CN103035904B - Modified lithium manganate material, and preparation method and application thereof - Google Patents
Modified lithium manganate material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a modified lithium manganate material, and a preparation method and application thereof. The modified lithium manganate material adopts a core-shell structure taking LiMn204 as a core and LiMn2-xMxO4-delta as a coating layer, wherein M is one of Al, Ti, Ce, Co and Ni, the value of x ranges from 0.05 to 0.5, and delta ranges from 0.01-0.1. The modified lithium manganate material is prepared by co-precipitation coating, hydro-thermal reaction and high-temperature heat treatment, and used as the cathode material of a lithium ion battery. The preparation process is simple and feasible, the components and the proportion of the raw materials are easy to control, the stability from batch to batch is good, the cost is low, and the synthesized lithium manganate material is high in specific capacity, high in current and excellent in cycle performance, and is expected to be applied in the field of power cells.
Description
(1) technical field:
The present invention relates to a kind of modified lithium manganate material LiMn of nucleocapsid structure
2-xm
xo
4-δ@LiMn
2o
4and preparation method thereof and as the application of anode material for lithium-ion batteries.
(2) background technology:
Since find spinel structure LiMn2O4 can as anode material for lithium-ion batteries since, learn due to its excellent electricity ization Yuan that Xing Neng ﹑ enriches and expect that the features such as the Lai good An of Yuan ﹑ full Xing Neng ﹑ environment-protecting asepsis have become that research is the most active, exploitation dynamics is maximum, one of the positive electrode of most application prospect, be subject to the favor of vast scientific research institution and commercial company.Present people tentatively realize the merchandized handling of spinel lithium manganate, are also necessarily applied in electric bicycle and electric automobile using it as the lithium-ion-power cell of positive electrode.
At present, the preparation method of LiMn2O4 mainly contains hydro thermal method, high temperature solid-state Fa ﹑ microwave He Cheng Fa ﹑ colloidal sol-Ning Jiao Fa ﹑ spray drying process etc.High temperature solid-state method technique is simple, be applicable to large-scale production, but reactant mixes usually uneven, and synthetic material particle is comparatively large, and in preparation process, easily occur impurity, these shortcomings cause material property poor, and lot stability can not be guaranteed; Microwave process for synthesizing is also a kind of Solid phase synthesis method, and it has the reaction time short (3-10min), and energy consumption is low, combined coefficient is high, the advantages such as uniform particles, but the method requires comparatively strict to process conditions and input cost is too high, is not suitable for carrying out large-scale production; The advantage of sol-gal process is that its precursor solution chemical uniformity is good, Gel heat-treatment temperature is low, powder granule particle diameter is little and narrowly distributing, powder sintering performance are good, course of reaction is easy to control, equipment is simple, but dry shrink large, suitability for industrialized production difficulty is comparatively large, synthesis cycle is long; Spray process more complicated, is unfavorable for industrialization.
The standby LiMn2O4 of Direct Hydrothermal legal system has larger capacity usually, and shows poor on cycle performance.Main cause comprises the following aspects: (1), in hydrothermal reaction process, the lithium manganate particle particle diameter of formation is less, and surface area is large; (2) the LiMn2O4 crystal face of Hydrothermal Synthesis is grown imperfect, and defect is more; (3) content that reduce active material due to the loss of manganese is understood in manganate cathode material for lithium and electrolyte contacts process; (4) manganate cathode material for lithium can cause structure dilation because of Jahn-Teller effect in charge and discharge process, affects stability.Therefore, people usually can carry out element doping or surface modification in preparation process, to keep higher volumetric properties, improve cyclical stability simultaneously.Because the capacity of LiMn2O4 itself is not high, if overall doping can cause the further decline of capacity, and simple surface modification can because adhesion is more weak or closed lithium ion diffusion admittance and affect material property.
(3) summary of the invention:
First object of the present invention is to provide a kind of modified lithium manganate material LiMn
2-xm
xo
4-δ@LiMn
2o
4, this modified lithium manganate material specific capacity is high, big current and cycle performance excellent, the change in volume that effectively can suppress again the stripping of manganese and cause because of Jahn-Teller effect.
The present invention's second object is to provide a kind of method of technique simple possible, the described modified lithium manganate material of preparation with low cost.
