CN1298210A - Cathode material for lithium ion battery and its making process - Google Patents

Cathode material for lithium ion battery and its making process Download PDF

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Publication number
CN1298210A
CN1298210A CN99117396A CN99117396A CN1298210A CN 1298210 A CN1298210 A CN 1298210A CN 99117396 A CN99117396 A CN 99117396A CN 99117396 A CN99117396 A CN 99117396A CN 1298210 A CN1298210 A CN 1298210A
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China
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cathode material
compound
lithium
manganese
discharge capacity
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CN99117396A
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于作龙
刘培松
张伯兰
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Chengdu Institute of Organic Chemistry of CAS
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Chengdu Institute of Organic Chemistry of CAS
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Priority to CN99117396A priority Critical patent/CN1298210A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides one metal ion doped Li-Mn composite oxide LiAxByMn2-x-yO4 and its preparation, where A is transition metal element and B is alkali earth metal or III A metal element. The joint action of the transition metal and alkali earth metal or III A metal element results in the prolonged circular use life of the material. When used for constant-current charge and discharge at the conditions of 3.3-4.35 V and 0.4 mA/sq cm, the material has the first discharge capacity greater than 115 mA.hr/g and the discharge capacity after 150 circulations over 100 mA.hr/g.

Description

A kind of cathode material for lithium ion battery and manufacture method thereof
The present invention relates to a kind of cathode material for lithium ion battery and manufacture method thereof, this material is the spinel structure LiA that mixes up metal ion xB yMn 2+x-yO 4
Lithium ion battery is because the advantage of its high voltage, high-energy-density receives people's very big concern.Lithium ion battery has been widely used on the electronic equipments such as mobile phone, notebook computer at present.The cathode material that lithium ion battery is commonly used has LiCoO 2, LiNiO 2, LiMn 2O 4LiCoO 2Chemical property is good, but since the Co price more expensive, environment is had pollution, not drawbacks limit such as overcharging resisting electricity, protective circuit complexity its use.LiNiO 2Preparation and purifying are very difficult.LiMn 2O 4Aboundresources, environmental pollution is few.Since belong to spinel structure, overcharging resisting, discharge, and fail safe is good, has been subjected to people's attention.But LiMn 2O 4Than LiCoO 2, LiNiO 2Capacity is low, and it is very fast to increase capacity attenuation with cycle-index.To be higher than 50 ℃ of capacity attenuations more obvious when ambient temperature.This mainly is LiMn 2O 4Middle Mn 3+D 4Electron configuration causes structure that the Jahn-Teller effect takes place, thereby influences the cyclicity of material.
In order to improve LiMn 2O 4Cycle life, to spinelle LiMn 2O 4Carry out cation and anion and mix up valence state and the Mn that improves manganese 3+Content, make manganese ion avoid d as far as possible 4Electron configuration reduces the generation of Jahn-Teller effect.Report has the anion of mixing up F-[Amatucci G G, Tarascon J M.USP5674646] and I-[Kim J, Manthiram A.Nature, 1997,390:265]; Mix up cation Co 2+[Wakihara M, et al.Solid State Ionics, 1992,57:311] and Ga 3+[Pistoia G, BellittoC, Antonini A.PCT WO97/37394] etc.By mixing up of yin, yang ion the cycle life that improves material is played a role.According to Yanko M.Todorov[Journal of Power Source, 1999,77:198] derive, the size of the specific capacity of material is relevant with valence state that mixes up ion and quantity after mixing up.Improving the material cycle performance behind the ion though mix up, is cost with the capacity of expendable material.
Consider above situation, the object of the invention provides a kind of higher capacity, has the cathode material of good charge-discharge performance.Principle of the present invention is achieved in that with at least a transition metal and replaces manganese, reduced Mn 3+Content, reduce the generation of Jahn-Teller effect, recycle the life-span can improve.Substitute manganese with alkaline-earth metal that has only a kind of valence state or III A family metallic element, lithium ion can not be deviate from from spinel structure fully when making charging, and the lithium ion of not deviating from has been kept structure and has not been destroyed.Transition metal and alkaline-earth metal or the metallic element acting in conjunction of III A family, material recycle the life-span and are improved.The present invention has following formation: (1) cathode material is to use molecular formula LiA xB yMn 2-x-yO 4The compound of expression.A is at least a transition metal, and B is at least a alkali earth metal or III A family metallic element.X and y satisfy 0＜x≤0.08,0＜y≤0.03 in molecular formula.If A, B are made up of two or more metallic elements, x and y are exactly the molal quantity summation of two or more metallic elements so.