CN103579613B - Method for preparing spinel-doped lithium-enriched lithium manganate anode material through doping zirconium - Google Patents
Method for preparing spinel-doped lithium-enriched lithium manganate anode material through doping zirconium 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
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- 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
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Abstract
The invention relates to a method for preparing a spinel-doped lithium-enriched lithium manganate anode material through doping zirconium. The method is characterized by respectively weighing compounds of lithium, manganese and zirconium according to the fact that the mol ratio of lithium ions (x) to manganese ions (y) to zirconium ions (z) is (0.95-1.06):(1.05-1.20):(0.05-0.20); y+z is greater than or equals to 1.20 and is less than or equals to 1.25. The compounds of the lithium, the manganese and the zirconium are mixed and added with wet milling mediums to prepare a precursor 1; the precursor 1 is dried to prepare a precursor 2; the LixMnyZrzO12 spinel-doped lithium-enriched lithium manganate anode material is prepared by the precursor 2 through the two-stage sintering method. Zirconium-doped samples prepared by the invention are high in structure stability, so that the lithium ions are conveniently embedded in and released out when charging and discharging, and excellent foundation is laid for the industrialization.
Description
Technical field
The invention belongs to the technical field of battery electrode material preparation is and in particular to one kind can be used for lithium battery, lithium ion
The preparation method of the rich lithium-spinel manganate cathode material for lithium 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 low
Advantage, the performance of positive electrode plays a part decision to the performance of lithium ion battery.
It is low that manganese-based anode material has a price, the advantages of green non-pollution, is the research emphasis of lithium ion battery.In 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 in discharge and recharge, studies seldom at present.Spinelle limn2o4Can be in 4v and 3v two
Voltage range plays a role.For 4v area, and deviate from the embedded of the tetrahedron 8a position of spinel structure with lithium ion
Relevant；For 3v area, relevant in the embedded of the octahedra 16c position of spinel structure and abjection with lithium ion.Lithium ion
The significant change of sample structure will not be caused in the embedded and abjection of the tetrahedral site of spinel structure.However, working as discharge and recharge
When depth is excessive, due to there is the john-teller distortion effect of lithium ion, embed in octahedron and abjection lithium ion can be led
Cause sample structure by cube becoming four directions, discharge capacity rapid decay.Therefore, suppress spinelle limn2o4John-teller
Distortion is the key improving its charge-discharge performance.Additionally, limn2o4Middle manganese can be dissolved in electrolyte, at higher voltages discharge and recharge
When electrolyte decomposition be likely to affect electrode material cycle performance.
In li4mn5o12Charge and discharge process in, the deintercalation of lithium ion reaction occurs mainly in 3v area, and its theoretical discharge holds
Amount is up to 163mah/g.With spinelle limn2o4The 148mah/g of theoretical capacity compares and significantly improves, and has that to become 3v area outstanding just
The probability of pole material.In this material charge and discharge process, structure cell expansion rate is less, has the advantages that cycle performance is outstanding.However,
li4mn5o12Heat stability bad.Li under high temperature1+ymn2-yo4(y < 0.33) is easily decomposed to limn2o4And li2mno3
[manthiram a., et al., ceram.trans, 1998,92:291-302.] is so that li4mn5o12It is difficult to use one
As method preparation.Have studied multiple synthetic methods it is intended to obtain more preferable preparation method.Including solid sintering technology,
Sol-gal process, hydro-thermal method and microwave sintering method etc..
Solid sintering technology is by the compound mixing of the compound of lithium and manganese, sintering preparation under aerobic or oxygen free condition.
Takada etc. [takada t., j. solid state chem., 1997,130:74-80.] is by lithium salts (lino3、
li2co3、li(ch3)) and manganese compound (mnco coo3、mn(no3)2、mn2o3And mno2) mixing, 500 DEG C of -800 DEG C of humidity provinces
Between be obtained 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 is first dried2O and mn (ac)2·4h2The mixed solution of o, is obtained li then at 500 DEG C of sintering
[liymn2-y]o4.Li [the li of their preparationsymn2-y]o4The discharge capacity in 3v area for the sample is 115-126mah/g.In 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 be obtained product the 1st circulation discharge capacity be 135mah/g.