The present invention's the 3rd object is the positive electrode described modified lithium manganate material being used as lithium ion battery.
Below technical scheme of the present invention is illustrated.
The invention provides a kind of modified lithium manganate material (LiMn
2-xm
xo
4-δ@LiMn
2o
4), described modified lithium manganate material is with LiMn
2o
4for core, with LiMn
2-xm
xo
4-δfor the nucleocapsid structure of coating layer; Wherein M is the one in Al, Ti, Ce, Co, Ni, and the value of x is 0.05 ~ 0.5, δ is 0.01 ~ 0.1.
Further, the LiMn of core
2o
4for spinel-type cubic crystal structure.
Further, the particle diameter of described described modified lithium manganate material is at 100 ~ 500 nm.
Further, the value of preferred x is 0.2 ~ 0.5, and preferred δ is 0.02 ~ 0.06.
LiMn
2-xm
xo
4-δ@LiMn
2o
4nucleocapsid structure effectively can promote the chemical valence of active material particle surface manganese, suppress because of the change in volume that Jahn-Teller effect causes in charge and discharge process, reduce the possibility of LiMn2O4 core and electrolyte contacts, the stripping of minimizing manganese simultaneously.
Present invention also offers a kind of method preparing described modified lithium manganate material, relatively inexpensive manganese dioxide is adopted to be main manganese source, take lithium hydroxide as coprecipitator and lithium source, form mixing coating layer by the mode of manganese ion, other metal ion (M=Al, Ti, Ce, Co, Ni etc.) co-precipitation on manganese dioxide surface, then generate LiMn through hydro-thermal reaction
2-xm
xo
4-δ@LiMn
2o
4nucleocapsid structure (being called presoma), then through subsequent heat treatment, the crystal face of presoma is reached full growth, reduces crystal defect, and maintain less particle diameter.Described preparation method specifically comprises the steps:
(1) manganese ion Yuan ﹑ M metal ion source is mixed with mixed solution, then manganese dioxide is placed in mixed solution, stir, getting lithium hydroxide solution is added dropwise in mixed system, makes hydroxide coating layer (MnM) OH forming manganese ion and M metal ion on manganese dioxide surface; In the integral molar quantity of manganese ion, M metal ion and manganese dioxide for 100%, wherein manganese ion mole accounts for 15% ~ 20%, the mol ratio of manganese ion and M metal ion is 3 ~ 39, and the mole of lithium hydroxide is equal with the total mole number of manganese ion, M metal ion and manganese dioxide;
(2) reaction system of step (1) is placed in hydrothermal reaction kettle, in 150 ~ 220
oc reaction 10 ~ 20 hours, obtains presoma;
(3) presoma is placed in air atmosphere in 600 ~ 800
oc high-temperature roasting 2 ~ 5 hours, obtained described modified lithium manganate material.
Manganese ion source of the present invention is one or more the combination in manganese nitrate, manganese oxalate, manganese acetate, manganese sulfate.
M metal ion source of the present invention is one or more the combination in the nitrate of M metal ion, oxalates, chloride, acetate, sulfate.
In described step (1), the mol ratio of manganese ion and M metal ion is 3 ~ 9.
Present invention also offers the application of described modified lithium manganate material as the positive electrode of lithium ion battery.
The method that the present invention prepares lithium cell anode material lithium manganate has following outstanding feature:
(1) the modified lithium manganate material LiMn that obtains of the present invention
2-xm
xo
4-δ@LiMn
2o
4, its special nucleocapsid structure can maintain the volumetric properties of LiMn2O4, the change in volume that effectively can suppress again the stripping of manganese and cause because of Jahn-Teller effect.
(2) the present invention adopt co-precipitation coated-mode of hydro-thermal reaction-high-temperature heat treatment prepares modified lithium manganate material LiMn
2-xm
xo
4-δ@LiMn
2o
4, this technique simple possible, material composition and proportioning easily control, good stability between batch, and with low cost, and the lithium manganate material specific capacity of synthesis is high, big current and cycle performance excellent, be expected to be applied in electrokinetic cell field.
