CN105958035A - Preparation method of lanthanum oxide-coated spinel lithium-rich lithium manganate - Google Patents

Preparation method of lanthanum oxide-coated spinel lithium-rich lithium manganate Download PDF

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CN105958035A
CN105958035A CN201610525411.1A CN201610525411A CN105958035A CN 105958035 A CN105958035 A CN 105958035A CN 201610525411 A CN201610525411 A CN 201610525411A CN 105958035 A CN105958035 A CN 105958035A
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lithium
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spinel
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童庆松
游帅帅
郭可可
赵南南
王蕾
张贵萍
曾观音
王彤
李秀华
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Fujian Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
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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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a preparation method of lanthanum oxide-coated spinel lithium-rich lithium manganate. The method is characterized by comprising the steps of: mixing spinel-type lithium-rich lithium manganate powder with a component LixMnyOz, lanthanum trioxide, lanthanide metal powder or lanthanum hydroxide coating agent powder according to the weight ratio of 1 to (0.001-0.12); adding a wet-milling medium and preparing a precursor through wet-milling and drying methods; and sintering the precursor at a temperature interval of 290-390 DEG C to prepare the lanthanum oxide-coated spinel lithium-rich lithium manganate. The raw material cost is relatively low; the charge-discharge property of a sample at a high temperature in a storage condition is improved; and a good foundation is laid for industrialization.

Description

The preparation method of the spinel lithium-rich LiMn2O4 of cladding lanthana
Technical field
The invention belongs to technical field prepared by battery electrode material, be specifically related to one and can be used for lithium battery, lithium ion The preparation method of the spinel lithium-rich LiMn2O4 of the cladding lanthana of battery, polymer battery and ultracapacitor.
Technical background
Lithium ion battery have cell voltage height, energy density height, memory-less effect, have extended cycle life, self discharge is low Advantage, the performance of positive electrode plays a part decision to the performance of lithium ion battery.
The advantages such as it is low that manganese-based anode material has price, green non-pollution, are the research emphasis of lithium ion battery.At manganio In positive electrode, that studies more has spinelle LiMn2O4, stratiform LiMnO2With layed solid-solution positive electrode.Wherein, layer Shape LiMnO2The less stable of structure when discharge and recharge, studies seldom at present.Spinelle LiMn2O4Can be 4V and 3V two Voltage range plays a role.The voltage platform correspondence lithium ion in the 4V district embedding in the tetrahedron 8a position of spinel structure and de- Go out；The embedding in the octahedra 16c position of spinel structure of the voltage platform correspondence lithium ion in 3V district and abjection.Lithium ion is at point The tetrahedral site of spinel structure embeds and deviates from not result in the significant change of structure.But, when depth of discharge is excessive, sample The structure of product can occur John-Teller to distort, and embeds and deviates from lithium ion structure can be caused by cube becoming in octahedron Four directions, discharge capacity rapid decay.Therefore, suppression spinelle LiMn2O4The John-Teller distortion of structure is to improve its charge and discharge The key of electrical property.Additionally, LiMn2O4Middle manganese is dissolved in electrolyte, and during high voltage discharge and recharge, the decomposition of electrolyte is also shadow Ring the key reason of electrode material cycle performance.
At Li4Mn5O12Charge and discharge process in, the deintercalation of lithium ion reaction mainly occurs in 3V district, and its theoretical discharge holds Amount is up to 163mAh/g.With spinelle LiMn2O4The theoretical capacity ratio of 148mAh/g be significantly improved, have that to become 3V district excellent The probability of elegant positive electrode.This material structure cell expansion rate in charge and discharge process is less, has the advantages such as cycle performance is outstanding. But, Li4Mn5O12Heat stability bad.Li under high temperature1+yMn2-yO4(y < 0.33) is easily decomposed to LiMn2O4With Li2MnO3[Manthiram A., et al., Ceram.Trans, 1998,92:291-302.] so that Li4Mn5O12Very Prepared by difficulty conventional method.Have studied multiple synthetic method, it is intended to obtain more preferably preparation method.Burn including solid phase Connection, sol-gal process, hydro-thermal method and microwave sintering method etc..