Shin etc. [shin y., et al., electrochim. acta, 2003,48 (24): 3,583 3592.] thinks 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 in 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 be obtained a nanometer li4mn5o12.Tian etc. [tian y., et al., chem. commun.,
2007:2072 2074.] the nano wire li for preparing4mn5o12In putting 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 be obtained
li4mn5o12.Yang etc. [yang x., et al., j. solid state chem., 2000,10:1903-1909.]
By γ-mno2Or β-mno2Or the lino of barium manganese ore or acid birnessite and melting3Mixing, can be obtained 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, sinters in 450 DEG C in air atmosphere, then
Ball milling obtains sample in ethanol.The highest discharge capacity of the sample of their preparations 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.] exists
Lioh and mn (ch3coo)2Mixed solution in add li2o2, li is first obtainedxmnyoz·nh2O, then through filtering, washing, be dried
Li is obtained 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, li2o2Initial oxidation [mn (h2o)6]2+, then sinter through 400 DEG C,
The li of preparation4mn5o12It is 160mah/g in the discharge capacity of the 1st circulation.
In order to improve solid sintering technology process conditions, 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 in 350 DEG C and 500 DEG C of sintering respectively4mn5o12.Preparation sample the 1st circulation discharge capacity be
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.] adopt 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.] in mn (ch3coo)2·4h2It is mixed into li in o solution2co3, it is dried and obtain
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.] synthesized li at 380 DEG C4mn5o12.Xia [xia y. y., et al., j. power
Sources, 1996,63 (1): 97-102.] etc. pass through injection method, sample is obtained in 260 DEG C of direct sinterings.In c/3 electric current
Under, the discharge capacity first of this sample is 80mah/g.
Above research shows, solid sintering technology prepares li4mn5o12Need to be in pure o2Or carry out in air atmosphere.This method
Shortcoming includes the composition of synthetic product and particle size distribution difference is big, and the capacity attenuation rate of sample charge and discharge cycles is high, and high current is put
Electrical property is not good, and high temperature cyclic performance is more undesirable.
In order to improve the uniformity of sample, reduce 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 is obtained micron spinelle li in 300 DEG C and 500 DEG C sintering respectively4mn5o12.
In order to improve the uniformity of sample, reduce the granularity of sample particle, reduce sintering temperature, hydro-thermal method is also used for making
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 be obtained threadiness presoma lixmnyoz·nh2O, then with lioh solution low-temperature hydrothermal
Reaction is obtained 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 is first obtained submicron mnooh in 140 DEG C -180 DEG C temperature range hydro-thermal reactions, is blended into lioh h2O, after 500
DEG C -900 DEG C of prepared li4mn5o12.Sun Shuying etc. [Sun Shuying etc., inorganic material Leader, 2010,25 (6): 626-630.] lead to
Cross hydro-thermal reaction, by mnso4·h2O and (nh4)2s2o8Prepared nanometer β-mno2, it is mixed into lino3Reacted by low-temperature solid-phase method more afterwards
Prepared li4mn5o12.
Because microwave sintering method has the advantages of sintering velocity is fast, and sintering process is easy, 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, using microwave-solid phase double sintering method, is prepared for spinelle li at 380 DEG C3.22na0.569mn5.78o12Sample
Product or li4mn5o12Positive electrode.Research shows, in 4.5-2.5v voltage range, the li of preparation3.22na0.569mn5.78o12Sample
It is 132mah/g in the discharge capacity of the 1st circulation, 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, li is obtained using liquid-phase combustion legal system4mn5o12.They find, acetate
The li of system synthesis4mn5o12The height that synthesizes compared with nitric acid salt system of thing phase purity.Kim etc. [kim h. u., et al.,
Phys. scr, 2010,139:1-6.] find, micro with being carried in 400 DEG C of samples sintering by liquid phase synthesis approach
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.] using the synthesis of water-in-oil microemulsion method
Nano spinel li4mn5o12.