(4) accompanying drawing explanation
Fig. 1 is by the LiMn prepared by embodiment 1
2-xm
xo
4-δ@LiMn
2o
4x-ray diffraction pattern;
Fig. 2 is by the LiMn prepared by embodiment 1
2-xm
xo
4-δ@LiMn
2o
4stereoscan photograph;
Fig. 3 is by the LiMn prepared by embodiment 1
2-xm
xo
4-δ@LiMn
2o
4electron probe micro-analysis figure;
Fig. 4 is by the LiMn prepared by embodiment 1
2-xm
xo
4-δ@LiMn
2o
4for positive pole, lithium sheet is the cycle characteristics curve chart of the lithium ion battery that negative pole assembles;
Fig. 5 building-up process schematic diagram of the present invention.
(5) embodiment
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto:
Embodiment 1:
Take ANN aluminium nitrate nonahydrate powder 0.188g, be made into 20ml solution, measure 50wt.% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, in instillation aluminum nitrate solution, stir.Take 0.696g manganese dioxide, insert mixed liquor, after stirring, take 0.42g mono-hydronium(ion) lithia, be dissolved in 10ml deionized water, slowly in instillation mixed liquor, stir 30 minutes.Above-mentioned mixed liquor is placed in hydrothermal reaction kettle with 200
oc reacts 20 hours, and filtration washing drying obtains finished product presoma, through 3 hours 750
oc heat treatment obtains LiMn
1.5al
0.5o
3.95evenly coated LiMn
2o
4powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
Done X-ray diffraction analysis to the modified lithium manganate material prepared in this way, as shown in Figure 1, prepared LiMn2O4 is spinel-type cubic system pure phase structure, there is not the peak of other impurity in spectrogram.Fig. 2 is LiMn
1.5m
0.5o
4-δ@LiMn
2o
4powder amplifies the stereoscan photograph of 30000 times, and as seen from the figure, product particle size is about 400 nanometers.Fig. 3 is LiMn
1.5m
0.5o
4-δ@LiMn
2o
4electron probe micro-analysis figure, as seen from the figure, prepared material has obvious clad structure.
By active material LiMn
1.5m
0.5o
3.95@LiMn
2o
4powder, acetylene black, Kynoar, with the mass ratio of 8:1:1, take altogether 0.5g and are dissolved in 1-methyl-2 pyrrolidones, be applied on aluminium foil and make positive plate after mixing.The electrode slice of oven dry is beaten its quality of precise after sheet, as anode.Be simultaneously to electrode with lithium sheet, micropore shaped polyethylene is barrier film, 1.0mol/L LiPF
6+ DMC is electrolyte, in the System One glove box being full of argon gas, be assembled into 2032 button cells with tablet press machine.
In 3.3V ~ 4.3V voltage range, constant current charge-discharge loop test is carried out to battery.Fig. 4 is with 1C(130mAg
-1) multiplying power charging, 1C(130mAg
-1) and 10C(1300mAg
-1) the cycle performance of battery figure of multiplying power discharging, as shown in Figure 4, this material has stable cycle performance under big current, the advantage that specific capacity is high.
Embodiment 2:
Take Nickelous nitrate hexahydrate powder 0.145g, be made into 20ml solution, measure 50wt.% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, in instillation nickel nitrate solution, stir.Take 0.696g manganese dioxide, insert mixed liquor, after stirring, take 0.42g mono-hydronium(ion) lithia, be dissolved in 10ml deionized water, slowly in instillation mixed liquor, stir 30 minutes.Above-mentioned mixed liquor is placed in hydrothermal reaction kettle with 200
oc reacts 20 hours, and filtration washing drying obtains finished product presoma, through 3 hours 750
oc heat treatment obtains LiMn
1.5ni
0.5o
3.95evenly coated LiMn
2o
4powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With obtained modified lithium manganate material for positive electrode, be assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, constant current charge-discharge loop test carried out, with 1C(130mAg to battery
-1) multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) discharge capacity first of multiplying power discharging and 50 weeks capability retentions be in table 1.
