CN105914360A - Method for preparing anode material of coated spinel lithium-rich lithium manganate - Google Patents
Method for preparing anode material of coated spinel lithium-rich lithium manganate Download PDFInfo
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a method for preparing an anode material of coated spinel lithium-rich lithium manganate. The method comprises the following steps: mixing spinel lithium-rich lithium manganate powder with alumina, aluminum hydroxide, aluminum chloride, zinc oxide, zinc hydroxide or zinc chloride powder according to a weight ratio of 1:0.001 to 0.15, and adding a wet grinding medium; preparing a precursor 2 by wet grinding and drying steps; sintering the precursor 2 at any temperature in a temperature interval of 250-360 DEG C to prepare the coated spinel lithium-rich lithium manganate. According to the invention, the costs of the raw materials are relatively low, and the prepared electrode material has excellent high current discharge performance after being stored, thereby laying a good foundation for industrialization.
Description
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 coating spinelle richness lithium LiMn2O4 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.The method that in document, the most useful cladding improves battery material performance.But, put down as a kind of voltage
Platform is positioned at the lithium ion battery material in 3V district, lithium ion embed in the structure of lithium ion battery material and the passage deviate from not
With.Knowable to industry general knowledge: the performance of anode material for lithium-ion batteries is by its structure, the process conditions that form and prepare certainly
Fixed.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+At positive pole
Middle embedding and abjection.The positive electrode of different structure, lithium ion embeds different with the passage deviate from the structure, therefore, different
The positive electrode of structure is diverse positive electrode (even if its chemical composition, as identical in chemistry skeleton symbol), by cladding side
Method is improved the performance tool of the lithium ion battery material in 3V district and is had an unexpected effect, and making originally cannot be in field of lithium ion battery
The battery material of application is possibly realized application.And compared with other battery material, this battery material has wide material sources, preparation
The sintering temperature of the more usual lithium ion battery material of temperature is much lower, and the battery material of preparation is for preparing the painting blade technolgy of battery core
Simply wait remarkable advantage.
Summary of the invention
For avoiding the deficiencies in the prior art, the present invention is by the Surface coating Al at spinel lithium-rich lithium manganate particle2O3Or
ZnO thin layer, improves sample charge-discharge performance under high temperature and storage condition.By realizing the technology that the purpose of the present invention is used
Scheme is:
Spinel lithium-rich LiMn2O4 powder is mixed according to weight ratio 1:0.001～0.15 with covering powder, adds solid total
1 times of wet grinding media to 25 times of volumes of volume, mixes 3 hours～15 hours with wet milling device wet grinding, prepares predecessor 1.Will
Predecessor 1 constant pressure and dry, the method being vacuum dried or being spray-dried prepare dry predecessor 2.Predecessor 2 is placed in sky
In gas, oxygen-enriched air or pure oxygen atmosphere, the arbitrary temperature 250 DEG C～360 DEG C temperature ranges sinters 3 hours～24 hours, from
So it is cooled to room temperature, prepares coating spinelle richness lithium LiMn2O4.
The chemical composition of described spinel lithium-rich LiMn2O4 is LixMnyOz.Here x, y and z meets with ShiShimonoseki simultaneously
It is formula: 3.8≤x≤4.3,4.8≤y≤5.3, z=(x+4y)/2.
The described powder that covering powder is aluminium oxide, aluminium hydroxide, aluminum chloride, zinc oxide, zinc hydroxide or zinc chloride
End.
Described constant pressure and dry is arbitrary temperature that predecessor 1 is placed in 140 DEG C～230 DEG C temperature ranges, at 1 air
Pressure is dried, and prepares predecessor 2.Described vacuum drying is that predecessor 1 is placed in the arbitrary of 100 DEG C～230 DEG C temperature ranges
Temperature, is dried under arbitrary pressure of 10Pa～10132Pa pressure range, prepares predecessor 2.Described spray drying
It is arbitrary temperature that predecessor 1 is placed in 130 DEG C～280 DEG C temperature ranges, is dried with spray dryer, prepares predecessor
2。
Described wet grinding media is deionized water or distilled water, or deionized water or distilled water weight content are at 1 wt %
～95 solution of ethanol, acetone, methanol or formaldehyde of wt % scope.
Described oxygen-enriched air is that oxygen volume content more than 21% and is less than the air between 100%.
Described wet milling device includes 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
The composition of standby electrode material is uniform, improves the charge-discharge performance under sample is deposited, lays a good foundation for industrialization.
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 that the sample prepared by the embodiment of the present invention 1 is bent with the relation of period at 300mA/g electric current discharge capacity
Line chart.
Fig. 3 is the discharge curve of the 1st circulation under 300mA/g electric current of the sample prepared by the embodiment of the present invention 1.
