CN105914365A - Method for treating spinel lithium-rich lithium manganate doped with divalent cations by using acidic salt - Google Patents

Method for treating spinel lithium-rich lithium manganate doped with divalent cations by using acidic salt Download PDF

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CN105914365A
CN105914365A CN201610523265.9A CN201610523265A CN105914365A CN 105914365 A CN105914365 A CN 105914365A CN 201610523265 A CN201610523265 A CN 201610523265A CN 105914365 A CN105914365 A CN 105914365A
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lithium
rich
spinel lithium
acid salt
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童庆松
郭可可
黄雪红
赵南南
游帅帅
王蕾
彭建明
曾观音
王彤
李秀华
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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
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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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  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a method for treating spinel lithium-rich lithium manganate doped with divalent cations by using an acidic salt. The method comprises the following steps: mixing anode material powder of spinel lithium-rich lithium manganate doped with divalent cations (Mg2 +, Zn2 +, Ca2 +, Co2 +, Ni2 + or Cu2 +) with the acidic salt according to a molar ratio of 1:0.0010 to 0.090, adding a wet grinding medium to prepare a precursor 1, and preparing a precursor 3 by wet grinding, washing and drying steps; and sintering the precursor 3 to prepare modified spinel lithium-rich lithium manganate. According to the invention, the costs of the raw materials are relatively low, and the high current discharge performance of a sample is obviously improved, thereby laying a good foundation for industrialization.