Embodiment 3:
Take six nitric hydrate cerium powder 0.217g, be made into 20ml solution, measure 50wt.% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, in instillation cerous nitrate solution, stir.Take 0.696g manganese dioxide, insert mixed liquor, after stirring, take 0.42g mono-hydronium(ion) lithia, be dissolved in 10ml deionized water, slowly in instillation mixed liquor, stir 30 minutes.Above-mentioned mixed liquor is placed in hydrothermal reaction kettle with 200
oc reacts 20 hours, and filtration washing drying obtains finished product presoma, through 3 hours 750
oc heat treatment obtains LiMn
1.5ce
0.5o
3.97evenly coated LiMn
2o
4powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With obtained modified lithium manganate material for positive electrode, be assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, constant current charge-discharge loop test carried out, with 1C(130mAg to battery
-1) multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) discharge capacity first of multiplying power discharging and 50 weeks capability retentions be in table 1.
Embodiment 4:
Take cabaltous nitrate hexahydrate powder 0.146g, be made into 20ml solution, measure 50wt.% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, in instillation cobalt nitrate solution, stir.Take 0.696g manganese dioxide, insert mixed liquor, after stirring, take 0.42g mono-hydronium(ion) lithia, be dissolved in 10ml deionized water, slowly in instillation mixed liquor, stir 30 minutes.Above-mentioned mixed liquor is placed in hydrothermal reaction kettle with 200
oc reacts 20 hours, and filtration washing drying obtains finished product presoma, through 3 hours 750
oc heat treatment obtains LiMn
1.5co
0.5o
3.95evenly coated LiMn
2o
4powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With obtained modified lithium manganate material for positive electrode, be assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, constant current charge-discharge loop test carried out, with 1C(130mAg to battery
-1) multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) discharge capacity first of multiplying power discharging and 50 weeks capability retentions be in table 1.
Embodiment 5:
Take ANN aluminium nitrate nonahydrate powder 0.376g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO
3)
2) solution 2.094ml, in instillation aluminum nitrate solution, after stirring, take 0.42g mono-hydronium(ion) lithia, be dissolved in 10ml deionized water, slowly in instillation mixed liquor, stir 30 minutes.Above-mentioned mixed liquor is placed in hydrothermal reaction kettle with 200
oc reacts 20 hours, and filtration washing drying obtains finished product presoma, through 3 hours 750
oc heat treatment obtains LiMn
1.8al
0.2o
3.98powder.
With obtained LiMn
1.8al
0.2o
3.98for positive electrode, be assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, constant current charge-discharge loop test carried out, with 1C(130mAg to battery
-1) multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) discharge capacity first of multiplying power discharging and 50 weeks capability retentions be in table 1.
Embodiment 6:
Take 0.87g manganese dioxide and 0.42g mono-hydronium(ion) lithia, be dissolved in 30ml deionized water, stir 30 minutes.Above-mentioned mixed liquor is placed in hydrothermal reaction kettle with 200
oc reacts 20 hours, and filtration washing drying obtains finished product LiMn
2o
4powder.
With obtained LiMn
2o
4for positive electrode, be assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, constant current charge-discharge loop test carried out, with 1C(130mAg to battery
-1) multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) discharge capacity first of multiplying power discharging and 50 weeks capability retentions be in table 1.
Embodiment 7:
Take six nitric hydrate cerium powder 0.217g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, in instillation cerous nitrate solution, stir.Take 0.696g manganese dioxide, insert mixed liquor, after stirring, take 0.42g mono-hydronium(ion) lithia, be dissolved in 10ml deionized water, slowly in instillation mixed liquor, stir 30 minutes.Above-mentioned mixed liquor is placed in hydrothermal reaction kettle with 220
oc reacts 15 hours, and filtration washing drying obtains finished product presoma, through 3 hours 750
oc heat treatment obtains LiMn
1.5ce
0.5o
3.97evenly coated LiMn
2o
4powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With obtained LiMn
1.5ce
0.5o
3.97evenly coated LiMn
2o
4powder is positive electrode, is assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, carries out constant current charge-discharge loop test, with 1C(130mAg to battery
-1) multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) discharge capacity first of multiplying power discharging and 50 weeks capability retentions be in table 1.