Spinelle li due to said method preparation4mn5o12In charge and discharge process, structural stability is not high, there is low temperature and puts
The problems such as under electricity, high temperature circulation and high current, discharge performance is poor.Adopt Surface coating, add high polymer, Doped anions
Or the method for 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.] polyvinylpyrrolidonesolution solution is mixed with the predecessor of 450 DEG C of preparations,
Process respectively through oxygen atmosphere at hydro-thermal K cryogenic treatment, application of vacuum, drying and 100 DEG C, prepared 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, sample is improved using cation and anion doped method
The performance of product.Zhang etc. [zhang d. b., et al., j. power sources, 1998,76:81-90.] with
cro2.65、li(oh)·h2O and mno2For raw material, sinter respectively at 300 DEG C and 450 DEG C in oxygen atmosphere, be prepared for
li4crymn5-yo12(y=0,0.3,0.9,1.5,2.1).Research shows, in 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.] in mn (ch3coo)2·4h2O and co
(ch3coo)2·4h2It is initially charged li in o mixed solution2co3, prepare precursor, respectively at 250 DEG C and 430-440 DEG C burnings after being dried
Knot, prepared 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,
li3.75mn4.5co0.075o12It is 150mah/g in the discharge capacity of the 1st circulation, the capacity attenuation rates of 50 circulations are 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 preparations4mn5o11.85f0.1It is 158mah/g in the discharge capacity of the 1st circulation.?
After discharge and recharge 50 circulation at 25 DEG C and 60 DEG C, the capacity attenuation rate of this sample is respectively 2.9% and 3.9%, illustrates in high temperature and low
The initial discharge capacity of the lower fluorine doped sample of temperature and cycle performance are improved.
Although above-mentioned preparation method can improve the chemical property of sample, but, due to the spinelle of current preparation
li4mn5o12During discharge and recharge, the stability of structure is still strong, and it is poor to there is discharge performance under the conditions of low temperature and heavy-current discharge,
The problems such as cycle performance is substantially decayed at high temperature.
Known following parameter, hf 298 zr-o= 760 kj mol−1, hf 298 mn-o= 402 kj mol−1, rzr-o
=59pm (oxidation state of zr is+4, and ligancy 4), rzr-o=72pm (oxidation state of zr is+4, and ligancy 6), rmn-o=39pm (oxidation state of mn is+4 and ligancy 4), rmn-o=53pm (oxidation state of mn is+4, and ligancy 6) [
John a. dean, handbook of chemistry(15thEdition)].Knowable to above parameter, zr-o key compares mn-o
The intensity of key is much bigger, and zirconium ion is bigger than the ionic radius of manganese ion, and therefore, replacing part manganese ion with a small amount of zirconium ion will not
Big impact is produced to the structure of the doped samples of preparation, improves the stability in charge and discharge process sample structure.Due to system
In the standby ratio of ionic radii sample mixing zirconium ion in zirconium sample, the ionic radius of manganese ion is big, when being conducive to lithium ion discharge and recharge
Embed and deviate from, be conducive to rising to prepare the voltage platform of sample.
Content of the invention
For avoiding the deficiencies in the prior art, the present invention improves the stability of sample structure using the method mixing zirconium, is conducive to
The embedded and abjection of lithium ion, is conducive to rising to prepare the voltage platform of sample.For realizing the technology of purpose of the present invention employing
Scheme is:
Step 1: compound that the mol ratio according to lithium ion, manganese ion, zirconium ion weighs lithium respectively for x: y: z,
The compound of manganese, the compound of zirconium.The span of described x, y and z meet simultaneously relationship below: 1.20≤y+z≤
1.25,0.95≤x≤1.06,1.05≤y≤1.20,0.05≤z≤0.20.
Step 2: the compound mixing of the compound of the lithium that step 1 is weighed, the compound of manganese and zirconium, add total solid
1 times of long-pending wet grinding media to 12 times of volumes, is mixed 3 hours～15 hours with wet milling device wet grinding, prepared predecessor 1.Will be front
Drive the dry predecessor 2 of the method preparation of thing 1 constant pressure and dry, vacuum drying or spray drying.By predecessor 2 be placed in air,
In oxygen-enriched air or pure oxygen atmosphere, doped spinel type richness lithium manganate cathode material for lithium is prepared using double sintering method.