Description

Acid salt processes the method for the spinel lithium-rich LiMn2O4 mixing bivalent cation
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 Battery, polymer battery and ultracapacitor, use acid salt to process the system of the spinel lithium-rich LiMn2O4 mixing bivalent cation Preparation Method.
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 is by divalent cation-doped spinel lithium-rich lithium manganate cathode material acid Salt treatment, improves the initial heavy-current discharge performance of sample.In document, the most useful acid salt improves the side of battery material performance Method.But, being positioned at the lithium ion battery material in 3V district as a kind of voltage platform, lithium ion is in the structure of lithium ion battery material Middle embedding is different with the passage of abjection.Knowable to industry general knowledge: the performance of anode material for lithium-ion batteries by its structure, form Determine with the process conditions of preparation.Lithium ion battery is dependent on lithium ion and moves work between a positive electrode and a negative electrode.In charge and discharge In electric process, Li+Positive pole embeds and deviates from.The positive electrode of different structure, lithium ion embeds in the structure and deviates from Passage is different, therefore, the positive electrode of different structure be diverse positive electrode (even if its chemical composition, such as chemistry letter Formula is identical), the performance tool of the lithium ion battery material being improved 3V district by acid salt is had an unexpected effect, and originally cannot make Battery material in field of lithium ion battery application is possibly realized application.And compared with other battery material, this battery material Have wide material sources, the more usual lithium ion battery material of preparation temperature sintering temperature much lower, the battery material of preparation is used for The painting blade technolgy of preparation battery core simply waits remarkable advantage.
Summary of the invention
For avoiding the deficiencies in the prior art, the present invention uses a small amount of Li on acid salt removing sample particle surface2O, improves The method mixing the spinel lithium-rich LiMn2O4 performance of bivalent cation, makes the initial heavy-current discharge performance of sample significantly change Kind.Be the technical scheme is that by realizing the purpose of the present invention
The spinel lithium-rich LiMn2O4 powder mixing bivalent cation is mixed according to mol ratio 1:0.0010～0.090 with acid salt Close, add wet grinding media according to 5 times to 50 times volumes of total solid capacity, mix 3 hours～15 hours with wet milling device wet grinding, Prepare predecessor 1.Predecessor 1 pressure filter, filter or centrifuge are removed wet grinding media, obtains predecessor 2.Use deionization Water or distilled water wash predecessor 2 are until the acidity of cleaning mixture is neutral, then prepare by constant pressure and dry or vacuum drying method The predecessor 3 being dried.Predecessor 3 is placed in air, oxygen-enriched air or pure oxygen atmosphere, 260 DEG C～390 DEG C temperature ranges Arbitrary temperature sinters 3 hours～24 hours, naturally cools to room temperature, and the spinel lithium-rich mangaic acid of bivalent cation is mixed in prepared modification Lithium.
The chemical composition of described spinel lithium-rich LiMn2O4 is Li4MnyMkO12.Described y and k meets relationship below: 4.9≤y+k≤5.2,0.002≤k≤0.10.
Described bivalent cation is Mg2+、Zn2+、Ca2+、Co2+、Ni2+Or Cu2+。
Described acid salt is ammonium hydrogen sulfate, ammonium hydrogen carbonate, ammonium citrate, monoammonium phosphate or ammonium dihydrogen phosphate.
Described wet grinding media is deionized water or distilled water, or the weight content of deionized water or distilled water is at 5 wt The solution of ethanol, acetone, methanol or the formaldehyde of %～95 wt % scopes.
Described constant pressure and dry is arbitrary temperature that predecessor 2 is placed in 160 DEG C～230 DEG C temperature ranges, at 1 air Pressure is dried, and prepares predecessor 3.Predecessor 2 is placed in 160 DEG C～230 DEG C of temperature ranges by described vacuum drying Arbitrary temperature, is dried under arbitrary pressure of 10Pa～10132Pa pressure range, prepares predecessor 3.
Described oxygen-enriched air is that oxygen volume content more than 21% and is less than the air between 100%.
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, sample The surface property of product granule is improved, and makes the initial heavy-current discharge performance of sample improve significantly, lays for industrialization Good basis.
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 Sample prepared by bright embodiment 1 is at the graph of relation of 260mA/g electric current discharge capacity Yu period.Fig. 3 is the present invention Sample prepared by embodiment 1 is the discharge curve of the 1st circulation under 260mA/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 composition4Mn4.95Mg0.05O12Spinel lithium-rich LiMn2O4 powder with ammonium dihydrogen phosphate according to mol ratio be 1:0.010 weighs, mixing, adds the distilled water of 50 times of volumes of total solid capacity, mixes 12 hours with super ball mill wet grinding, Prepare predecessor 1.Predecessor 1 is removed filtrate with filter, obtains predecessor 2.It is washed with deionized predecessor 2 until washing Wash the acidity of liquid for neutrality, then predecessor 2 is placed under 190 DEG C and 1005Pa and is vacuum dried, prepare predecessor 3.By front Drive thing 3 to be placed in the oxygen-enriched air atmosphere of oxygen volume content 57%, sinter 20 hours at 380 DEG C, naturally cool to room temperature, system Modified must mix magnesia spinel richness lithium LiMn2O4.
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, sample The surface property of product granule is improved, and makes the initial heavy-current discharge performance of sample improve significantly, lays for industrialization Good basis.
Embodiment 2
