CN1560936A - A kind of preparation method of lithium manganese oxide and its application in battery - Google Patents

A kind of preparation method of lithium manganese oxide and its application in battery Download PDF

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Publication number
CN1560936A
CN1560936A CNA2004100057326A CN200410005732A CN1560936A CN 1560936 A CN1560936 A CN 1560936A CN A2004100057326 A CNA2004100057326 A CN A2004100057326A CN 200410005732 A CN200410005732 A CN 200410005732A CN 1560936 A CN1560936 A CN 1560936A
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solution
lithium
manganese oxide
lithium manganese
gel
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CN1249832C (en
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童庆松
杨勇
林素英
张华香
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Xiamen University
Fujian Normal University
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Fujian Normal University
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

This invention provides a method for synthesizing LiMn oxide by low temperature two-stage sintering and its usage in Li ionic cells or Li cells including: weighing Li hydroxide, Mn acetate, citric acid and complexon III, mixing the soluble Mn2+ solution with the citric acid solution to solution I, mixing the Li hydroxide solution with the complexon III solution to form solution II mixed with I and heated to get a gel to be sintered by microwave which can be used as the positive material of Li ionic cells or Li cells. The quick warm-up temperature can be realized in a short period by the microwave sintering method changing the method of conventional long time high temperature sintering to make the chemical composition and granularity of the synthesizer uniform and keep the measurement ratio of the original synthesizer. The chelatc method can improve its uniformity.

Description

A kind of preparation method of lithium manganese oxide and the application in battery thereof
Technical field
The present invention relates to a kind of preparation method of synthetic lithium manganese oxide, and utilize the synthetic lithium manganese oxide of this method as the application of electrode material in lithium ion battery and lithium battery.
Background technology
Along with popularizing rapidly of removable electronic products such as portable computer, mobile phone, the demand that has driven chargeable battery increases greatly.Compare with all kinds of chargeable batteries, lithium ion battery has the specific capacity height, discharge and recharge memory-less effect, advantage such as have extended cycle life.Compare with the fail safe of lithium battery, it has greatly improved again.Therefore, chargeable lithium ion battery has become the focus of the research and development of international battery of new generation.
The negative material of lithium ion battery mainly contains the lithium material by one or more and forms, as lithium metal, lithium～metal alloy, lithium metal oxide, lithium carbon composite etc.With respect to positive electrode, the capacity of existing negative material is higher, as lithium carbide (LiC 6) capacity be 372mAh/g, tin lithium (Li 21Sn 5) capacity reach 761mAh/g.Li 21Sn 5The capacity of negative material can reach 948mAh/g.Therefore the raising of the positive electrode ratio of performance to price has prior meaning to the improvement of lithium ion battery performance.
The positive electrode of lithium ion battery mainly is to be made by one or more lithium metal oxides with layer structure or transition metal oxide configuration.As stratiform lithium and cobalt oxides (LiCoO 2), lithium nickel oxide (LiNiO 2), spinel lithium manganese oxide (LiMn 2O 4), LiFePO4 (Li xFePO 4) wait anodal theoretical capacity to be generally 100 to 170mAh/g.People are devoted to the research of high power capacity positive electrode in recent years, though LiCoO 2Realized commercialization, but, its use has been restricted because there are the restriction of aspects such as price, resource, environment in cobalt and associated materials.LiNiO 2Though compare LiCoO 2Cheaply, but practical LiNiO 2Synthetic difficult the realization.By contrast, the manganese series compound has aboundresources, advantage such as cheap, but the LiMn of the spinel-type of broad research at present 2O 4Still exist capacity relatively low, shortcoming such as capacity attenuation is fast in discharging and recharging.Through effort for many years, still fail to solve the problem that the capacity of both positive and negative polarity is difficult to mate.