(2) cathode material is to use molecular formula LiA xB yMn 2-x-yO 4The compound of expression, A is at least a transition metal, although be not particularly limited, transition metal is preferably chosen from Cr, Fe, Co, Ni, Cu, Zn, Cd; B is a kind of alkaline-earth metal or III A family metallic element at least, and alkaline-earth metal is preferably from Mg, Ca, Sr, Ba, and III A family element is chosen from Al, In, Tl.Here narrate the preparation of cathode material of the present invention.
With lithium compound, manganese compound with mix up metallic compound and mix back heating mutually.Perhaps can and mix up metallic compound and mix the back heating at first mutually, heating after will mixing again with lithium compound through the mixture of heating then manganese compound.Can and mix up metallic compound and mix the back heating at first mutually lithium compound equally, heating after will mixing again with manganese compound through the mixture of heating then.
Lithium compound is a raw material, is that example comprises: lithium carbonate, lithium nitrate, lithium hydroxide with conventional salt; Manganese compound comprises chemical manganese bioxide CMD, electrolytic manganese dioxide EMD.As the raw material that mixes up metal ion, can use metal oxide, nitrate, hydroxide.
Be a kind of in order to lithium compound, manganese compound with the method for optimizing that mixes up that metallic compound mixes and the compound that is obtained is heated below.
In the aqueous solution of water miscible lithium salts and manganese salt, the citric acid of molal quantitys such as adding and lithium, manganese, the water-soluble metal ionic compound that will mix up is dispersed in the solution of lithium, manganese, and the moisture of evaporation gained solution.In the method, because the complexing of citric acid and metal ion is evenly fully mixed raw material.Therefore the material that obtains has at last been got rid of the uneven phenomenon of solid phase method blending constituent.
Result as further studying, found that a kind of preferred material combination is as follows: be that lithium compound, manganese nitrate or manganese acetate are manganese compound with the lithium nitrate, the metallic compound that soluble metal nitrate work mixes up.In the time of will being used for cell cathode by the LiMn2O4 that mixes up metal ion that these raw materials obtain, find that this material can realize long circulation life.
Above-claimed cpd is to heat in air atmosphere, heats better in flow air atmosphere, and preferably heats in oxygen flow.
Heating-up temperature is between 500 ℃ to 800 ℃, and is more preferably in the scope between 700 ℃ and 800 ℃.When heating-up temperature surpasses 800 ℃, take place between the particle to reunite to make granular size inhomogeneous; Heating-up temperature is lower than 500 ℃, and raw material reaction not exclusively makes in the synthetic material and contains impurity.
Heating time is more than 8 hours, preferably 12 hours to 24 hours.
In order better to illustrate the present invention, be elaborated below in conjunction with embodiment and accompanying drawing.
Embodiment 1
With the lithium nitrate is the lithium predecessor, and manganese acetate is the manganese predecessor, and chromic nitrate, nickel nitrate, aluminum nitrate are for mixing up metal precursor.1.66g lithium nitrate and 10.6g manganese acetate are dissolved in the deionized water, mix, stir; Chromic nitrate, nickel nitrate, aluminum nitrate are dissolved in the solution.Add an amount of citric acid then, regulator solution pH value 3-4.Obtain starching the attitude thick liquid at 70 ℃ of-80 ℃ of transpiring moistures then, 110 ℃ of vacuumizes obtain loose block presoma.With 400 ℃ of predecomposition of presoma 1 hour, be warmed up to 750 ℃ of roastings 12 hours, obtaining material component is LiCr 0.02Ni 0.03Al 0.02Mn 1.93O 4Black powder, be the spinel structure (see figure 1).With this material and acetylene black, polytetrafluoroethylene is to mix at 85: 10: 5 by weight, is coated on the aluminum foil current collector.Electrolyte 1mol/L LiClO 4/ EC+DEC (1: 1vol.), do electrode, and U.S. Cellgard2400 is a barrier film, is assembled into simulated battery in the glove box of applying argon gas by lithium metal.At current density 0.4mA/cm 2Constant current charge-discharge under the condition, deboost 3.3V-4.35V.Material is discharge capacity 114.6mAh/g first.20 discharge capacities that circulate are 112.7mAh/g.Circulate after 150 times, discharge capacity also remains on the above (see figure 2) of 100mAh/g.