It is Li by chemical composition4Mn5.1Zn0.10O12Spinel lithium-rich LiMn2O4 powder and ammonium hydrogen sulfate according to mol ratio 1: 0.090 weighs, mixing, adds the ethanol solution of deionized water weight content 95 wt % according to 30 times of volumes of total solid capacity, Mix 15 hours with general milling machine wet grinding, prepare predecessor 1.Predecessor 1 is removed centrifugal liquid with centrifuge, obtains predecessor 2.With distilled water wash predecessor 2 until the acidity of cleaning mixture is neutral, then it is placed in predecessor 2 under 230 DEG C and 1013Pa Row is dried, and prepares predecessor 3.Predecessor 3 is placed in the oxygen-enriched air atmosphere of oxygen volume content 99%, sinters 24 at 390 DEG C Hour, naturally cooling to room temperature, gahnite richness lithium LiMn2O4 is mixed in prepared modification.
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, sample The surface property of product granule is improved, and makes the initial heavy-current discharge performance of sample improve significantly, lays for industrialization Good basis.
Embodiment 3
It is Li by chemical composition4Mn4.898Ca0.002O12Spinel lithium-rich LiMn2O4 powder with ammonium hydrogen sulfate according to mol ratio be 1:0.0050 weighs, mixing, and the acetone adding deionized water weight content 5 wt % according to 5 times of volumes of total solid capacity is molten Liquid, mixes 3 hours with super ball mill wet grinding, prepares predecessor 1.Predecessor 1 is removed filtrate with pressure filter, obtains forerunner Thing 2.It is washed with deionized predecessor 2 until the acidity of cleaning mixture is neutrality, then predecessor 2 is placed under 230 DEG C and 10Pa Vacuum drying, prepares predecessor 3.Predecessor 3 is placed in the oxygen-enriched air atmosphere of oxygen volume content 22%, at 260 DEG C of sintering 3 hours, naturally cooling to room temperature, calcium spinel lithium-rich LiMn2O4 is mixed in prepared modification.
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, sample The surface property of product granule is improved, and makes the initial heavy-current discharge performance of sample improve significantly, lays for industrialization Good basis.
Embodiment 4
It is Li by chemical composition4Mn4.8Co 0.10O12Spinel lithium-rich LiMn2O4 powder and ammonium hydrogen carbonate be 1 according to mol ratio: 0.0050 weighs, mixing, adds deionized water according to 20 times of volumes of above total solid capacity, mixes 15 with wet milk wet grinding little Time, prepare predecessor 1.Predecessor 1 is removed filtrate with filter, obtains predecessor 2.It is washed with deionized predecessor 2 straight Acidity to cleaning mixture is neutral, then predecessor 2 is placed in constant pressure and dry under 230 DEG C and 1 atmospheric pressure, prepares predecessor 3.Will Predecessor 3 is placed in the oxygen-enriched air atmosphere of oxygen volume content 33%, sinters 24 hours at 390 DEG C, naturally cools to room temperature, Prepare modified Co-doped spinel richness lithium LiMn2O4.
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, sample The surface property of product granule is improved, and makes the initial heavy-current discharge performance of sample improve significantly, lays for industrialization Good basis.
Embodiment 5
It is Li by chemical composition4Mn5.18Ni0.002O12Spinel lithium-rich LiMn2O4 powder and ammonium hydrogen carbonate be 1 according to mol ratio: 0.090 weighs, mixing, adds the methanol solution of distilled water weight content 5 wt % according to 5 times of volumes of above total solid capacity, Mix 15 hours with general milling machine wet grinding, prepare predecessor 1.Predecessor 1 is removed centrifugal liquid with centrifuge, obtains predecessor 2.With distilled water wash predecessor 2 until the acidity of cleaning mixture is neutral, then predecessor 2 is placed under 160 DEG C and 1 atmospheric pressure Constant pressure and dry, prepares predecessor 3.Predecessor 3 is placed in air atmosphere, sinters 24 hours at 260 DEG C, naturally cool to room Temperature, nickel spinel lithium-rich LiMn2O4 is mixed in prepared modification.
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, sample The surface property of product granule is improved, and makes the initial heavy-current discharge performance of sample improve significantly, lays for industrialization Good basis.
Embodiment 6
It is Li by chemical composition4Mn5.098Zn0.002O12Spinel lithium-rich LiMn2O4 powder and monoammonium phosphate according to mol ratio 1:0.0010 weighs, mixing, adds the third of deionized water weight content 80 wt % according to 5 times of volumes of above total solid capacity Ketone solution, mixes 5 hours with wet milk wet grinding, prepares predecessor 1.Predecessor 1 is removed filtrate with pressure filter, obtains predecessor 2.With distilled water wash predecessor 2 until the acidity of cleaning mixture is neutral, then predecessor 2 is placed in 180 DEG C and 1 atmospheric pressure Constant pressure and dry under power, prepares predecessor 3.Predecessor 3 is placed in pure oxygen atmosphere, sinters 20 hours at 390 DEG C, naturally cool to Room temperature, gahnite richness lithium LiMn2O4 is mixed in prepared modification.
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, sample The surface property of product granule is improved, and makes the initial heavy-current discharge performance of sample improve significantly, lays for industrialization Good basis.
Embodiment 7
It is Li by chemical composition4Mn4.892Mg0.008O12Spinel lithium-rich LiMn2O4 powder and ammonium dihydrogen phosphate according to mol ratio 1:0.0090 weighs, mixing, adds deionized water according to 60 times of volumes of above total solid capacity, mixes 3 with wet milk wet grinding Hour, prepare predecessor 1.Predecessor 1 is removed filtrate with filter, obtains predecessor 2.It is washed with deionized predecessor 2 Until the acidity of cleaning mixture is neutral, then predecessor 2 is dried at 230 DEG C and 10132Pa vacuum under pressure, prepares predecessor 3. Being placed in air atmosphere by predecessor 3, sinter 24 hours at 300 DEG C, naturally cool to room temperature, it is rich that magnesia spinel is mixed in prepared modification Lithium LiMn2O4.
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, sample The surface property of product granule is improved, and makes the initial heavy-current discharge performance of sample improve significantly, lays for industrialization Good basis.