Described double sintering method is carried out as follows: the predecessor 2 being dried is placed in air, oxygen-enriched air or pure oxygen atmosphere
In, sinter 3 hours～15 hours in the arbitrary temperature of 150 DEG C～300 DEG C of temperature ranges, then according to 1 DEG C/min～30 DEG C/
The firing rate of minute is heated to arbitrary temperature of 400 DEG C～600 DEG C of temperature ranges by previous sintering temperature, and keeping temperature sinters
3 hours～24 hours, prepare doped spinel type richness lithium manganate cathode material for lithium.
The compound of described lithium is lithium carbonate, Lithium hydrate, lithium acetate, lithium nitrate, lithium chloride or Lithium Citrate de.
The compound of described zirconium is zirconium oxide, zirconium carbonate, zirconium hydroxide, acetic acid zirconium, zirconium nitrate or zirconium chloride.
The compound of described manganese is manganese carbonate, basic carbonate manganese, manganous hydroxide, manganese acetate, manganese nitrate, manganese chloride or lemon
Lemon acid manganese.
Described constant pressure and dry is arbitrary temperature that predecessor 1 is placed in 120 DEG C～280 DEG C of temperature ranges, and dried
Journey is carried out at 1 atmosphere pressure, prepared predecessor 2.Described vacuum drying is that predecessor 1 is placed in 80 DEG C～280 DEG C temperature
Interval arbitrary temperature, is dried under arbitrary pressure of 10pa～10132pa pressure range, prepares predecessor 2.Described
Spray drying be arbitrary temperature that predecessor 1 is placed in 120 DEG C～280 DEG C of temperature ranges, done using spray dryer
Dry, prepare predecessor 2.
Described wet grinding media is deionized water, distilled water, ethanol, acetone, methanol or formaldehyde.
Described oxygen-enriched air is that oxygen volume content is 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 methods, the cost of material of the present invention is relatively low, and raw material sources extensively mix zirconium in charge and discharge process
The structural stability of sample is high, is conducive to embedded during lithium ion discharge and recharge and deviates from, is that industrialization is laid a good foundation.
Brief description
Fig. 1 is discharge curve (the charging and discharging currents 200ma/ of the 1st circulation of the sample prepared by the embodiment of the present invention 1
G).
Fig. 2 is the xrd diffraction pattern of sample prepared by the embodiment of the present invention 1 and corresponding jcpds card.
Specific embodiment
With reference to embodiment, the present invention is further detailed.Embodiment is only supplementing further to the present invention
And explanation, rather than the restriction to invention.
Embodiment 1
Mol ratio according to lithium ion, manganese ion, zirconium ion weighs Lithium hydrate, carbon respectively for 1: 1.15: 0.08
Sour manganese, acetic acid zirconium.
The Lithium hydrate weighing, manganese carbonate and acetic acid zirconium are mixed, add the distilled water of 6 times of volumes of total solid capacity,
Mixed 10 hours with super ball mill wet grinding, prepared predecessor 1.Predecessor 1 is placed under 180 DEG C and 1000 pa, vacuum is done
Dry, prepare predecessor 2.Predecessor 2 is placed in the oxygen-enriched air atmosphere of oxygen volume content 51%, little in 260 DEG C of sintering 10
When, it is heated to 500 DEG C then according to 5 DEG C/min of firing rates by 260 DEG C, keeping temperature sinters 15 hours, preparation doping point
Spar type richness lithium manganate cathode material for lithium.
Compared with other inventive methods, the cost of material of the present invention is relatively low, and raw material sources extensively, mix zirconium in charge and discharge process
The stability of sample structure is high, is conducive to embedded during lithium ion discharge and recharge and deviates from, is that industrialization is laid a good foundation.
Embodiment 2
According to lithium ion, manganese ion, zirconium ion mol ratio for 0.95: 1.05: 0.20 weigh respectively lithium carbonate,
Manganese carbonate, zirconium oxide.