Solid sintering technology is the compound mixing of the compound by lithium and manganese, sintering preparation under aerobic or oxygen free condition. Takada etc. [Takada T., J. Solid State Chem., 1997,130:74-80.] are by lithium salts (LiNO3、 Li2CO3、Li(CH3) and manganese compound (MnCO COO)3、Mn(NO3)2、Mn2O3And MnO2) mixing, 500 DEG C of-800 DEG C of humidity provinces Between prepare Li4Mn5O12.Kang etc. [Kang S. H., et al., Electrochem. Solid-State Lett., 2000,3 (12): 536-639.] and Fumio etc. [Fumio S., et al., J. Power Sources, 1997,68 (2): 609-612.] LiOH H first it is dried2O and Mn (Ac)2·4H2The mixed solution of O, prepares Li then at 500 DEG C of sintering [LiyMn2-y]O4.Li [the Li that they prepareyMn2-y]O4The sample discharge capacity in 3V district is 115-126mAh/g.At oxygen gas In atmosphere, Takada etc. [Takada T., et al., J. Power Sources, 1997,68:613-617.] finds, 500 DEG C of sintering CH3COOLi and Mn (NO3)2Fused mass prepare product the 1st circulation discharge capacity be 135mAh/g. Shin etc. [Shin Y., et al., Electrochim. Acta, 2003,48 (24): 3,583 3592.] think sintering When temperature is less than 500 DEG C, Mn3+Amount increase make discharge capacity increase.[Kajiyama A., the et al., J. such as Kajiyama Japan Soc. Powder & Powder Metallurgy, 2000,47 (11): 1139-1143； Nakamura T. Et al., Solid State Ionics, 1999,25:167-168.] by LiOH H2O and γ-Mn2O3Mixing, they Find, the Li of preparation in oxygen atmosphere4Mn5O12Chemical property better than prepare at air atmosphere.[the Xu such as Xu Meihua M. H., et al., J. Phys. Chem, 2010,114 (39): 16,143 16147.] and Tian etc. [Tian Y., Et al., Chem. Commun., 2007:2072 2074.] by MnSO4Add LiNO3And NaNO3Fuse salt in, 470 DEG C of-480 DEG C of temperature ranges can prepare nanometer Li4Mn5O12.Tian etc. [Tian Y., et al., Chem. Commun., 2007:2072 2074.] the nano wire Li for preparing4Mn5O12Putting that (under 0.2C multiplying power electric current) the 1st circulation and the 30th circulate Capacitance is respectively 154.3mAh/g and 140mAh/g.Thackeray etc. [Thackeray M. M, et al., J. Solid State Chem., 1996,125:274-277.；Michael M., et al., American Ceram. Soc. Bull, 1999,82 (12): 3347-3354.] by LiOH H2O and γ-MnO2Mixing, 600 DEG C of sintering can prepare Li4Mn5O12.Yang etc. [Yang X., et al., J. Solid State Chem., 2000,10:1903-1909.] By γ-MnO2Or β-MnO2Or barium manganese ore or acid birnessite and melted LiNO3Mixing, can prepare at 400 DEG C Li1.33Mn1.67O4.Liu Cong [Liu Cong. the synthesis of lithium ion battery mangaic acid lithium cathode material and performance [D]. Guangdong: south China is pedagogical University, 2009.] first by LiOH H2O and electrolysis MnO2Dehydrated alcohol mixes, in 450 DEG C of sintering in air atmosphere, then Ball milling obtains sample in ethanol.The high discharge capacity of the sample that they prepare is 161.1mAh/g, the electric discharge of the 30th circulation Capacity is higher than 120mAh/g.
Kim etc. [Kim J., et al., J. Electrochem. Soc, 1998,145 (4): 53-55.] exist LiOH and Mn (CH3COO)2Mixed solution in add Li2O2, first prepare LixMnyOz·nH2O, then filter, wash, be dried Li is prepared with solid-phase sintering4Mn5O12.They find, the initial discharge capacity of the sample of 500 DEG C of preparations is 153mAh/g, and 40 follow The capacity attenuation rate of ring is 2%.Manthiram etc. [Manthiram A., et al., J. Chem. Mater, 1998,10 (10): 2895-2909.] research shows, in LiOH solution, and Li2O2Initial oxidation [Mn (H2O)6]2+, then through 400 DEG C of sintering, The Li of preparation4Mn5O12Discharge capacity in the 1st circulation is 160mAh/g.
