CN106129355A - The preparation method of the spinel lithium-rich LiMn2O4 of the compound of cladding niobium - Google Patents
The preparation method of the spinel lithium-rich LiMn2O4 of the compound of cladding niobium Download PDFInfo
- Publication number
- CN106129355A CN106129355A CN201610526423.6A CN201610526423A CN106129355A CN 106129355 A CN106129355 A CN 106129355A CN 201610526423 A CN201610526423 A CN 201610526423A CN 106129355 A CN106129355 A CN 106129355A
- Authority
- CN
- China
- Prior art keywords
- niobium
- predecessor
- lithium
- preparation
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to be coated with the preparation method of the spinel lithium-rich lithium manganate cathode material of the compound of niobium, it is characterised in that Li will be consisted ofxMnyOzSpinel type lithium-rich LiMn2O4 powder mix with niobium pentaoxide, niobium phosphate or sulphuric acid niobium.The predecessor 2 being dried by wet grinding, drying and other steps preparation.Being placed in air or pure oxygen atmosphere by predecessor 2, sintering prepares the spinel lithium-rich LiMn2O4 of the compound of cladding niobium.The cost of material of the present invention is relatively low, and the sample capacity of preparation is high, improves the charge-discharge performance under sample storage condition, lays a good foundation for industrialization.
Description
Technical field
The invention belongs to technical field prepared by battery electrode material, be specifically related to a kind of for lithium battery, lithium-ion electric
Pond, polymer battery and ultracapacitor, the preparation method of the spinel lithium-rich LiMn2O4 of the compound of cladding niobium.
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 compound at spinel lithium-rich lithium manganate particle Surface coating niobium
Method, stops contacting of electrolyte and spinel lithium-rich LiMn2O4 sample particle to a certain extent, improve sample at high temperature and
Charge-discharge performance under storage condition.The method that in document, the most useful cladding improves battery material performance.But, as one
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 deviate from logical
Road is different.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
Determine.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+Just
Embed in extremely and abjection.The positive electrode of different structure, lithium ion embeds different with the passage deviate from the structure, therefore, no
Isostructural positive electrode is diverse positive electrode (even if its chemical composition, as identical in chemistry skeleton symbol), by cladding
Method is improved the performance tool of the lithium ion battery material in 3V district and is had an unexpected effect, and makes originally to lead at lithium ion battery
The battery material of territory application is possibly realized application.And compared with other battery material, this battery material has wide material sources, system
The sintering temperature of the standby more usual lithium ion battery material of temperature is much lower, and the battery material of preparation is for preparing the smear work of battery core
Skill simply waits remarkable advantage.
Summary of the invention
For avoiding the deficiencies in the prior art, the present invention is by the change of the Surface coating niobium at spinel lithium-rich lithium manganate particle
Compound thin layer, stops electrolyte and spinelle Li to a certain extent4Mn5O12Granule depositing and contact during discharge and recharge, improves
Sample charge-discharge performance under high temperature and 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 1:0.001~0.090
Close, add 1 times of wet grinding media to 20 times of volumes of total solid capacity, mix 3 hours~10 hours with wet milling device wet grinding, system
Obtain predecessor 1.Predecessor 1 method of constant pressure and dry or spray drying is prepared dry predecessor 2.Predecessor 2 is placed in
In air or pure oxygen atmosphere, the arbitrary temperature 260 DEG C~360 DEG C temperature ranges sinters 3 hours~16 hours, naturally cools to
Room temperature, prepares the spinel lithium-rich LiMn2O4 of the compound of cladding niobium.
Here x, y and z meets relationship below simultaneously: 3.9≤x≤4.1,4.8≤y≤5.0, z=(x
+ 4y)/2.
Described covering is niobium pentaoxide, niobium phosphate or sulphuric acid niobium.
Described wet grinding media is deionized water, distilled water, ethanol, acetone, methanol or formaldehyde.
The method of described constant pressure and dry is arbitrary temperature that predecessor 1 is placed in 140 DEG C~280 DEG C temperature ranges, 1
It is dried under individual atmospheric pressure, prepares predecessor 2.The method of described spray drying is that predecessor 1 is placed in 140 DEG C~280 DEG C of temperature
Arbitrary temperature that degree is interval, with being dried that spray dryer is carried out, prepares predecessor 2.