The result of study of numerous documents shows that in the charge and discharge process, the capacity attenuation of lithium manganese oxide is mainly caused by following four kinds of factors: spinel lithium-manganese oxide can be dissolved in the nonaqueous electrolyte lentamente; Manganese is in high oxidation state and causes the lattice instability in the spinel lithium-manganese oxide; As spinel lithium manganese oxide (Li xMn 2O 4) by deep discharge, the average oxidation number that particularly is discharged to manganese is less than 3.5 o'clock, the Li of spinel structure xMn 2O 4Meeting spontaneous generation Jahn～Teller effect, lattice is changed to tetragonal crystal system by cubic system, because of deformation causes Li xMn 2O 4The stability decreases of lattice; Li xMn 2O 4The phasor complexity, form and synthesis condition to Li xMn 2O 4Chemical property significant effects is arranged, the homogeneity question of exist forming.
Charge and discharge cycles and high temperature at lithium ion battery are deposited in the process, and the capacity of lithium manganese oxide is decay rapidly, and this becomes the matter of utmost importance that influences in the lithium ion battery applications.In order to address this problem, improve the charge-discharge performance of spinel lithium-manganese oxide, carried out number of research projects both at home and abroad, obtained many achievements, conclude to get up to be summarized as follows.
From the up-to-date research trends of preparation method two big classes are arranged.The first kind is with physics method, chemical method, doping method and the good Li of filling property of ion-exchange legal system xMn 2O 4The MnO that selects big tunnel is also arranged 2Sample is as the report of positive electrode.Doping method comprises physical doping method and chemical doping method.By the lithium manganese oxide in preparation Stability Analysis of Structures or the big tunnel during discharging and recharging that mix, to realize the purpose of filling property of improvement.Selecting ion-exchange is in order to seek gentle preparation condition.In addition, also have many colloidal sol～gel method metal pointing spar type Li of using xMn 2O 4Report.Second class is by preparation nanometer Li xMn 2O 4Method obtain the good sample of filling property.This preparation method with citric acid or oxalic acid or acetic acid or other organic acid as medium, with sol-gal process, colloidal sol～gel～esterification process or its method synthesis of nano Li that derives xMn 2O 4Prepared Li xMn 2O 4Nano particle has nano-meter characteristic, obtains to discharge and recharge the little sample of reaction resistance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the synthetic lithium manganese oxide of low temperature double sintering method and prepared lithium manganese oxide Li thereof of adopting xMn yO z(3.3≤x≤4.3; 4.7≤y≤5.7; 11.5≤z≤12.5) the application in lithium ion battery and lithium battery.
The preparation method of the said lithium manganese oxide of the present invention is:
1, preparation solution I.Press (0.9～1.3): (1.81～2.3): (1.81～2.3): the mol ratio of (0.9～1.6) takes by weighing lithium hydroxide, manganese acetate, citric acid and disodium EDTA respectively, mixes soluble M n 2+Salting liquid and citric acid solution form solution I.
2, preparation solution II.Lithium hydroxide solution and disodium EDTA solution are mixed according to the above ratio, make its dissolving form solution II.
3, solution I and solution II are mixed, form solution III, the pH value of regulator solution III is 4～9, and heating concentrated solution III obtains stabilizing gel.
4, gel is carried out microwave sintering, the steps include:
1) gel is placed microwave oven, handle 0.5～5h; 2) roasting 20～80h then, sintering temperature is controlled at 200～800 ℃, and the flow of sintering process control air is 5～240mL/min; 3) with soluble sodium ion in the distilled water washed product; 4) after the washing, oven dry gets product lithium manganese oxide Li to the end xMn yO z, 3.3≤x≤4.3 wherein; 4.7≤y≤5.7; 11.5≤z≤12.5;
Or 1) with gel roasting 20～80h, sintering temperature is controlled at 200～800 ℃, and the flow of sintering process control air is 5～240mL/min; 2) gel is placed microwave oven, handle 0.5～5h; 3) with soluble sodium ion in the distilled water washed product; 4) after the washing, oven dry gets product lithium manganese oxide Li to the end xMn yO z, 3.3≤x≤4.3 wherein; 4.7≤y≤5.7; 11.5≤z≤12.5.
Above-described roasting time is preferably 50～79h.
The prepared lithium manganese oxide of the present invention can be used for lithium ion battery or lithium battery, can be used as the positive electrode of lithium ion battery or lithium battery.