In order to improve the process conditions of solid-phase sintering, double sintering method is used for preparation process.[the Li righteous army such as Li righteous army Deng, non-ferrous metal, 2007,59 (3): 25-29.] by LiOH, Mn (C2O4)2And H2C2O4Mixture be placed in air atmosphere In, prepare micron Li at 350 DEG C and 500 DEG C of sintering respectively4Mn5O12.The sample of preparation in the discharge capacity of the 1st circulation is 151mAh/g.Gao etc. [Gao J., et al., Appl. Phys. Lett., 1995,66 (19): 2487-2489.； Gao J., et al., J. Electrochem. Soc., 1996,143 (6): 1783-1788.] use two step heatings It is prepared for spinelle Li1+xMn2-xO4x(0<x≤0.2).[Robertson A. D., et al., the J. such as Robertson Power Sources, 2001,97-97:332-335.] at Mn (CH3COO)2·4H2O solution is mixed into Li2CO3, it is dried and obtains Obtain precursor.It is prepared for Li respectively at 250 DEG C and 300-395 DEG C of sintering4Mn5O12.Sample the 1st circulation and the electric discharge of the 50th circulation Capacity is respectively 175mAh/g and 120mAh/g.Wang etc. [Wang G. X., et al., J. Power Sources, 1998,74 (2): 198-201.] Li has been synthesized at 380 DEG C4Mn5O12.Xia [Xia Y. Y., et al., J. Power Sources, 1996,63 (1): 97-102.] etc. by injection method, sample is prepared at 260 DEG C of direct sinterings.At C/3 electric current Under, the discharge capacity first of this sample is 80mAh/g.
More than research shows, solid sintering technology prepares Li4Mn5O12Need to be at pure O2Or air atmosphere is carried out.This method Shortcoming includes that the composition of synthetic product and particle size distribution are relatively big, and the capacity attenuation rate of charge and discharge cycles is high, heavy-current discharge performance The best, high temperature cyclic performance is more undesirable.
In order to improve the uniformity of sample, reducing the granularity of sample particle, sol-gal process is used for preparing Li4Mn5O12 [Hao Y. J., et al., J. Solid State Electrochem., 2009,13:905 912；Meng Lili etc., Inorganic chemicals industry, 2009,46 (5): 37-39；Chu H. Y., et al., J. Appl. Electrochem, 2009, 39: 2007-2013.].Can feelings etc. [can feelings etc., battery, 2004,34 (3): 176-177.] by LiOH 2H2O、Mn (CH3COO)2·4H2The mixture of O and citric acid prepares micron spinelle Li at 300 DEG C and 500 DEG C sintering respectively4Mn5O12。
In order to improve the uniformity of sample, reducing the granularity of sample particle, reduce sintering temperature, hydro-thermal method is also used for system Standby process.Zhang [Zhang Y. C., et al., Mater. Res. Bull., 2002,37 (8): 1411-1417.； Zhang Yongcai. hydro-thermal studies [D] with solvent-thermal process metastable phase functional material. Beijing: Beijing University of Technology, 2003.； Zhang Y. C., et al., J. Solid State Ionics, 2003,158 (1): 113-117.] etc. first by H2O2、 LiOH and Mn (NO3)2Mixed solution reaction prepare threadiness presoma LixMnyOz·nH2O, then with LiOH solution low-temperature hydrothermal Reaction prepares nanometer Li4Mn5O12.Generation superfine [generation is superfine. a kind of synthesis Li4Mn5O12The method [P] of sub-micrometer rod. CN 201010033605.2, applying date 2010.01.04.] and by MnSO4·H2O、KMnO4With mixing of cetyl trimethylammonium bromide Compound prepares submicron MnOOH 140 DEG C-180 DEG C temperature range hydro-thermal reactions, is blended into LiOH H2O, finally in 500 DEG C- 900 DEG C of prepared Li4Mn5O12.Sun Shuying etc. [Sun Shuying etc., inorganic material Leader, 2010,25 (6): 626-630.] pass through Hydro-thermal reaction, by MnSO4·H2O and (NH4)2S2O8Prepare nanometer β-MnO2, it is mixed into LiNO3After again by low-temperature solid-phase method reaction system Obtain Li4Mn5O12。