The lithium carbonate weighing, manganese carbonate and zirconium oxide are mixed, add the deionized water of 1 times of volume of total solid capacity,
Mixed 3 hours with general milling machine wet grinding, prepared predecessor 1.Predecessor 1 is placed under 80 DEG C and 10pa, vacuum drying, preparation
Predecessor 2.Predecessor 2 is placed in the oxygen-enriched air atmosphere of oxygen volume content 22%, sinters 3 hours at 150 DEG C, then press
It is heated to 400 DEG C according to 1 DEG C/min of firing rate by 150 DEG C, keeping temperature sinters 3 hours, prepare doped spinel type richness lithium
Manganate cathode material for lithium.
Compared with other inventive methods, the cost of material of the present invention is relatively low, mixes the steady of zirconium sample structure in charge and discharge process
Qualitative height, is conducive to embedded during lithium ion discharge and recharge and deviates from, be that industrialization is laid a good foundation.
Embodiment 3
Mol ratio according to lithium ion, manganese ion, zirconium ion weighs citric acid respectively for 1.06: 1.15: 0.05
Lithium, manganese chloride, zirconium nitrate.
The Lithium Citrate de weighing, manganese chloride and zirconium nitrate are mixed, is added the first of 12 times of volumes of total solid capacity
Alcohol, is mixed 15 hours with wet milk wet grinding, prepared predecessor 1.Predecessor 1 is vacuum dried under 280 DEG C and 10132pa, system
Standby predecessor 2.Predecessor 2 is placed in the oxygen-enriched air atmosphere of oxygen volume content 99%, 300 DEG C sinter 15 hours, then
It is heated to 600 DEG C according to 30 DEG C/min of firing rates by 300 DEG C, keeping temperature sinters 24 hours, prepares doped spinel type
Rich lithium manganate cathode material for lithium.
Compared with other inventive methods, the cost of material of the present invention is relatively low, and raw material sources extensively, mix zirconium in charge and discharge process
The structural stability of sample is high, is conducive to embedded during lithium ion discharge and recharge and deviates from, is that industrialization is laid a good foundation.
Embodiment 4
Mol ratio according to lithium ion, manganese ion, zirconium ion weighs lithium acetate, vinegar respectively for 0.95: 1.05: 0.20
Sour manganese, zirconium carbonate.
The lithium acetate weighing, manganese acetate and zirconium carbonate are mixed, are added the acetone of 8 times of volumes of total solid capacity,
Mixed 8 hours with wet milk wet grinding, prepared predecessor 1.By predecessor 1 at 120 DEG C, before spray dryer preparation drying
Drive thing 2.Predecessor 2 is placed in pure oxygen atmosphere, 180 DEG C sinter 10 hours, then according to 1 DEG C/min of firing rate by
180 DEG C are heated to 400 DEG C, and keeping temperature sinters 8 hours, prepare doped spinel type richness lithium manganate cathode material for lithium.
Compared with other inventive methods, the cost of material of the present invention is relatively low, and raw material sources extensively, mix zirconium in charge and discharge process
The structural stability of sample is high, is conducive to embedded during lithium ion discharge and recharge and deviates from, is that industrialization is laid a good foundation.
Embodiment 5
Mol ratio according to lithium ion, manganese ion, zirconium ion weighs lithium chloride, nitric acid respectively for 1: 1.10: 0.15
Manganese, zirconium carbonate.
The lithium chloride weighing, manganese nitrate and zirconium carbonate are mixed, is added the deionization of 1 times of volume of total solid capacity
Water, is mixed 3 hours with general milling machine wet grinding, prepared predecessor 1.Predecessor 1 is placed in normal pressure under 120 DEG C and 1 atmospheric pressure
It is dried, prepare predecessor 2.Predecessor 2 is placed in air atmosphere, sinters 12 hours at 290 DEG C, then according to 5 DEG C/min
Firing rate is heated to 580 DEG C by 290 DEG C, and keeping temperature sinters 8 hours, prepares doped spinel type richness lithium lithium manganate cathode material
Material.