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 composition4Mn5O12Spinel lithium-rich LiMn2O4 powder and alumina powder mix according to weight ratio 1:0.075
Close, add the ethanol solution that distilled water weight content is 50 wt % of 18 times of volumes of total solid capacity, wet with super ball mill
Mill mixing 9 hours, prepares predecessor 1.Predecessor 1 is placed in 190 DEG C and 900 Pa vacuum under pressure are dried, prepare predecessor 2.
Predecessor 2 is placed in the oxygen-enriched air atmosphere of oxygen volume content 51%, sinters 8 hours at 350 DEG C, naturally cool to room temperature,
Prepare coating spinelle richness lithium LiMn2O4.
Compared with other inventive method, preparation process of the present invention is simple, and the sample of preparation has outstanding charge and discharge cycles
Performance and storing performance, lay a good foundation for industrialization.
Embodiment 2
It is Li by chemical composition4.3Mn5.3O12.75Spinel lithium-rich LiMn2O4 powder and aluminum chloride powder be 1 according to weight ratio:
0.15 mixing, adds the distilled water of 25 times of volumes of total solid capacity, mixes 15 hours with wet milk wet grinding, prepares predecessor 1.
Predecessor 1 is dried at 100 DEG C and 10Pa vacuum under pressure, prepares predecessor 2.Predecessor 2 is placed in oxygen volume content 99%
Oxygen-enriched air atmosphere in, 250 DEG C sinter 24 hours, naturally cool to room temperature, prepare coating spinelle richness lithium LiMn2O4.
Compared with other inventive method, preparation process of the present invention is simple, improves the charge-discharge performance under sample is deposited, for
Industrialization is laid a good foundation.
Embodiment 3
It is Li by chemical composition3.8Mn4.8O11.5Spinel lithium-rich LiMn2O4 powder and Zinc oxide powder be 1 according to weight ratio:
0.001 mixing, adds the deionized water of 1 times of volume of total solid capacity, mixes 3 hours with general milling machine wet grinding, before preparing
Drive thing 1.Predecessor 1 is dried at 230 DEG C and 10132Pa vacuum under pressure, prepares predecessor 2.Predecessor 2 is placed in carrier of oxygen
In the oxygen-enriched air atmosphere of long-pending content 22%, sinter 3 hours at 360 DEG C, naturally cool to room temperature, prepare coating spinelle richness lithium
LiMn2O4.
Compared with other inventive method, preparation process of the present invention is simple, improves the charge-discharge performance under sample is deposited, for
Industrialization is laid a good foundation.
Embodiment 4
It is Li by chemical composition3.8Mn5.3O12.5Spinel lithium-rich LiMn2O4 powder and aluminum chloride powder be 1 according to weight ratio:
0.15 mixing, adds the acetone soln of the deionized water weight content 95 wt % of 25 times of volumes of total solid capacity, uses super ball
Grinding machine wet grinding mixes 3 hours, prepares predecessor 1.Predecessor 1 is placed at 130 DEG C, is dried with spray dryer, preparation
Predecessor 2.Predecessor 2 is placed in the oxygen-enriched air atmosphere of oxygen volume content 99%, sinters 24 hours at 350 DEG C, the coldest
But to room temperature, coating spinelle richness lithium LiMn2O4 is prepared.
Compared with other inventive method, the preparation process of the present invention is simple, improves the charge-discharge performance under sample is deposited,
Lay a good foundation for industrialization.
Embodiment 5
It is Li by chemical composition4Mn5O12Spinel lithium-rich LiMn2O4 powder and aluminium-hydroxide powder be 1:0.1 according to weight ratio
Mixing, adds the methanol solution of the deionized water weight content 1 wt % of 5 times of volumes of total solid capacity, mixes with wet milk wet grinding
Close 8 hours, prepare predecessor 1.Predecessor 1 is placed at 280 DEG C, is dried with spray dryer, prepare predecessor 2.By forerunner
Thing 2 is placed in air atmosphere, sinters 9 hours at 360 DEG C, naturally cools to room temperature, prepares coating spinelle richness lithium LiMn2O4.
Compared with other inventive method, preparation process of the present invention is simple, improves the charge-discharge performance under sample is deposited, for
Industrialization is laid a good foundation.
Embodiment 6
It is Li by chemical composition3.95Mn5O11.975Spinel lithium-rich LiMn2O4 powder and alumina powder be 1 according to weight ratio:
0.05 mixing, adds the deionized water of 18 times of volumes of total solid capacity, mixes 15 hours with general milling machine wet grinding, before preparing
Drive thing 1.By predecessor 1 constant pressure and dry under 140 DEG C and 1 atmospheric pressure, prepare predecessor 2.Predecessor 2 is placed in pure oxygen atmosphere
In, sinter 24 hours at 280 DEG C, naturally cool to room temperature, prepare coating spinelle richness lithium LiMn2O4.
Compared with other inventive method, preparation process of the present invention is simple, improves the charge-discharge performance under sample is deposited, for
Industrialization is laid a good foundation.