Prepare in the method for lithium manganese oxide existing, adopt high temperature and long sintering process more.Because at high temperature with for a long time in the sintering process, the volatile quantity of lithium is bigger, the composition that often causes the preparation product and original metering are than different.If use the said microwave sintering method of the present invention instead, then can realize being rapidly heated of short time, changed the technology of habitual long-time high temperature sintering for a long time, make the chemical composition and the uniform granularity of synthetic product, kept the metering ratio of former synthetic.The disodium EDTA and the citric acid that use in building-up process are chelating agent, adopt a flat iron plate for making cakes method of closing can improve the uniformity of synthetic product, reduce lithium manganese oxide solubility in electrolyte solution, improve the overall performance of lithium ion battery.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
The LiOHH that mixes 0.130mol 2O and 0.230mol citric acid add thermal agitation 0.5h and make it water-soluble.The Mn (Ac) that mixes 0.230mol again 24H 2O and 0.120molNa 2EDTA2H 2O adds thermal agitation 0.5h it is dissolved in another part water.Two parts of solution are mixed, and the pH value of regulator solution is about 6.2, stirs 0.5h.Heating is condensed into gelinite on electric furnace.Gelinite is heated 5h in microwave oven, then under 260 ℃ in Muffle furnace roasting 20h, the flow of sintering process control air is 240mL/min.Bubbling air in heating, insulation and temperature-fall period.Sintering finishes the back with the distilled water washing, removes water-soluble sodium ion, and the oven dry sample obtains product.
Embodiment 2
The LiOHH that mixes 0.10mol 2O and 0.220mol citric acid add thermal agitation 0.5h and make it soluble in water.The Mn (Ac) that mixes 0.220mol again 24H 2The Na of O and 0.110mol 2EDTA2H 2O adds thermal agitation 0.5h it is dissolved in another part water.Mix two parts of solution, the pH value of regulator solution is 7.2, stirs 0.5h, and heating is condensed into gelinite on electric furnace.Gelinite is heated 2h in microwave oven, then under 400 ℃ in Muffle furnace roasting 56h, the flow of sintering process control air is 150mL/min, sintering finishes the back with the distilled water washing, removes water-soluble sodium ion, the oven dry sample obtains product.
Embodiment 3
The LiOHH that mixes 0.09mol 2The citric acid of O and 0.2mol adds thermal agitation 0.5h and makes it soluble in water.The Mn (Ac) that mixes 0.185mol again 24H 2The Na of O and 0.110mol 2EDTA2H 2O adds thermal agitation 0.5h and makes it soluble in water.Mix two kinds of solution, the pH value of regulator solution is 8.5, stirs 0.5h, and heating is condensed into gelinite on electric furnace.Place microwave oven to heat 0.5h gelinite, then under 200 ℃ in Muffle furnace 80 h of roasting, the flow of sintering process control air is 5mL/min, sintering finishes the back with the distilled water washing, removes water-soluble sodium ion, the oven dry sample obtains product.
Embodiment 4
The LiOHH that mixes 0.095mol 2The citric acid of O and 0.190mol adds thermal agitation 0.5h and makes it soluble in water.The Mn (Ac) that mixes 0.181mol again 24H 2The Na of O and 0.09mol 2EDTA2H 2O adds thermal agitation 0.5h it is dissolved in another part water.Mix two kinds of solution, the pH value of regulator solution is 9, stirs 0.5h, and heating is condensed into gelinite on electric furnace.With gel roasting 80h, sintering temperature is controlled at 220 ℃.Slowly be cooled to below 100 ℃, the flow of sintering process control air is 5mL/min; Gel is placed microwave oven, with carrying out annealing in process behind the strong microwave heating treatment 0.6h; Sintering finishes the back with the distilled water washing, removes water-soluble sodium ion, and the oven dry sample obtains product.