Compared with other inventive methods, the cost of material of the present invention is relatively low, and raw material sources extensively, mix zirconium in charge and discharge process
The structural stability of sample is high, is conducive to embedded during lithium ion discharge and recharge and deviates from, is that industrialization is laid a good foundation.
Embodiment 6
According to lithium ion, manganese ion, zirconium ion mol ratio for 0.98: 1.20: 0.05 weigh respectively lithium carbonate,
Manganese acetate, zirconium oxide.
The lithium carbonate weighing, manganese acetate and zirconium oxide are mixed, adds the ethanol of 12 times of volumes of total solid capacity, with wet
Grinding machine wet grinding mixes 15 hours, prepared predecessor 1.By predecessor 1 under 280 DEG C and 1 atmospheric pressure constant pressure and dry, prepare forerunner
Thing 2.Predecessor 2 is placed in air atmosphere, sinters 3 hours at 300 DEG C, then according to 2 DEG C/min of firing rates by 300
DEG C it is heated to 500 DEG C, keeping temperature sinters 20 hours, prepare doped spinel type richness lithium manganate cathode material for lithium.
Compared with other inventive methods, the cost of material of the present invention is relatively low, and raw material sources extensively, mix zirconium in charge and discharge process
The structural stability of sample is high, is conducive to embedded during lithium ion discharge and recharge and deviates from, is that industrialization is laid a good foundation.
Embodiment 7
Mol ratio according to lithium ion, manganese ion, zirconium ion weighs lithium acetate, vinegar respectively for 0.95: 1.05: 0.20
Sour manganese, zirconium carbonate.
The lithium acetate weighing, manganese acetate and zirconium carbonate are mixed, are added the acetone of 8 times of volumes of total solid capacity,
Mixed 8 hours with wet milk wet grinding, prepared predecessor 1.By predecessor 1 at 260 DEG C, before spray dryer preparation drying
Drive thing 2.Predecessor 2 is placed in pure oxygen atmosphere, 180 DEG C sinter 10 hours, then according to 1 DEG C/min of firing rate by
180 DEG C are heated to 400 DEG C, and keeping temperature sinters 8 hours, prepare doped spinel type richness lithium manganate cathode material for lithium.
Compared with other inventive methods, the cost of material of the present invention is relatively low, and raw material sources extensively, mix zirconium in charge and discharge process
The structural stability of sample is high, is conducive to embedded during lithium ion discharge and recharge and deviates from, is that industrialization is laid a good foundation.
Embodiment 8
Mol ratio according to lithium ion, manganese ion, zirconium ion weighs lithium chloride, nitric acid respectively for 1: 1.10: 0.15
Manganese, zirconium carbonate.
The lithium chloride weighing, manganese nitrate and zirconium carbonate are mixed, is added the deionization of 1 times of volume of total solid capacity
Water, is mixed 3 hours with general milling machine wet grinding, prepared predecessor 1.Predecessor 1 is placed at 280 DEG C, is entered with spray dryer
Row constant pressure and dry, prepares predecessor 2.Predecessor 2 is placed in air atmosphere, 290 DEG C sinter 12 hours, then according to 5 DEG C/
The firing rate of minute is heated to 580 DEG C by 290 DEG C, and keeping temperature sinters 8 hours, prepares doped spinel type richness lithium LiMn2O4
Positive electrode.
Compared with other inventive methods, the cost of material of the present invention is relatively low, and raw material sources extensively, mix zirconium in charge and discharge process
The structural stability of sample is high, is conducive to embedded during lithium ion discharge and recharge and deviates from, is that industrialization is laid a good foundation.