Embodiment 2
Except that sintering temperature is 700 ℃, other condition is with embodiment 1.Material is discharge capacity 113.1mAh/g first, efficient 98.1%.Discharge capacity 107.5mAh/g after 20 times circulates.
Embodiment 3
Except that roasting time 24 hours, other condition is with embodiment 1.Material discharges first and holds 114.2mAh/g, efficient 98%.Discharge capacity 110.8mAh/g after 20 times circulates.
Embodiment 4
Remove roasting time after 6 hours, take out and grind, outside the roasting 6 hours, other condition is with embodiment 1 again.Record material discharge capacity 111.7mAh/g first, efficient 97.6%.Circulating, discharge capacity is 105.6mAh/g after 20 times.
Embodiment 5
Except that the amount of metal ion Al is 0.04, other condition is with embodiment 1.Material discharge capacity first is 107.1mAh/g, and efficient is 97.2%.Circulate after 20 times, discharge capacity is 104.7mAh/g.
Embodiment 6
Removing calcination atmosphere is oxygen, and outside the flow 40ml/min, other condition is with embodiment 1.Material is discharge capacity 115.1mAh/g first, and efficient is 98.5%.Circulate after 20 times, discharge capacity is 109.8mAh/g.
Embodiment 7
Except being the manganese source with the manganese nitrate, other condition is with embodiment 1.The material discharging capacity is 109.5mAh/g, and efficient is 98.4%.Circulate after 20 times, discharge capacity is 106.4mAh/g.Comparative Examples 1
Except that not mixing up the metal ion, consist of LiMn 2O 4The preparation of cathode material similar to embodiment 1.Method of measurement is similar to embodiment 1.Discharge capacity is 120.2mAh/g first, and efficient is 98.6%.Circulate after 20 times, discharge capacity is 112.3mAh/g; When probe temperature was 55 ℃, material is discharge capacity 122.5mAh/g first, and efficient is 98.7%.Circulating, discharge capacity is 102.1mAh/g after 10 times.Comparative Examples 2
Except that the amount of only mixing up metal ion chromium and chromium is 0.05, consist of LiCr 0.05Mn 1.95O 4The preparation of cathode material similar to embodiment 1.Material is discharge capacity 113.6mAh/g first, and efficient is 98%.Circulating, discharge capacity is 108.7mAh/g after 20 times.Comparative Examples 3
Except that the amount of only mixing up metal ion nickel and nickel is 0.05, consist of LiNi 0.05Mn 1.95O 4The preparation of cathode material similar to embodiment 1.Material discharge capacity first is 109.6mAh/g, and circulating, discharge capacity is 106.3mAh/g after 20 times.Comparative Examples 4
Except that the amount of only mixing up ion cobalt and cobalt is 0.05, consist of LiCo 0.05Mn 1.95O 4The preparation of cathode material similar to embodiment 1.Material discharge capacity first is 113.6mAh/g, and circulating, discharge capacity is 109.5mAh/g after 20 times.Comparative Examples 5
Except that only mix up metal ion chromium and nickel and chromium, the nickel total amount is 0.05, consists of LiCr 0.02Ni 0.03Mn 1.95O 4The preparation of cathode material similar to embodiment 1.Material discharge capacity first is 112.4mAh/g, and circulating, discharge capacity is 108.7mAh/g after 20 times.Comparative Examples 6
Except that with the Mg substitute for Al, consist of LiCr 0.02Ni 0.03Mg 0.02Mn 1.93O 4The preparation of cathode material similar to embodiment 1.Material discharge capacity first is 110.4mAh/g, and circulating, discharge capacity is 107.1mAh/g after 20 times.Comparative Examples 7
Except that with the Sr substitute for Al, consist of LiCr 0.02Ni 0.03Sr 0.02Mn 1.93O 4The preparation of cathode material similar to embodiment 1.Material discharge capacity first is 109.3mAh/g, and circulating, discharge capacity is 106.5mAh/g after 20 times.Comparative Examples 8
Except that with the La substitute for Al, consist of LiCr 0.02Ni 0.03La 0.02Mn 1.93O 4The preparation of cathode material similar to embodiment 1.Material discharge capacity first is 103.8mAh/g, and circulating, discharge capacity is 98.3mAh/g after 20 times.Comparative Examples 9
Except that with the Tl substitute for Al, consist of LiCr 0.02Ni 0.03Tl 0.02Mn 1.93O 4The preparation of cathode material similar to embodiment 1.Material discharge capacity first is 113.2mAh/g, and circulating, discharge capacity is 108.8mAh/g after 20 times.Comparative Examples 10
Except that substituting the Ni, consist of LiCr with Co 0.02Co 0.03Al 0.02Mn 1.93O 4The preparation of cathode material similar to embodiment 1.Material discharge capacity first is 112.8mAh/g, and circulating, discharge capacity is 108.3mAh/g after 20 times.

