and permanganate or persulfate under the liquid-phase condition, and spherical MnO2 (manganese dioxide) is first generated by controlling the pH value, temperature and the feeding speed of reaction liquid; the spherical MnO2 is uniformly mixed with LiOH (lithium hydroxide) or LiNO3 (lithium nitrate) or Li2CO3 (lithium carbonate) and a doping agent (zinc, aluminum or chromium) so as to obtain a mixture; the mixture is calcined under the temperature of 500 to 850 DEG C and is naturally cooled along with a furnace; and then the doped spherical LiMn2O4 is obtained through ball milling. The preparation process has the characteristics of simple preparation method, low energy consumption, easy material obtaining and high efficiency; an obtained product has excellent physical, chemical and electrochemical performances. Therefore, the doped spherical LiMn2O4 is the excellent anode material for the lithium ion battery.

Description

technical field

[0001] The invention relates to a doped spherical lithium manganate and a preparation method thereof. The doped spherical lithium manganate is used as a positive electrode material of a lithium ion battery and belongs to the technical field of new energy materials. Background technique

[0002] As a clean energy source, lithium-ion batteries can provide power for automobiles and other machines. They have high specific energy and good cycle life performance. The cathode material of lithium-ion batteries is the key to determine their performance. The currently used and researched lithium-ion battery cathode materials mainly include: LiCoO 2 , LiNiO 2 , LiMn 2 o 4 three kinds. Lithium manganate LiMn 2 o 4 It has the advantages of low price, good safety, superior rate discharge performance, and no environmental pollution, so it is a hot topic of research at home and abroad. At present, there are two main methods for the preparation of lithium manganate, on...

Examples

Embodiment 1

[0019] First, the industrial grade manganese sulfate is formulated into 0.15M aqueous solution 100L and the equal volume industrial grade potassium permanganate is formulated into 0.1M aqueous solution respectively; In the kettle, stir and add 43.5g of soluble sodium fluorosilicate, heat to 20°C, adjust the pH value of the reaction system to 3 with sulfuric acid aqueous solution, and stir for 1 hour after the addition is completed. After the formation of spherical manganese dioxide, separate the two Manganese oxide precipitation; the precipitation is washed twice with water with a pH of 5, washed with 20 L of washing water, then washed with deionized water, filtered and dried to obtain spherical manganese dioxide; take 2 kg of manganese dioxide, 0.42 kg of lithium hydroxide, and 10.4 g of zinc, Add organic alcohol solvent and mix evenly, then dry, then calcinate the dried product in a high-temperature furnace, the temperature is controlled at 600 ° C, for 15 hours, after coolin...

Embodiment 2

[0021] First, the industrial-grade manganese chloride is formulated into 1.0M aqueous solution 100L and the same volume of industrial-grade sodium hypochlorite is formulated into a 1.0M aqueous solution; the above-mentioned two equal-volume aqueous solutions are simultaneously added to the reactor at a flow rate of 18L / h , Stir and add 194g of soluble potassium fluorosilicate, heat to 70°C, adjust the pH value of the reaction system to 0.1 with aqueous hydrochloric acid solution, stir for 1.5 hours after the addition, after the spherical manganese dioxide is formed, the manganese dioxide precipitate is separated ; Precipitation with a pH of 3.5. Wash the precipitate with water twice, the washing water is 45L, then wash with deionization, filter and dry to obtain spherical manganese dioxide; take 2kg of manganese dioxide, 0.89kg of lithium nitrate, 10.4g of zinc and aluminum, add organic ether solvent and mix well After drying, burn the dried material in a high-temperature furn...