Due to microwave sintering method, to have sintering velocity fast, the advantages such as sintering process is easy, and microwave sintering method or solid-phase sintering- The method that microwave sintering combines is used for synthesizing LiMn2O4.[Ahniyaz A., et al., the J. Eng. such as Ahniyaz Mater. Technol., 2004,264-268:133-136.] by γ-MnOOH, LiOH and H2O2Mixture pass through microwave Sintering process has synthesized LiMn2O4.Tong Qingsong seminar is with LiOH and Mn (CH3COO)2For raw material [woods element English etc., Fujian chemical industry, 2004,2:1-4.；Tong Qingsong etc., electrochemistry, 2005,11 (4): 435-439.] or with LiOH and MnC2O4[virgin for raw material Celebrating pine etc., Fujian Normal University's journal, 2006,22 (1): 60-63.], with disodium EDTA (EDTA) and lemon Lemon acid is chelating agent, uses microwave-solid phase double sintering method, is prepared for spinelle Li at 380 DEG C3.22Na0.569Mn5.78O12Sample Product or Li4Mn5O12Positive electrode.Research shows, at 4.5-2.5V voltage range, the Li of preparation3.22Na0.569Mn5.78O12Sample Discharge capacity in the 1st circulation is 132mAh/g, and the capacity attenuation rate of 100 circulations is 6.8%.Through 4 months deposit, this sample Product initial discharge capacity is 122mAh/g, and the capacity attenuation rate of 100 circulations is 17.4%.
Guo Junming etc. [Guo Junming etc., functional material, 2006,37:485-488.] with lithium nitrate and manganese nitrate (or with Lithium acetate and manganese acetate) it is raw material, make fuel with carbamide, use liquid-phase combustion legal system to obtain Li4Mn5O12.They find, acetate The Li of system synthesis4Mn5O12The height that synthesizes compared with nitrate system of thing phase purity.Kim etc. [Kim H. U., et al., Phys. Scr, 2010,139:1-6.] find, with by liquid phase synthesis approach in the samples of 400 DEG C of sintering with trace Mn2O3.Under 1C multiplying power electric current, the discharge capacity of sample the 1st circulation is 44.2mAh/g.Zhao etc. [Zhao Y., et al., Electrochem. Solid-State Lett., 2010,14:1509 1513.] use the synthesis of water-in-oil microemulsion method Nano spinel Li4Mn5O12。
Spinel lithium-rich Li prepared due to said method4Mn5O12The structural stability of charge and discharge process is the highest, exists low The problems such as temperature discharge performance, high temperature cyclic performance and heavy-current discharge performance are poor.Used Surface coating, add high polymer, The method of Doped anions or cation is modified.
In order to improve Li4Mn5O12Cycle performance, Liu Cong [Liu Cong, the synthesis of lithium ion battery mangaic acid lithium cathode material and Performance, South China Normal University's academic dissertation, 2009.] predecessor of polyvinylpyrrolidonesolution solution with 450 DEG C of preparations is mixed, Respectively through hydro-thermal K cryogenic treatment, application of vacuum, it is dried and oxygen atmosphere process at 100 DEG C, prepares Li4Mn5O12.Research table Bright, under 0.5C multiplying power electric current, sample is respectively 137mAh/g and 126mAh/ in the discharge capacity of the 1st circulation and the 50th circulation g。
In order to improve spinelle Li further4Mn5O12Performance, used cation and anion doped method to improve sample The performance of product.Such as, Zhang etc. [Zhang D. B., et al., J. Power Sources, 1998,76:81- 90.] with CrO2.65、Li(OH)·H2O and MnO2For raw material, respectively at 300 DEG C and 450 DEG C sintering in oxygen atmosphere, it is prepared for Li4CryMn5-yO12(y=0,0.3,0.9,1.5,2.1).Research shows, at 0.25mA/cm2Under electric current, Li4Cr1.5Mn3.5O12Sample Product are respectively 170mAh/g and 152Ah/g in the discharge capacity of the 1st circulation and the 100th circulation.[the Robertson such as Robertson A. D., et al., J. Power Sources, 2001,97-97:332-335.] at Mn (CH3COO)2·4H2O and Co (CH3COO)2·4H2O mixed solution is initially charged Li2CO3, prepare precursor, after drying respectively at 250 DEG C and 430-440 DEG C of burning Knot, prepares Li4-xMn5-2xCo3xO12Sample.This sample the 1st circulation and the 50th circulation discharge capacity be respectively 175mAh/g and 120mAh/g.With Li4Mn5O12Compare, during charge and discharge cycles, Li4-xMn5-2xCo3xO12Structure more stable.Wherein, Li3.75Mn4.5Co0.075O12Discharge capacity in the 1st circulation is 150mAh/g, and the capacity attenuation rate of 50 circulations is close to 0%.Choi etc. [Choi W., et al., Solid State Ionics, 2007,178:1541-1545.] is by LiOH, LiF and Mn (OH)2Mixing, prepares Li respectively at 500 DEG C and 600 DEG C of double sinterings in