Claims (9)

1. the cathode material of a lithium rechargeable battery is characterized in that by chemical formula be LiA xB yMn 2-x-yO 4The compound of expression constitutes, and wherein A is at least a transition metal beyond the Mn; B is element in the III A family or the element in the II A family alkaline-earth metal.X is the molal quantity of elements A, if A is made of multiple transition metal, x is exactly the molal quantity summation of all transition metals.Y is the molal quantity of element B, if B is made of multiple III A or II A family metallic element, y is exactly the molal quantity summation of all metallic elements.X, y satisfy respectively: 0＜x≤0.08 0＜y≤0.03
2. according to the cathode material of claim 1, it is characterized in that A be element Cr, Co, Ni element any one or multiple.
3. according to the cathode material of claim 1, it is characterized in that B is any one or two kinds of among Al, In, Tl or Mg, Ca, the Sr.
4. according to the cathode material of claim 1, it is characterized in that by heating lithium compound, manganese compound and mix up that the mixture of metallic compound obtains.
5. according to the cathode material of claim 1, it is characterized in that being dispersed in the aqueous solution that contains lithium salts and manganese salt, the solution transpiring moisture that obtains to obtain a mixture, is obtained the mixture heating by the metallic compound that mixes up with solubility.
6. according to the cathode material of claim 5, lithium-containing compound is selected from lithium nitrate or lithium acetate, contains manganese compound and selects from manganese acetate.
7. according to the cathode material of claim 1, it is characterized in that 500 ℃-800 ℃ of sintering temperatures, best 700 ℃-800 ℃.
8. according to the cathode material of claim 1, it is characterized in that heating time more than 8 hours, preferably 12 hours to 24 hours.
9. according to the cathode material of claim 1, it is characterized in that heating atmosphere is an air atmosphere, flow air atmosphere is better, preferably the oxygen atmosphere of Liu Donging.
CN99117396A 1999-11-30 1999-11-30 Cathode material for lithium ion battery and its making process Pending CN1298210A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1324735C (en) * 2003-04-03 2007-07-04 索尼株式会社 Cathode material, method of manufacturing the same, and battery using the same
CN100373668C (en) * 2004-05-28 2008-03-05 北京化工大学 Laminar vanadium-manganese oxide as positive electrode material of lithium ion cell and preparation method thereof
CN103066268A (en) * 2012-12-07 2013-04-24 上海锦众信息科技有限公司 Preparation method of chromium-doped anode composite material of lithium ion battery
EP2650951A1 (en) * 2010-12-09 2013-10-16 Nec Corporation Positive electrode active material for secondary battery and secondary battery using same
CN115241425A (en) * 2022-07-01 2022-10-25 湖南顺隆新能源科技有限公司 Lithium manganate positive electrode material and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1324735C (en) * 2003-04-03 2007-07-04 索尼株式会社 Cathode material, method of manufacturing the same, and battery using the same
CN100373668C (en) * 2004-05-28 2008-03-05 北京化工大学 Laminar vanadium-manganese oxide as positive electrode material of lithium ion cell and preparation method thereof
EP2650951A1 (en) * 2010-12-09 2013-10-16 Nec Corporation Positive electrode active material for secondary battery and secondary battery using same
EP2650951A4 (en) * 2010-12-09 2015-04-22 Nec Corp Positive electrode active material for secondary battery and secondary battery using same
JP5942852B2 (en) * 2010-12-09 2016-06-29 日本電気株式会社 Positive electrode active material for secondary battery and secondary battery using the same
CN103066268A (en) * 2012-12-07 2013-04-24 上海锦众信息科技有限公司 Preparation method of chromium-doped anode composite material of lithium ion battery
CN115241425A (en) * 2022-07-01 2022-10-25 湖南顺隆新能源科技有限公司 Lithium manganate positive electrode material and preparation method thereof
CN115241425B (en) * 2022-07-01 2023-09-05 湖南顺隆新能源科技有限公司 Lithium manganate positive electrode material and preparation method thereof

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