Embodiment 7
It is Li by chemical composition4Mn5.1O12.2Spinel lithium-rich LiMn2O4 powder and zinc chloride powder be 1 according to weight ratio:
0.09 mixing, adds the distilled water of 2 times of volumes of total solid capacity, mixes 5 hours with super ball mill wet grinding, prepares predecessor
1.Predecessor 1 is placed in constant pressure and dry under 230 DEG C and 1 atmospheric pressure, prepares predecessor 2.Predecessor 2 is placed in oxygen volume contain
In the oxygen-enriched air atmosphere of amount 83%, sinter 3 hours at 250 DEG C, naturally cool to room temperature, prepare coating spinelle richness lithium mangaic acid
Lithium.
Compared with other inventive method, preparation process of the present invention is simple, improves the charge-discharge performance under sample is deposited, for
Industrialization is laid a good foundation.
Claims (5)
1. the preparation method of coating spinelle richness lithium manganate cathode material for lithium, it is characterised in that preparation process is by following steps group
Become: spinel lithium-rich LiMn2O4 powder is mixed according to weight ratio 1:0.001～0.15 with covering powder, add total solid
1 times of long-pending wet grinding media to 25 times of volumes, mixes 3 hours～15 hours with wet milling device wet grinding, prepares predecessor 1；By front
Drive thing 1 constant pressure and dry, be vacuum dried or spray drying prepares dry predecessor 2；Predecessor 2 is placed in air, oxygen-enriched sky
In gas or pure oxygen atmosphere, the arbitrary temperature 250 DEG C～360 DEG C temperature ranges sinters 3 hours～24 hours, naturally cools to room
Temperature, prepares coating spinelle richness lithium LiMn2O4；
The chemical composition of described spinel lithium-rich LiMn2O4 is LixMnyOz；Here x, y and z meets relationship below simultaneously:
3.8≤x≤4.3,4.8≤y≤5.3, z=(x+4y)/2:
The described powder that covering powder is aluminium oxide, aluminium hydroxide, aluminum chloride, zinc oxide, zinc hydroxide or zinc chloride.
The preparation method of coating spinelle richness lithium manganate cathode material for lithium 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 140 DEG C～230 DEG C temperature ranges, does at 1 atmosphere pressure
Dry, prepare predecessor 2；Described vacuum drying is arbitrary temperature that predecessor 1 is placed in 100 DEG C～230 DEG C temperature ranges,
It is dried under arbitrary pressure of 10Pa～10132Pa pressure range, prepares predecessor 2；Described spray drying is by front
Drive thing 1 and be placed in arbitrary temperature of 130 DEG C～280 DEG C temperature ranges, be dried with spray dryer, prepare predecessor 2.
The preparation method of coating spinelle richness lithium manganate cathode material for lithium the most according to claim 1, it is characterised in that institute
The wet grinding media stated is deionized water or distilled water, or deionized water or distilled water weight content are at 1 wt %～95 wt
The solution of the ethanol of % scope, acetone, methanol or formaldehyde.
The preparation method of coating spinelle richness lithium manganate cathode material for lithium the most according to claim 1, it is characterised in that institute
The oxygen-enriched air stated is that oxygen volume content more than 21% and is less than the air between 100%.
The preparation method of coating spinelle richness lithium manganate cathode material for lithium 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.
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| CN109817909A (en) * | 2019-01-07 | 2019-05-28 | 新乡市中天新能源科技股份有限公司 | A kind of preparation method of high temperature resistant circular form manganate cathode material for lithium |
| CN111162249A (en) * | 2018-11-07 | 2020-05-15 | 天津国安盟固利新材料科技股份有限公司 | Positive electrode material for improving first discharge capacity and preparation method thereof |
| CN114864894A (en) * | 2022-05-05 | 2022-08-05 | 重庆理英新能源科技有限公司 | High-pressure-resistant coating-layer-modified lithium-rich manganese-based positive electrode material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109148853A (en) * | 2018-08-21 | 2019-01-04 | 成都巴莫科技有限责任公司 | A kind of dual cladding richness oxidate for lithium solid-solution material and preparation method thereof |
| CN111162249A (en) * | 2018-11-07 | 2020-05-15 | 天津国安盟固利新材料科技股份有限公司 | Positive electrode material for improving first discharge capacity and preparation method thereof |
| CN109817909A (en) * | 2019-01-07 | 2019-05-28 | 新乡市中天新能源科技股份有限公司 | A kind of preparation method of high temperature resistant circular form manganate cathode material for lithium |
| CN114864894A (en) * | 2022-05-05 | 2022-08-05 | 重庆理英新能源科技有限公司 | High-pressure-resistant coating-layer-modified lithium-rich manganese-based positive electrode material and preparation method and application thereof |
| CN114864894B (en) * | 2022-05-05 | 2023-08-08 | 重庆理英新能源科技有限公司 | High-pressure-resistant coating modified lithium-rich manganese-based positive electrode material and preparation method and application thereof |
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