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
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 260mA/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 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 composition4Mn5O12Spinel type lithium-rich LiMn2O4 powder and niobium pentaoxide be 1 according to weight ratio:
0.050 mixing, adds the distilled water of 10 times of volumes of total solid capacity, mixes 10 hours with super ball mill wet grinding, before preparing
Drive thing 1.Predecessor 1 is dried under 230 DEG C and 1 atmospheric pressure, prepares predecessor 2.Predecessor 2 is placed in air atmosphere,
Sinter 10 hours at 300 DEG C, naturally cool to room temperature, prepare the spinel lithium-rich LiMn2O4 of the compound of cladding niobium.
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 composition4.1Mn5.0O12.05Spinel type lithium-rich LiMn2O4 powder and niobium phosphate be 1 according to weight ratio:
0.001 mixing, adds the deionized water of 20 times of volumes of total solid capacity, mixes 5 hours with wet milk wet grinding, prepares predecessor
1.Predecessor 1 is dried under 280 DEG C and 1 atmospheric pressure, prepares predecessor 2.Predecessor 2 is placed in air atmosphere, 360
DEG C sintering 16 hours, naturally cools to room temperature, prepares the spinel lithium-rich LiMn2O4 of compound of cladding niobium.
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 composition3.9Mn4.9O11.75Spinel type lithium-rich LiMn2O4 powder and niobium pentaoxide according to weight ratio 1:
0.090 mixing, adds the ethanol of 1 times of volume of total solid capacity, mixes 3 hours with general milling machine wet grinding, prepares predecessor
1.Predecessor 1 is dried under 140 DEG C and 1 atmospheric pressure, prepares predecessor 2.Predecessor 2 is placed in air atmosphere, 260
DEG C sintering 3 hours, naturally cools to room temperature, prepares the spinel lithium-rich LiMn2O4 of compound of cladding niobium.
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 composition3.9Mn5.0O11.95Spinel type lithium-rich LiMn2O4 powder and niobium phosphate according to weight ratio 1:
0.005 mixing, adds the ethanol of 5 times of volumes of total solid capacity, mixes 3 hours with general milling machine wet grinding, prepares predecessor
1.Predecessor 1 is dried under 150 DEG C and 1 atmospheric pressure, prepares predecessor 2.Predecessor 2 is placed in air atmosphere, 320
DEG C sintering 16 hours, naturally cools to room temperature, prepares the spinel type lithium-rich LiMn2O4 of compound of cladding niobium.
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 sulphuric acid niobium according to weight ratio 1:
0.070 mixing, adds the acetone of 1 times of volume of total solid capacity, mixes 3 hours with super ball mill wet grinding, prepares predecessor
1.By predecessor 1 at 280 DEG C, it is dried with spray dryer, prepares predecessor 2.Predecessor 2 is placed in pure oxygen atmosphere
In, sinter 12 hours at 260 DEG C, naturally cool to room temperature, prepare the spinel lithium-rich LiMn2O4 of the compound of cladding niobium.
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 composition4Mn5O12Spinel type lithium-rich LiMn2O4 powder and niobium pentaoxide according to weight ratio 1:0.009
Mixing, adds the acetone of 20 times of volumes of total solid capacity, mixes 10 hours with wet milk wet grinding, prepares predecessor 1.By forerunner
Thing 1, at 140 DEG C, is dried with spray dryer, prepares predecessor 2.Predecessor 2 is placed in pure oxygen atmosphere, at 350 DEG C of sintering
16 hours, naturally cool to room temperature, prepare the spinel lithium-rich LiMn2O4 of the compound of cladding niobium.
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 composition3.9Mn4.8O11.55Spinel type lithium-rich LiMn2O4 powder and niobium phosphate according to weight ratio 1:
0.050 mixing, adds the formaldehyde of 20 times of volumes of total solid capacity, mixes 3 hours with wet milk wet grinding, prepares predecessor 1.Will
Predecessor 1, at 260 DEG C, is dried with spray dryer, prepares predecessor 2.Predecessor 2 is placed in pure oxygen atmosphere,
360 DEG C sinter 16 hours, naturally cool to room temperature, prepare the spinel type lithium-rich LiMn2O4 of the compound of cladding niobium.