air atmosphere4Mn5O12−ηFη(0≤η≤0.2).Its In, under 0.2C multiplying power electric current, the Li of 500 DEG C of preparations4Mn5O11.85F0.1Discharge capacity in the 1st circulation is 158mAh/g.? At 25 DEG C and 60 DEG C after discharge and recharge 50 circulation, the capacity attenuation rate of this sample is respectively 2.9% and 3.9%, illustrates at high temperature and low Initial discharge capacity and the cycle performance of the lower fluorine doped sample of temperature are improved.In recent years, Tong Qingsong seminar is at doping rich lithium point Spar Li4Mn5O12Series of studies work has been carried out in field, uses slurry mixing, is dried, prepares in conjunction with double sintering technical process Mix nickel richness lithium-spinel Li4Mn5O12(patent of invention 201310618022X), mix the rich lithium-spinel of tetravalence rare earth ion Li4Mn5O12(patent of invention 201310624811.4), mix gadolinium richness lithium-spinel Li4Mn5O12(patent of invention 2013106246161.1), mix yttrium richness lithium-spinel Li4Mn5O12(patent of invention 201310624942.2), to mix zirconium richness lithium point brilliant Stone Li4Mn5O12(patent of invention 201310624867.X), mix the rich lithium-spinel Li of monovalent ion4Mn5O12(patent of invention 201310617973.5), mix the rich lithium-spinel Li of bivalent cation4Mn5O12(patent of invention 201310618294.X), mix The rich lithium-spinel Li of titanic ion4Mn5O12(patent of invention 2013106246195), mix the rich lithium-spinel of vanadium Li4Mn5O12(patent of invention 201310617989.6), mix the rich lithium-spinel Li of stannum4Mn5O12(patent of invention 201310618248.X) etc. series of patents.These patented methods significantly improve the heavy-current discharge of rich lithium-spinel LiMn2O4 The voltage platform that performance or the cycle performance of sample or sample are discharged, improves the chemical property of sample in different aspects.
Although above-mentioned preparation method can improve the chemical property of sample, but, the spinelle Li of preparation at present4Mn5O12 When discharge and recharge, the stability of structure is the most bad, has that discharge performance under the conditions of low temperature and heavy-current discharge is poor, high temperature circulation The problems such as performance substantially decay.To this end, the present invention uses the method at spinel lithium-rich lithium manganate particle Surface coating insoluble matter, Stop contacting of electrolyte and spinel lithium-rich LiMn2O4 sample particle to a certain extent, improve sample and at high temperature and deposit bar Charge-discharge performance under part.Document has had the method that cladding improves battery material performance.But, as a kind of voltage platform Being positioned at the lithium ion battery material in 3V district, lithium ion embeds different with the passage deviate from the structure of lithium ion battery material. Knowable to industry general knowledge: the performance of anode material for lithium-ion batteries is determined by its structure, the process conditions that form and prepare.Lithium Ion battery is dependent on lithium ion and moves work between a positive electrode and a negative electrode.In charge and discharge process, Li+Positive pole embeds And abjection.The positive electrode of different structure, lithium ion embeds different with the passage deviate from the structure, therefore, different structure Positive electrode is diverse positive electrode (even if its chemical composition, as identical in chemistry skeleton symbol), is improved by method for coating The performance tool of the lithium ion battery material in 3V district has an unexpected effect, and making originally cannot be in field of lithium ion battery application Battery material is possibly realized application.And compared with other battery material, this battery material has wide material sources, preparation temperature relatively The generally sintering temperature of lithium ion battery material is much lower, and the battery material of preparation is simple etc. for the painting blade technolgy preparing battery core Remarkable advantage.