Claims (6)

1. the method that acid salt processes the spinel lithium-rich LiMn2O4 mixing bivalent cation, it is characterised in that preparation process is by following Step forms:
The spinel lithium-rich LiMn2O4 powder mixing bivalent cation is mixed according to mol ratio 1:0.0010～0.090 with acid salt Close, add wet grinding media according to 5 times to 50 times volumes of total solid capacity, mix 3 hours～15 hours with wet milling device wet grinding, Prepare predecessor 1；Predecessor 1 pressure filter, filter or centrifuge are removed wet grinding media, obtains predecessor 2；Use deionization Water or distilled water wash predecessor 2 are until the acidity of cleaning mixture is neutral, then prepare by constant pressure and dry or vacuum drying method The predecessor 3 being dried；Predecessor 3 is placed in air, oxygen-enriched air or pure oxygen atmosphere, 260 DEG C～390 DEG C temperature ranges Arbitrary temperature sinters 3 hours～24 hours, naturally cools to room temperature, and the spinel lithium-rich mangaic acid of bivalent cation is mixed in prepared modification Lithium；
The chemical composition of described spinel lithium-rich LiMn2O4 is Li4MnyMkO12；Described y and k meets relationship below: 4.9 ≤ y+k≤5.2,0.002≤k≤0.10；
Described bivalent cation is Mg2+、Zn2+、Ca2+、Co2+、Ni2+Or Cu2+。
Acid salt the most according to claim 1 processes the method for the spinel lithium-rich LiMn2O4 mixing bivalent cation, and it is special Levy and be that described acid salt is ammonium hydrogen sulfate, ammonium hydrogen carbonate, ammonium citrate, monoammonium phosphate or ammonium dihydrogen phosphate.
Acid salt the most according to claim 1 processes the method for the spinel lithium-rich LiMn2O4 mixing bivalent cation, and it is special Levy and be that described wet grinding media is deionized water or distilled water, or the weight content of deionized water or distilled water is at 5 wt % ～95 solution of ethanol, acetone, methanol or formaldehyde of wt % scope.
Acid salt the most according to claim 1 processes the method for the spinel lithium-rich LiMn2O4 mixing bivalent cation, and it is special Levy and be that described constant pressure and dry is arbitrary temperature that predecessor 2 is placed in 160 DEG C～230 DEG C temperature ranges, at 1 atmospheric pressure Under be dried, prepare predecessor 3；Described vacuum drying is that predecessor 2 is placed in appointing of 160 DEG C～230 DEG C temperature ranges One temperature, is dried under arbitrary pressure of 10Pa～10132Pa pressure range, prepares predecessor 3.
Acid salt the most according to claim 1 processes the method for the spinel lithium-rich LiMn2O4 mixing bivalent cation, and it is special Levy and be that described oxygen-enriched air is that oxygen volume content more than 21% and is less than the air between 100%.
Acid salt the most according to claim 1 processes the method for the spinel lithium-rich LiMn2O4 mixing bivalent cation, and it is special Levy and be that described wet milling device is general milling machine, super ball mill or wet milk.
CN201610523265.9A 2016-07-06 2016-07-06 Method for treating spinel lithium-rich lithium manganate doped with divalent cations by using acidic salt Pending CN105914365A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6361755B1 (en) * 1998-03-24 2002-03-26 Board Of Regents, The University Of Texas System Low temperature synthesis of Li4Mn5O12 cathodes for lithium batteries
CN102208640A (en) * 2011-04-22 2011-10-05 王明月 Modified lithium manganese oxide electrode material for lithium ion secondary battery and synthesizing method thereof
CN102881879A (en) * 2012-10-15 2013-01-16 福建师范大学 Method for preparing lithium-rich solid solution cathode material through gas oxidation and acid solution combined treatment
CN103594703A (en) * 2013-11-28 2014-02-19 福建师范大学 Preparation method of divalent cation-doped spinel lithium-rich lithium manganate cathode material
CN103700839A (en) * 2014-01-06 2014-04-02 中信国安盟固利电源技术有限公司 Method for reducing content of residual alkaline in nickel cobalt manganese acid lithium
CN104871272A (en) * 2012-11-19 2015-08-26 弗劳恩霍弗应用技术研究院 Solid/gel electrolyte battery having a binder composed of an inorganic-organic hybrid polymer and method for the production of said battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6361755B1 (en) * 1998-03-24 2002-03-26 Board Of Regents, The University Of Texas System Low temperature synthesis of Li4Mn5O12 cathodes for lithium batteries
CN102208640A (en) * 2011-04-22 2011-10-05 王明月 Modified lithium manganese oxide electrode material for lithium ion secondary battery and synthesizing method thereof
CN102881879A (en) * 2012-10-15 2013-01-16 福建师范大学 Method for preparing lithium-rich solid solution cathode material through gas oxidation and acid solution combined treatment
CN104871272A (en) * 2012-11-19 2015-08-26 弗劳恩霍弗应用技术研究院 Solid/gel electrolyte battery having a binder composed of an inorganic-organic hybrid polymer and method for the production of said battery
CN103594703A (en) * 2013-11-28 2014-02-19 福建师范大学 Preparation method of divalent cation-doped spinel lithium-rich lithium manganate cathode material
CN103700839A (en) * 2014-01-06 2014-04-02 中信国安盟固利电源技术有限公司 Method for reducing content of residual alkaline in nickel cobalt manganese acid lithium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J.R. CROY，ET AL.: "Li2MnO3-based composite cathodes for lithium batteries: A novel synthesis approach and new structures", 《ELECTROCHEMISTRY COMMUNICATIONS》 *

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