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 (4)
1. the preparation method of the spinel lithium-rich LiMn2O4 of the compound of cladding niobium, it is characterised in that preparation process is by following steps
Composition:
Li will be consisted ofxMnyOzSpinel type lithium-rich LiMn2O4 powder and covering mix according to weight ratio 1:0.001~0.090
Close, add 1 times of wet grinding media to 20 times of volumes of total solid capacity, mix 3 hours~10 hours with wet milling device wet grinding, system
Obtain predecessor 1.Predecessor 1 method of constant pressure and dry or spray drying is prepared dry predecessor 2.Predecessor 2 is placed in
In air or pure oxygen atmosphere, the arbitrary temperature 260 DEG C~360 DEG C temperature ranges sinters 3 hours~16 hours, naturally cools to
Room temperature, prepares the spinel lithium-rich LiMn2O4 of the compound of cladding niobium;
Here x, y and z meets relationship below simultaneously: 3.9≤x≤4.1,4.8≤y≤5.0, and z=(x+
4y)/2;
Described covering is niobium pentaoxide, niobium phosphate or sulphuric acid niobium.
The preparation method of the spinel lithium-rich LiMn2O4 of the compound of cladding niobium the most according to claim 1, its feature exists
It is deionized water, distilled water, ethanol, acetone, methanol or formaldehyde in described wet grinding media.
The preparation method of the spinel lithium-rich LiMn2O4 of the compound of cladding niobium the most according to claim 1, its feature exists
Method in described constant pressure and dry is arbitrary temperature that predecessor 1 is placed in 140 DEG C~280 DEG C temperature ranges, at 1 air
Pressure is dried, and prepares predecessor 2;The method of described spray drying is that predecessor 1 is placed in 140 DEG C~280 DEG C of temperature ranges
Arbitrary temperature, with spray dryer carry out be dried, prepare predecessor 2.
The preparation method of the spinel lithium-rich LiMn2O4 of the compound of cladding niobium the most according to claim 1, its feature exists
General milling machine, super ball mill or wet milk is included in described wet milling device.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610526423.6A CN106129355A (en) | 2016-07-06 | 2016-07-06 | The preparation method of the spinel lithium-rich LiMn2O4 of the compound of cladding niobium |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610526423.6A CN106129355A (en) | 2016-07-06 | 2016-07-06 | The preparation method of the spinel lithium-rich LiMn2O4 of the compound of cladding niobium |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106129355A true CN106129355A (en) | 2016-11-16 |
Family
ID=57282558
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610526423.6A Pending CN106129355A (en) | 2016-07-06 | 2016-07-06 | The preparation method of the spinel lithium-rich LiMn2O4 of the compound of cladding niobium |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106129355A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108199024A (en) * | 2017-12-30 | 2018-06-22 | 国联汽车动力电池研究院有限责任公司 | A kind of rich lithium material of surface recombination cladding and preparation method thereof |
CN111217395A (en) * | 2020-03-16 | 2020-06-02 | 陕西海恩新材料有限责任公司 | High-energy-density lithium manganate cathode material and preparation method thereof |
CN112510195A (en) * | 2020-05-25 | 2021-03-16 | 广西富丰矿业有限公司 | Niobium-doped high-compaction high-capacity lithium manganate and preparation method thereof |
CN113851633A (en) * | 2021-11-29 | 2021-12-28 | 中南大学 | Niobium-doped high-nickel ternary cathode material coated with niobium phosphate and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102244231A (en) * | 2010-05-14 | 2011-11-16 | 中国科学院物理研究所 | Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery |
CN103107337A (en) * | 2012-04-01 | 2013-05-15 | 湖南大学 | Method for improving cycling stability of lithium ion battery anode material |
CN103441252A (en) * | 2013-08-12 | 2013-12-11 | 天津巴莫科技股份有限公司 | Method for preparing lithium-enriched manganese-based anode material of nano-oxide-coated lithium ion battery |
-
2016
- 2016-07-06 CN CN201610526423.6A patent/CN106129355A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102244231A (en) * | 2010-05-14 | 2011-11-16 | 中国科学院物理研究所 | Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery |
CN103107337A (en) * | 2012-04-01 | 2013-05-15 | 湖南大学 | Method for improving cycling stability of lithium ion battery anode material |