Embodiment 5
The LiOHH that mixes 0.11mol 2The citric acid of O and 0.181mol adds thermal agitation 0.5h and makes it soluble in water.The Mn (Ac) that mixes 0.21mol again 24H 2The Na of O and 0.10mol 2EDTA2H 2O adds thermal agitation 0.5h it is dissolved in another part water.Mix two kinds of solution, the pH value of regulator solution is 4, stirs 0.5h, and heating is condensed into gelinite on electric furnace.With gel roasting 20h, sintering temperature is controlled at 800 ℃.Slowly be cooled to below 100 ℃, the flow of sintering process control air is 240mL/min; Intermediate product is placed microwave oven, with carrying out annealing in process behind the strong microwave heating treatment 2.5h; Sintering finishes the back with the distilled water washing, removes water-soluble sodium ion, and the oven dry sample obtains product.
Embodiment 6
The LiOHH that mixes 0.12mol 2The citric acid of O and 0.21mol adds thermal agitation 0.5h and makes it soluble in water.The Mn (Ac) that mixes 0.19mol again 24H 2The Na of O and 0.16mol 2EDTA2H 2O adds thermal agitation 0.5h it is dissolved in another part water.Mix two kinds of solution, the pH value of regulator solution is 5.5, stirs 0.5h, and heating is condensed into gelinite on electric furnace.With gel roasting 60h, sintering temperature is controlled at 500 ℃.Slowly be cooled to below 100 ℃, the flow of sintering process control air is 110mL/min.Intermediate product is placed microwave oven, with carrying out annealing in process behind the strong microwave heating treatment 0.5h; Sintering finishes the back with the distilled water washing, removes water-soluble sodium ion, and the oven dry sample obtains product.

Claims (6)

1、一种锂锰氧化物的制备方法，其特征在于其步骤如下：1, a kind of preparation method of lithium manganese oxide, it is characterized in that its steps are as follows: 1)、制备溶液I，分别称取氢氧化锂、醋酸锰、柠檬酸和乙二胺四乙酸二钠盐，混合可溶性Mn2+盐溶液与柠檬酸溶液，形成溶液I；1), prepare solution I, weigh lithium hydroxide, manganese acetate, citric acid and edetate disodium salt respectively, mix soluble Mn 2+ salt solution and citric acid solution, form solution I; 2)、制备溶液II，将氢氧化锂溶液和乙二胺四乙酸二钠盐溶液混合，使其溶解形成溶液II；2), preparing solution II, mixing lithium hydroxide solution and ethylenediaminetetraacetic acid disodium salt solution, and dissolving them to form solution II; 3)、将溶液I和溶液II混合，形成溶液III，调节溶液III的pH值为4～9，加热浓缩溶液III得到凝胶；3), mixing solution I and solution II to form solution III, adjusting the pH value of solution III to 4-9, heating and concentrating solution III to obtain a gel; 4)、对凝胶进行微波烧结，得产物锂锰氧化物；4), carry out microwave sintering to gel, obtain product lithium manganese oxide; 5)、所述的氢氧化锂、醋酸锰、柠檬酸和乙二胺四乙酸二钠盐按0.9～1.3∶1.81～2.3∶1.81～2.3∶0.9～1.6的摩尔比称取。5) The lithium hydroxide, manganese acetate, citric acid and disodium edetate are weighed in a molar ratio of 0.9-1.3:1.81-2.3:1.81-2.3:0.9-1.6. 2、如权利要求1所述的一种锂锰氧化物的制备方法，其特征在于所说的微波烧结其步骤为：2. The preparation method of a kind of lithium manganese oxide as claimed in claim 1, characterized in that the steps of said microwave sintering are: 1)将凝胶置于微波炉中，处理0.5～5h；2)然后焙烧20～80h，焙烧温度控制在200～800℃，烧结过程控制空气的流量为5～40mL/min；3)用蒸馏水洗涤产物中可溶性的钠离子；4)洗涤后，烘干，得到最后的产物锂锰氧化物LixMnyOz，其中3.3≤x≤4.3；4.7≤y≤5.7；11.5≤z≤12.5。