Summary of the invention
For avoiding the deficiencies in the prior art, the present invention is by spinel lithium-rich lithium manganate particle Surface coating lanthana Thin layer, stops electrolyte and spinelle Li to a certain extent4Mn5O12Granule depositing and contact during discharge and recharge, improves sample Charge-discharge performance at high temperature and under storage condition.Be the technical scheme is that by realizing the purpose of the present invention
Li will be consisted ofxMnyOzSpinel type lithium-rich LiMn2O4 powder and covering mix according to weight ratio 1:0.001～0.12 Close, add 1 times of wet grinding media to 10 times of volumes of total solid capacity, mix 3 hours～15 hours with wet milling device wet grinding, system Obtain predecessor 1.Predecessor 1 constant pressure and dry, the method that is vacuum dried or is spray-dried are prepared dry predecessor 2.By front Driving thing 2 to be placed in air, oxygen-enriched air or pure oxygen atmosphere, the arbitrary temperature 290 DEG C～390 DEG C temperature ranges sinters 3 hours ～24 hours, naturally cool to room temperature, prepare the spinel lithium-rich LiMn2O4 of cladding lanthana.
Here x, y and z meets relationship below simultaneously: 3.8≤x≤4.1,5.0≤y≤5.2, z=(x + 4y)/2.
Described covering is lanthanum sesquioxide, lanthanoid metal powder or lanthanum hydroxide.The D50 particle diameter of covering powder is received 1 In rice～150 nanometer range.
Described wet grinding media is deionized water, distilled water, ethanol, acetone, methanol or formaldehyde.
Described constant pressure and dry is arbitrary temperature that predecessor 1 is placed in 170 DEG C～230 DEG C temperature ranges, at 1 air Pressure is dried, and prepares predecessor 2.Described vacuum drying is in arbitrary temperature of 170 DEG C～230 DEG C temperature ranges by predecessor 1 Degree, is dried under arbitrary pressure of 10Pa～10132Pa pressure range, prepares predecessor 2.Described spray drying method be by Predecessor 1, in arbitrary temperature of 170 DEG C～230 DEG C temperature ranges, with being dried that spray dryer is carried out, prepares predecessor 2.
Described oxygen-enriched air is that oxygen volume content more than 50% and is less than the air between 90%.
Described wet milling device is general milling machine, super ball mill or wet milk.
Compared with other inventive method, the cost of material of the present invention is relatively low, and raw material sources are extensive, and preparation process is simple, system Standby electrode material composition uniformly, has outstanding charge-discharge performance and storing performance, lays good base for industrialization Plinth.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of the JCPDS card of the sample prepared by the embodiment of the present invention 1 and correspondence.Fig. 2 is this The sample prepared by bright embodiment 1 discharge capacity under 280mA/g electric current and the graph of relation of period.Fig. 3 is this Sample prepared by bright embodiment 1 is the discharge curve of the 1st circulation under 280mA/g electric current.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further detailed.Embodiment is only supplementing further the present invention With explanation rather than the restriction to invention.
Embodiment 1
It is Li by chemical composition4Mn5O12Three oxidations that spinel type lithium-rich LiMn2O4 powder and granule D50 particle diameter are 20 nanometers Two lanthanums are 1:0.10 mixing according to weight ratio, add the distilled water of 10 times of volumes of total solid capacity, with super ball mill wet grinding Mix 10 hours, prepare predecessor 1.Predecessor 1 is dried at 200 DEG C and 100Pa vacuum under pressure, prepares predecessor 2.By front Drive thing 2 to be placed in the oxygen-enriched air atmosphere of oxygen volume content 62%, sinter 20 hours 300 DEG C of temperature, naturally cool to room Temperature, prepares the spinel lithium-rich LiMn2O4 of cladding lanthana.
Compared with other inventive method, the cost of material of the present invention is relatively low, and raw material sources are extensive, and preparation process is simple, system Standby electrode material composition uniformly, has outstanding charge-discharge performance and storing performance, lays good base for industrialization Plinth.