Embodiment 8:
Take six nitric hydrate cerium powder 0.217g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO3) 2) solution 0.349ml, in instillation cerous nitrate solution, stir.Take 0.696g manganese dioxide, insert mixed liquor, after stirring, take 0.42g mono-hydronium(ion) lithia, be dissolved in 10ml deionized water, slowly in instillation mixed liquor, stir 30 minutes.Above-mentioned mixed liquor is placed in hydrothermal reaction kettle with 200
oc reacts 20 hours, and filtration washing drying obtains finished product presoma, through 3 hours 650
oc heat treatment obtains LiMn
1.5ce
0.5o
3.97evenly coated LiMn
2o
4powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With obtained LiMn
1.5ce
0.5o
3.97evenly coated LiMn
2o
4powder is positive electrode, is assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, carries out constant current charge-discharge loop test, with 1C(130mAg to battery
-1) multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) discharge capacity first of multiplying power discharging and 50 weeks capability retentions be in table 1.
Embodiment 9:
Take six nitric hydrate cerium powder 0.130g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO
3)
2) solution 0.396ml, in instillation cerous nitrate solution, stir.Take 0.696g manganese dioxide, insert mixed liquor, after stirring, take 0.42g mono-hydronium(ion) lithia, be dissolved in 10ml deionized water, slowly in instillation mixed liquor, stir 30 minutes.Above-mentioned mixed liquor is placed in hydrothermal reaction kettle with 200
oc reacts 20 hours, and filtration washing drying obtains finished product presoma, through 3 hours 750
oc heat treatment obtains LiMn
1.7ce
0.3o
3.96evenly coated LiMn
2o
4powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With obtained LiMn
1.7ce
0.3o
3.96evenly coated LiMn
2o
4powder is positive electrode, is assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, carries out constant current charge-discharge loop test, with 1C(130mAg to battery
-1) multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) discharge capacity first of multiplying power discharging and 50 weeks capability retentions be in table 1.
Embodiment 10:
Take ANN aluminium nitrate nonahydrate powder 0.188g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, in instillation aluminum nitrate solution, stir.Take 0.696g manganese dioxide, insert mixed liquor, after stirring, take 0.42g mono-hydronium(ion) lithia, be dissolved in 10ml deionized water, slowly in instillation mixed liquor, stir 30 minutes.Above-mentioned mixed liquor is placed in hydrothermal reaction kettle with 220
oc reacts 15 hours, and filtration washing drying obtains finished product presoma, through 3 hours 750
oc heat treatment obtains LiMn
1.5al
0.5o
3.95evenly coated LiMn
2o
4powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With obtained LiMn
1.5al
0.5o
3.95evenly coated LiMn
2o
4powder is positive electrode, is assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, carries out constant current charge-discharge loop test, with 1C(130mAg to battery
-1) multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) discharge capacity first of multiplying power discharging and 50 weeks capability retentions be in table 1.
Embodiment 11:
Take ANN aluminium nitrate nonahydrate powder 0.188g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO
3)
2) solution 0.349ml, in instillation aluminum nitrate solution, stir.Take 0.696g manganese dioxide, insert mixed liquor, after stirring, take 0.42g mono-hydronium(ion) lithia, be dissolved in 10ml deionized water, slowly in instillation mixed liquor, stir 30 minutes.Above-mentioned mixed liquor is placed in hydrothermal reaction kettle with 200
oc reacts 20 hours, and filtration washing drying obtains finished product presoma, through 3 hours 650
oc heat treatment obtains LiMn
1.5al
0.5o
3.95evenly coated LiMn
2o
4powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With obtained LiMn
1.5al
0.5o
3.95evenly coated LiMn
2o
4powder is positive electrode, is assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, carries out constant current charge-discharge loop test, with 1C(130mAg to battery
-1) multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) discharge capacity first of multiplying power discharging and 50 weeks capability retentions be in table 1.
Embodiment 12:
Take ANN aluminium nitrate nonahydrate powder 0.113g, be made into 20ml solution, measure 50% manganese nitrate (Mn (NO
3)
2) solution 0.396ml, in instillation aluminum nitrate solution, stir.Take 0.696g manganese dioxide, insert mixed liquor, after stirring, take 0.42g mono-hydronium(ion) lithia, be dissolved in 10ml deionized water, slowly in instillation mixed liquor, stir 30 minutes.Above-mentioned mixed liquor is placed in hydrothermal reaction kettle with 200
oc reacts 20 hours, and filtration washing drying obtains finished product presoma, through 3 hours 750
oc heat treatment obtains LiMn
1.7al
0.3o
3.95evenly coated LiMn
2o
4powder, the metering of coating layer element chemistry is than being determined by x-ray photoelectron power spectrum (XPS).