1) Put the gel in a microwave oven and treat it for 0.5-5 hours; 2) Then roast it for 20-80 hours, the roasting temperature is controlled at 200-800°C, and the flow rate of the air is controlled at 5-40mL/min during the sintering process; 3) Wash it with distilled water Soluble sodium ions in the product; 4) After washing and drying, the final product lithium manganese oxide Li x Mn y O z is obtained, wherein 3.3≤x≤4.3; 4.7≤y≤5.7; 11.5≤z≤12.5. 3、如权利要求1所述的一种锂锰氧化物的制备方法，其特征在于所说的微波烧结其步骤为：3. The preparation method of a kind of lithium manganese oxide as claimed in claim 1, characterized in that the steps of said microwave sintering are: 1)将凝胶焙烧20～80h，焙烧温度控制在200～800℃，烧结过程的控制空气的流量为5～240mL/min；2)将凝胶置于微波炉中，处理0.5～5h；3)用蒸馏水洗涤产物中可溶的钠离子；4)洗涤后，烘干，得到最后的产物锂锰氧化物LixMnyOz，其中3.3≤x≤4.3；4.7≤y≤5.7；11.5≤z≤12.5。1) Calcinate the gel for 20-80 hours, control the calcining temperature at 200-800°C, and control the air flow rate during the sintering process to 5-240mL/min; 2) Put the gel in a microwave oven and process it for 0.5-5 hours; 3) Wash the soluble sodium ions in the product with distilled water; 4) After washing, dry to obtain the final product lithium manganese oxide Li x Mn y O z , wherein 3.3≤x≤4.3; 4.7≤y≤5.7; 11.5≤z ≤12.5. 4、如权利要求2或3所述的一种锂锰氧化物的制备方法，其特征在于所说的焙烧时间为50～79h。4. A method for preparing lithium manganese oxide according to claim 2 or 3, characterized in that the calcination time is 50-79 hours. 5、如权利要求1所制备的锂锰氧化物用于锂离子电池或锂电池。5. The lithium manganese oxide prepared according to claim 1 is used in lithium ion battery or lithium battery. 6、如权利要求1所制备的锂锰氧化物作为锂离子电池或锂电池的正极材料。6. The lithium manganese oxide prepared according to claim 1 is used as a positive electrode material of a lithium ion battery or a lithium battery.
CNB2004100057326A 2004-02-16 2004-02-16 Preparing method of lithium manganese oxide and its application in battery Expired - Fee Related CN1249832C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100438155C (en) * 2006-01-13 2008-11-26 厦门大学 Manganese ion lithium silicate/carbon composite anode material for rechargeable lithium battery and method for preparing the same
CN100503451C (en) * 2007-03-30 2009-06-24 中国科学院青海盐湖研究所 Lithium ion battery anode material Li1+xV3O8Preparation method of (1)
CN102394295A (en) * 2011-11-23 2012-03-28 东莞新能源科技有限公司 Lithium ion battery and its positive material
CN104843795A (en) * 2015-04-30 2015-08-19 昆明理工大学 Microwave-assisted method for preparing manganite crystal whiskers
WO2016070205A3 (en) * 2014-10-31 2016-09-09 Csir Production of a spinel material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100438155C (en) * 2006-01-13 2008-11-26 厦门大学 Manganese ion lithium silicate/carbon composite anode material for rechargeable lithium battery and method for preparing the same
CN100503451C (en) * 2007-03-30 2009-06-24 中国科学院青海盐湖研究所 Lithium ion battery anode material Li1+xV3O8Preparation method of (1)
CN102394295A (en) * 2011-11-23 2012-03-28 东莞新能源科技有限公司 Lithium ion battery and its positive material
CN102394295B (en) * 2011-11-23 2015-09-30 东莞新能源科技有限公司 A kind of lithium ion battery and positive electrode thereof
WO2016070205A3 (en) * 2014-10-31 2016-09-09 Csir Production of a spinel material
CN107108260A (en) * 2014-10-31 2017-08-29 科学与工业研究理事会 Preparation of spinel materials
CN107108260B (en) * 2014-10-31 2019-08-23 科学与工业研究理事会 Preparation of spinel materials
CN104843795A (en) * 2015-04-30 2015-08-19 昆明理工大学 Microwave-assisted method for preparing manganite crystal whiskers

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