Embodiment 2
It is Li by chemical composition4.1Mn5.2O12.45Spinel type lithium-rich LiMn2O4 powder and granule D50 particle diameter be 1 nano metal Lanthanum powder is 1:0.12 mixing according to weight ratio, adds the ethanol of 9 times of volumes of total solid capacity, mixes 15 with wet milk wet grinding little Time, prepare predecessor 1.Predecessor 1 is dried at 230 DEG C and 10132Pa vacuum under pressure, prepares predecessor 2.By predecessor 2 It is placed in the oxygen-enriched air atmosphere of oxygen volume content 89%, sinters 24 hours at 330 DEG C, naturally cool to room temperature, prepare cladding The spinel lithium-rich LiMn2O4 of lanthana.
Compared with other inventive method, the cost of material of the present invention is relatively low, and raw material sources are extensive, and preparation process is simple, system Standby electrode material composition uniformly, has outstanding charge-discharge performance and storing performance, lays good base for industrialization Plinth.
Embodiment 3
It is Li by chemical composition3.8Mn5O11.9The hydrogen that spinel type lithium-rich LiMn2O4 powder and granule D50 particle diameter are 150 nanometers Lanthana is 1:0.001 mixing according to weight ratio, prepares mixture.Add the first of 1 times of volume of the cumulative volume of mixture solid Alcohol, mixes 3 hours with general milling machine wet grinding, prepares predecessor 1.Predecessor 1 is done at 170 DEG C and 10Pa vacuum under pressure Dry, prepare predecessor 2.Predecessor 2 is placed in the oxygen-enriched air atmosphere of oxygen volume content 51%, sinters 3 hours at 290 DEG C, Naturally cool to room temperature, prepare the spinel lithium-rich LiMn2O4 of cladding lanthana.
Compared with other inventive method, the cost of material of the present invention is relatively low, and raw material sources are extensive, and preparation process is simple, system Standby electrode material composition uniformly, has outstanding charge-discharge performance and storing performance, lays good base for industrialization Plinth.
Embodiment 4
It is Li by chemical composition3.8Mn5.2O12.3Spinel type lithium-rich LiMn2O4 powder and granule D50 particle diameter be 100 nanometers Lanthanum sesquioxide is 1:0.09 mixing according to weight ratio, prepares mixture.Add 5 times of volumes of the total solid capacity of mixture Distilled water, mixes 3 hours with general milling machine wet grinding, prepares predecessor 1.Predecessor 1 is done under 170 DEG C and 1 atmospheric pressure Dry, prepare predecessor 2.Predecessor 2 is placed in the oxygen-enriched air atmosphere of oxygen volume content 89%, little at 390 DEG C of sintering 24 Time, naturally cool to room temperature, prepare the spinel type lithium-rich LiMn2O4 of cladding lanthana.
Compared with other inventive method, the cost of material of the present invention is relatively low, and raw material sources are extensive, and preparation process is simple, system Standby electrode material composition uniformly, has outstanding charge-discharge performance and storing performance, lays good base for industrialization Plinth.
Embodiment 5
It is Li by chemical composition4.1Mn4.9O11.85Spinel type lithium-rich LiMn2O4 powder and granule D50 particle diameter be 150 nanometers Lanthanum hydroxide is 1:0.12 mixing according to weight ratio, adds the ethanol of 1 times of volume of total solid capacity, with super ball mill wet grinding Mix 15 hours, prepare predecessor 1.Predecessor 1 is dried under 230 DEG C and 1 atmospheric pressure, prepares predecessor 2.By predecessor 2 are placed in air atmosphere, sinter 3 hours at 290 DEG C, naturally cool to room temperature, prepare the spinel lithium-rich manganese of cladding lanthana Acid lithium.
Compared with other inventive method, the cost of material of the present invention is relatively low, and raw material sources are extensive, and preparation process is simple, system Standby electrode material composition uniformly, has outstanding charge-discharge performance and storing performance, lays good base for industrialization Plinth.
Embodiment 6
It is Li by chemical composition4.05Mn5O12.025Spinel type lithium-rich LiMn2O4 powder and granule D50 particle diameter be 50 nanometers Lanthanoid metal powder is 1:0.001 mixing according to weight ratio, prepares mixture.Add 8 times of volumes of the total solid capacity of mixture Deionized water, mixes 15 hours with wet milk wet grinding, prepares predecessor 1.By predecessor 1 at 170 DEG C, enter with spray dryer Row is dried, and prepares predecessor 2.Predecessor 2 is placed in pure oxygen atmosphere, sinters 6 hours at 380 DEG C, naturally cool to room temperature, system The spinel lithium-rich LiMn2O4 of lanthana must be coated with.