CN103441252A (en) * | 2013-08-12 | 2013-12-11 | 天津巴莫科技股份有限公司 | Method for preparing lithium-enriched manganese-based anode material of nano-oxide-coated lithium ion battery |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108199024A (en) * | 2017-12-30 | 2018-06-22 | 国联汽车动力电池研究院有限责任公司 | A kind of rich lithium material of surface recombination cladding and preparation method thereof |
CN108199024B (en) * | 2017-12-30 | 2021-02-09 | 国联汽车动力电池研究院有限责任公司 | Surface composite coated lithium-rich material and preparation method thereof |
CN111217395A (en) * | 2020-03-16 | 2020-06-02 | 陕西海恩新材料有限责任公司 | High-energy-density lithium manganate cathode material and preparation method thereof |
CN112510195A (en) * | 2020-05-25 | 2021-03-16 | 广西富丰矿业有限公司 | Niobium-doped high-compaction high-capacity lithium manganate and preparation method thereof |
CN113851633A (en) * | 2021-11-29 | 2021-12-28 | 中南大学 | Niobium-doped high-nickel ternary cathode material coated with niobium phosphate and preparation method thereof |
CN113851633B (en) * | 2021-11-29 | 2022-04-08 | 中南大学 | Niobium-doped high-nickel ternary cathode material coated with niobium phosphate and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102201573A (en) | Rich-lithium positive electrode material of lithium ion battery having coreshell structure and preparation method of rich-lithium positive electrode material | |
CN105470455A (en) | Modified lithium ion battery positive electrode material and preparation method therefor | |
CN103606669B (en) | Mix the preparation method of the spinel lithium-rich lithium manganate cathode material of trivalent scandium or chromium | |
CN109301207A (en) | A kind of surface layer doping Ce3+And surface layer coats CeO2NCM tertiary cathode material and preparation method thereof | |
CN108172820A (en) | Adulterate Y in a kind of surface layer3+NCM tertiary cathode materials preparation method | |
CN106129355A (en) | The preparation method of the spinel lithium-rich LiMn2O4 of the compound of cladding niobium | |
CN105914360A (en) | Method for preparing anode material of coated spinel lithium-rich lithium manganate | |
CN105932274A (en) | Preparation method of titanium-dioxide-coated spinel lithium-rich lithium manganite positive electrode material | |
CN108767254A (en) | A kind of surface texture and chemical composition synchronization modulation method of stratiform lithium-rich anode material | |
CN103594706B (en) | Mix the preparation method of yttrium spinel lithium-rich lithium manganate cathode material | |
CN103594703B (en) | Mix the preparation method of the spinel lithium-rich lithium manganate cathode material of bivalent cation | |
CN103594704B (en) | The preparation method of the spinel lithium-rich lithium manganate cathode material of doping titanic ion | |
CN105932264A (en) | Preparation method of lithium-rich spinel lithium manganite compound | |
CN103594700B (en) | Mix the preparation method of the rich lithium manganate cathode material for lithium of vanadic spinel | |
CN103594701B (en) | Mix the preparation method of nickel spinel type lithium-rich lithium manganate cathode material | |
CN103594702B (en) | The standby method of mixing the spinel lithium-rich lithium manganate cathode material of tin of double sintering legal system | |
CN103746105B (en) | The method of spinel type lithium-rich lithium manganate cathode material is prepared by doping molybdenum ion | |
CN105914361A (en) | Method for preparing anode material of spinel lithium-rich lithium manganate containing magnesium oxide | |
CN105958034A (en) | Method for preparing silicon oxide coated spinel lithium-rich lithium manganate material | |
CN105591098A (en) | Li-rich positive electrode material with La doping and lithium amount change at same time and preparing method thereof | |
CN103579611B (en) | Mix the preparation method of boron spinel lithium-rich lithium manganate cathode material | |
CN103594705B (en) | The preparation method of the spinel lithium-rich lithium manganate cathode material of doping tetravalence rare earth ion | |
CN103606668B (en) | The preparation method of the spinel lithium-rich lithium manganate cathode material of doping monovalent ion | |
CN103579613B (en) | Method for preparing spinel-doped lithium-enriched lithium manganate anode material through doping zirconium | |
CN105958035A (en) | Preparation method of lanthanum oxide-coated spinel lithium-rich lithium manganate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161116 |