Embodiment 3

[0023] First, the manganese nitrate of industrial grade is formulated into 2.0M aqueous solution 100L and the sodium peroxodisulfate of equal volume industrial grade is formulated into 2.0M aqueous solution respectively; In the kettle, stir and add 43.5g of soluble sodium fluorosilicate, heat to 90°C, adjust the pH value of the reaction system to 0.01 with aqueous sulfuric acid solution, and stir for another 2 hours after the addition is complete. Manganese oxide precipitation; the precipitation is washed with 2.5 water for 3 times with a pH of 2.5, 100 L of washing water, then washed with deionized water, and filtered and dried to obtain spherical manganese dioxide; take 2 kg of manganese dioxide, 0.556 kg of lithium carbonate, 10 g of zinc, and 15g, zirconium 6.2g, add organic ketone solvent and mix evenly, then dry, then calcinate the dried product in a high temperature furnace, the temperature is controlled at 900°C, for 6 hours, after cooling, grind and sieve, the sieve is...

technical field

[0001] The invention relates to a doped spherical lithium manganate and a preparation method thereof. The doped spherical lithium manganate is used as a positive electrode material of a lithium ion battery and belongs to the technical field of new energy materials. Background technique

[0002] As a clean energy source, lithium-ion batteries can provide power for automobiles and other machines. They have high specific energy and good cycle life performance. The cathode material of lithium-ion batteries is the key to determine their performance. The currently used and researched lithium-ion battery cathode materials mainly include: LiCoO 2 , LiNiO 2 , LiMn 2 o 4 three kinds. Lithium manganate LiMn 2 o 4 It has the advantages of low price, good safety, superior rate discharge performance, and no environmental pollution, so it is a hot topic of research at home and abroad. At present, there are two main methods for the preparation of lithium manganate, on...

Examples

Embodiment 1

[0019] First, the industrial grade manganese sulfate is formulated into 0.15M aqueous solution 100L and the equal volume industrial grade potassium permanganate is formulated into 0.1M aqueous solution respectively; In the kettle, stir and add 43.5g of soluble sodium fluorosilicate, heat to 20°C, adjust the pH value of the reaction system to 3 with sulfuric acid aqueous solution, and stir for 1 hour after the addition is completed. After the formation of spherical manganese dioxide, separate the two Manganese oxide precipitation; the precipitation is washed twice with water with a pH of 5, washed with 20 L of washing water, then washed with deionized water, filtered and dried to obtain spherical manganese dioxide; take 2 kg of manganese dioxide, 0.42 kg of lithium hydroxide, and 10.4 g of zinc, Add organic alcohol solvent and mix evenly, then dry, then calcinate the dried product in a high-temperature furnace, the temperature is controlled at 600 ° C, for 15 hours, after coolin...

Embodiment 2

[0021] First, the industrial-grade manganese chloride is formulated into 1.0M aqueous solution 100L and the same volume of industrial-grade sodium hypochlorite is formulated into a 1.0M aqueous solution; the above-mentioned two equal-volume aqueous solutions are simultaneously added to the reactor at a flow rate of 18L / h , Stir and add 194g of soluble potassium fluorosilicate, heat to 70°C, adjust the pH value of the reaction system to 0.1 with aqueous hydrochloric acid solution, stir for 1.5 hours after the addition, after the spherical manganese dioxide is formed, the manganese dioxide precipitate is separated ; Precipitation with a pH of 3.5. Wash the precipitate with water twice, the washing water is 45L, then wash with deionization, filter and dry to obtain spherical manganese dioxide; take 2kg of manganese dioxide, 0.89kg of lithium nitrate, 10.4g of zinc and aluminum, add organic ether solvent and mix well After drying, burn the dried material in a high-temperature furn...

Embodiment 3

[0023] First, the manganese nitrate of industrial grade is formulated into 2.0M aqueous solution 100L and the sodium peroxodisulfate of equal volume industrial grade is formulated into 2.0M aqueous solution respectively; In the kettle, stir and add 43.5g of soluble sodium fluorosilicate, heat to 90°C, adjust the pH value of the reaction system to 0.01 with aqueous sulfuric acid solution, and stir for another 2 hours after the addition is complete. Manganese oxide precipitation; the precipitation is washed with 2.5 water for 3 times with a pH of 2.5, 100 L of washing water, then washed with deionized water, and filtered and dried to obtain spherical manganese dioxide; take 2 kg of manganese dioxide, 0.556 kg of lithium carbonate, 10 g of zinc, and 15g, zirconium 6.2g, add organic ketone solvent and mix evenly, then dry, then calcinate the dried product in a high temperature furnace, the temperature is controlled at 900°C, for 6 hours, after cooling, grind and sieve, the sieve is...