Claims (8)
1. prepare the method for doped spinel richness lithium manganate cathode material for lithium it is characterised in that preparation process is by following by mixing zirconium
Step forms:
Step 1: the mol ratio according to lithium ion, manganese ion, zirconium ion weighs the compound of lithium, manganese respectively for x: y: z
Compound, the compound of zirconium；The span of described x, y and z meets following calculating formula: 1.20≤y+z≤1.25 simultaneously,
0.95≤x≤1.06,1.05≤y≤1.20,0.05≤z≤0.20；
Step 2: the compound mixing of the compound of the lithium that step 1 is weighed, the compound of manganese and zirconium, add total solid capacity
1 times of wet grinding media to 12 times of volumes, is mixed 3 hours～15 hours with wet milling device wet grinding, prepared predecessor 1；By predecessor 1
With the predecessor 2 that the method preparation of constant pressure and dry, vacuum drying or spray drying is dry；Predecessor 2 is placed in air, oxygen-enriched sky
In gas or pure oxygen atmosphere, doped spinel type richness lithium manganate cathode material for lithium is prepared using double sintering method；
Described double sintering method is carried out as follows: the predecessor 2 being dried is placed in air, oxygen-enriched air or pure oxygen atmosphere,
Arbitrary temperature of 150 DEG C～300 DEG C of temperature ranges sinters 3 hours～15 hours, then according to 1 DEG C/min～30 DEG C/min
Firing rate is heated to arbitrary temperature of 400 DEG C～600 DEG C of temperature ranges by previous sintering temperature, and keeping temperature sinters 3 hours
～24 hours, prepare doped spinel type richness lithium manganate cathode material for lithium.
2. according to claim 1 by mixing the method that zirconium prepares doped spinel richness lithium manganate cathode material for lithium, it is special
The compound levying the lithium described in being is lithium carbonate, Lithium hydrate, lithium acetate, lithium nitrate, lithium chloride or Lithium Citrate de.
3. according to claim 1 by mixing the method that zirconium prepares doped spinel richness lithium manganate cathode material for lithium, it is special
The compound levying the zirconium described in being is zirconium oxide, zirconium carbonate, zirconium hydroxide, acetic acid zirconium, zirconium nitrate or zirconium chloride.
4. according to claim 1 by mixing the method that zirconium prepares doped spinel richness lithium manganate cathode material for lithium, it is special
The compound levying the manganese described in being is manganese carbonate, basic carbonate manganese, manganous hydroxide, manganese acetate, manganese nitrate, manganese chloride or Fructus Citri Limoniae
Sour manganese.
5. according to claim 1 by mixing the method that zirconium prepares doped spinel richness lithium manganate cathode material for lithium, it is special
Levy and be that described constant pressure and dry is arbitrary temperature that predecessor 1 is placed in 120 DEG C～280 DEG C of temperature ranges, and dry run
Carry out at 1 atmosphere pressure, prepared predecessor 2；Described vacuum drying is that predecessor 1 is placed in 80 DEG C～280 DEG C humidity provinces
Between arbitrary temperature, be dried under arbitrary pressure of 10pa～10132pa pressure range, prepare predecessor 2；Described
Spray drying is arbitrary temperature that predecessor 1 is placed in 120 DEG C～280 DEG C of temperature ranges, is dried using spray dryer,
Prepare predecessor 2.
6. according to claim 1 by mixing the method that zirconium prepares doped spinel richness lithium manganate cathode material for lithium, it is special
Levy and be that described wet grinding media is deionized water, distilled water, ethanol, acetone, methanol or formaldehyde.
7. according to claim 1 by mixing the method that zirconium prepares doped spinel richness lithium manganate cathode material for lithium, it is special
Levy and be that described oxygen-enriched air is that oxygen volume content is more than 21% and is less than the air between 100%.
8. according to claim 1 by mixing the method that zirconium prepares doped spinel richness lithium manganate cathode material for lithium, it is special
Levy and be that described wet milling device includes general milling machine or super ball mill.
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| 锂离子电池阴极材料LiMn2-xZrxO4的性能表征;唐致远等;《物理化学学报》;20050131;第21卷(第1期);89-92 * |
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Effective date of registration: 20180130 Address after: Economic Development Zone, Guizhou province Bijie city Nayong County 553300 Patentee after: Guizhou only high new energy technology Co., Ltd. Address before: 350108 Minhou County, Fujian Province town of Fujian Normal University, Patentee before: Fujian Normal University |