Compared with other inventive method, the cost of material of the present invention is relatively low, and raw material sources are extensive, and preparation process is simple, system Standby electrode material composition uniformly, has outstanding charge-discharge performance and storing performance, lays good base for industrialization Plinth.
Embodiment 7
It is Li by chemical composition4Mn5.1O12.2Three oxygen that spinel type lithium-rich LiMn2O4 powder and granule D50 particle diameter are 1 nanometer Changing two lanthanums according to weight ratio is 1:0.05 mixing, prepares mixture.Add the first of 9 times of volumes of the total solid capacity of mixture Aldehyde, mixes 5 hours with wet milk wet grinding, prepares predecessor 1.By predecessor 1 at 230 DEG C, it is dried with spray dryer, Prepare predecessor 2.Predecessor 2 is placed in pure oxygen atmosphere, sinters 6 hours at 310 DEG C, naturally cool to room temperature, prepare cladding The spinel type lithium-rich LiMn2O4 of lanthana.
Compared with other inventive method, the cost of material of the present invention is relatively low, and raw material sources are extensive, and preparation process is simple, system Standby electrode material composition uniformly, has outstanding charge-discharge performance and storing performance, lays good base for industrialization Plinth.

Claims (5)

1. the preparation method of the spinel lithium-rich LiMn2O4 of cladding lanthana, it is characterised in that preparation process is by following steps group Become:
Li will be consisted ofxMnyOzSpinel type lithium-rich LiMn2O4 powder and covering powder according to weight ratio 1:0.001～ 0.12 mixing, adds 1 times of wet grinding media to 10 times of volumes of total solid capacity, mixes 3 hours～15 with wet milling device wet grinding Hour, prepare predecessor 1；Predecessor 1 constant pressure and dry, the method that is vacuum dried or is spray-dried are prepared dry predecessor 2；Being placed in air, oxygen-enriched air or pure oxygen atmosphere by predecessor 2, the arbitrary temperature 290 DEG C～390 DEG C temperature ranges sinters 3 hours～24 hours, naturally cool to room temperature, prepare the spinel lithium-rich LiMn2O4 of cladding lanthana；
Here x, y and z meets relationship below simultaneously: 3.8≤x≤4.1,5.0≤y≤5.2, and z=(x+ 4y)/2；
Described covering is lanthanum sesquioxide, lanthanoid metal powder or lanthanum hydroxide；The granule D50 particle diameter of covering powder is received 1 In rice～150 nanometer range.
The preparation method of the spinel lithium-rich LiMn2O4 of cladding lanthana the most according to claim 1, it is characterised in that institute The wet grinding media stated is deionized water, distilled water, ethanol, acetone, methanol or formaldehyde.
The preparation method of the spinel lithium-rich LiMn2O4 of cladding lanthana the most according to claim 1, it is characterised in that institute The constant pressure and dry stated is arbitrary temperature that predecessor 1 is placed in 170 DEG C～230 DEG C temperature ranges, is dried at 1 atmosphere pressure, Prepare predecessor 2；Described vacuum drying is in arbitrary temperature of 170 DEG C～230 DEG C temperature ranges by predecessor 1, at 10Pa ～be dried under arbitrary pressure of 10132Pa pressure range, prepare predecessor 2；Described spray drying method is to be existed by predecessor 1 Arbitrary temperature of 170 DEG C～230 DEG C temperature ranges, with being dried that spray dryer is carried out, prepares predecessor 2.
The preparation method of the spinel lithium-rich LiMn2O4 of cladding lanthana the most according to claim 1, it is characterised in that institute The oxygen-enriched air stated is that oxygen volume content more than 50% and is less than the air between 90%.
The preparation method of the spinel lithium-rich LiMn2O4 of cladding lanthana the most according to claim 1, it is characterised in that institute The wet milling device stated is general milling machine, super ball mill or wet milk.
CN201610525411.1A 2016-07-06 2016-07-06 Preparation method of lanthanum oxide-coated spinel lithium-rich lithium manganate Pending CN105958035A (en)

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