With obtained LiMn
1.7al
0.3o
3.95evenly coated LiMn
2o
4powder is positive electrode, is assembled into 2032 button cells according to the method for embodiment 1, in 3.3V ~ 4.3V voltage range, carries out constant current charge-discharge loop test, with 1C(130mAg to battery
-1) multiplying power charging, it is at 1C(130mAg
-1) and 10C(1300mAg
-1) discharge capacity first of multiplying power discharging and 50 weeks capability retentions be in table 1.
Table 1: with the LiMn prepared by embodiment 1 ~ 12
2-xm
xo
4-δ@LiMn
2o
4for positive pole, lithium sheet is that the lithium ion battery chemical property that negative pole assembles compares
Claims (7)
1. a modified lithium manganate material, is characterized in that: described modified lithium manganate material is with LiMn
2o
4for core, with LiMn
2-xm
xo
4-δfor the nucleocapsid structure of coating layer; Wherein M is the one in Al, Ti, Ce, Co, Ni, and the value of x is 0.05 ~ 0.5, δ is 0.01 ~ 0.1;
The preparation method of described modified lithium manganate material comprises the steps:
(1) manganese ion Yuan ﹑ M metal ion source is mixed with mixed solution, then manganese dioxide is placed in mixed solution, stir, getting lithium hydroxide solution is added dropwise in mixed system, makes hydroxide coating layer (MnM) OH forming manganese ion and M metal ion on manganese dioxide surface; In the integral molar quantity of manganese ion, M metal ion and manganese dioxide for 100%, wherein manganese ion mole accounts for 15% ~ 20%, the mol ratio of manganese ion and M metal ion is 3 ~ 39, and the mole of lithium hydroxide is equal with the total mole number of manganese ion, M metal ion and manganese dioxide;
(2) reaction system of step (1) is placed in hydrothermal reaction kettle, in 150 ~ 220 DEG C of reactions 10 ~ 20 hours, obtains presoma;
(3) presoma is placed in air atmosphere in 600 ~ 800 DEG C of high-temperature roastings 2 ~ 5 hours, obtained described modified lithium manganate material.
2. modified lithium manganate material as claimed in claim 1, is characterized in that: described LiMn
2o
4it is spinel-type cubic crystal structure.
3. modified lithium manganate material as claimed in claim 1, is characterized in that: the particle diameter of described modified lithium manganate material is at 100 ~ 500nm.
4. modified lithium manganate material as claimed in claim 1, is characterized in that: the value of x is 0.2 ~ 0.5, δ is 0.02 ~ 0.06.
5. modified lithium manganate material according to claim 1, it is characterized in that: described manganese ion source is one or more the combination in manganese nitrate, manganese oxalate, manganese acetate, manganese sulfate, described M metal ion source is one or more the combination in the nitrate of M metal ion, oxalates, chloride, acetate, sulfate.
6. modified lithium manganate material according to claim 1, is characterized in that: in described step (1), makes the mol ratio of manganese ion and M metal ion be 3 ~ 9.
7. modified lithium manganate material as claimed in claim 1 is as the application of the positive electrode of lithium ion battery.
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| CN201210562918.6A CN103035904B (en) | 2012-12-21 | 2012-12-21 | Modified lithium manganate material, and preparation method and application thereof |
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| CN201210562918.6A CN103035904B (en) | 2012-12-21 | 2012-12-21 | Modified lithium manganate material, and preparation method and application thereof |
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| CN103035904B true CN103035904B (en) | 2015-03-04 |
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| CN107204460A (en) * | 2017-05-11 | 2017-09-26 | 绍兴文理学院 | A kind of preparation method without crystal defect tertiary cathode material |
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| CN111509224B (en) * | 2020-04-17 | 2021-07-23 | 中南大学 | Linked modified lithium-rich manganese-based cathode material and preparation method thereof |
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